JP2006070185A - Polyurethane-based curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane-based curable composition excellent in adhesiveness to a top coat with keeping both excellent curing properties at normal temperature and retention of sufficient pot life. <P>SOLUTION: The polyurethane-based curable composition is obtained by reacting an active hydrogen compound with an isocyanate compound. The active hydrogen compound contains ≥20 mass% modified aromatic polyamine obtained by reacting a monoepoxide compound with an aromatic polyamine compound having ≥2 primary amino groups and ≥1 aromatic rings in a ratio of 0.05-1 mole monoepoxide compound to 1 mole primary amino group of the aromatic polyamine compound and realizes both excellent curing properties at normal temperature and excellent pot life. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyurethane-based curable composition that can be cured at room temperature and is effective as a coating material such as a paint or a waterproof material.

  A polyurethane-based curable composition obtained by curing a two-component room-temperature curable composition comprising a main component mainly composed of an isocyanate group-terminated polyurethane prepolymer and a curing agent containing an active hydrogen compound has excellent flexibility. Depending on the nature, it is used in a wide range of applications such as paints, waterproofing materials, flooring materials, sealing materials, and elastic paving materials.

  For example, as a polyurethane-based curable composition used for waterproofing materials, a main component mainly composed of an isocyanate group-terminated polyurethane prepolymer obtained by a reaction between a polyol such as polyoxypropylene polyol and tolylene diisocyanate, A two-component polyurethane-based curable composition in which a polyoxypropylene polyol and a curing agent mainly composed of 4,4′-methylenebis (2-chloroaniline) are mixed has been used preferably. It has become.

  In the following Patent Document 1, a) as a polyisocyanate, an isocyanate group-terminated polyurethane prepolymer obtained by reaction of tolylene diisocyanate and a polyol, an aliphatic or alicyclic diisocyanate monomer, an oligomer or an aliphatic or alicyclic diisocyanate monomer A mixture of an isocyanate group-terminated polyurethane prepolymer obtained by the reaction of a polyol with b), and b) the mixing ratio of the mixture is such that the molar ratio based on the respective isocyanate groups is 98/2 to 70/30, c) The main agent and the curing agent are mixed and mixed so that the equivalent ratio of the isocyanate group in the main agent and the amino group in the curing agent is 0.8 to 2.0, and cured. A room temperature curable polyurethane waterproof material is disclosed.

Further, in Patent Document 2 below, a main component mainly composed of an isocyanate group-terminated polyurethane prepolymer obtained by the reaction of tolylene diisocyanate and a polyol, and a curing agent containing an aromatic polyamine crosslinking agent and a plasticizer are mixed. In the method for producing a room temperature-curing fast-curing polyurethane coating waterproof material that is coated and cured, a) a polyoxypropylene polyol and / or a polyoxyethylene propylene polyol as a main raw material of a polyol to be reacted with the tolylene diisocyanate B) The main component of the aromatic polyamine crosslinking agent in the curing agent is diethyltoluenediamine; c) The amount of the plasticizer used in the curing agent is 20 to 130 with respect to 100 parts by weight of the isocyanate-terminated prepolymer. D) the main agent and the curing agent It is characterized in that it is mixed at the construction site so that the equivalent ratio of the isocyanate group of the prepolymer in it and the amino group of the aromatic polyamine in the curing agent is 0.8 to 2.0, and is applied and cured. A room temperature curing type fast curing polyurethane coating waterproofing material that retains the pot life is disclosed.
JP-A-11-240932 Japanese Patent Laid-Open No. 08-143816

  However, conventionally used polyurethane-based curable compositions are 4,4′-methylenebis (2-chloroaniline) (hereinafter referred to as MOCA) as an active hydrogen compound in the curing agent. However, since this MOCA is a designated chemical substance, there is a problem in safety, and there are certain restrictions in manufacturing and use.

  MOCA is solid at room temperature, has high crystallinity, and has poor solubility in plasticizers and solvents. Therefore, it is usually used after being dissolved in polyoxypropylene polyol at a concentration of 20 to 40% by mass. However, the melting point is as high as 98 ° C. or higher, and it is difficult to handle, and it takes a lot of time to dissolve the MOCA in order to incorporate it into the composition of the curing agent.

  On the other hand, polyurethane-based curable compositions using MOCA as an active hydrogen compound have an appropriate balance between pot life at room temperature and curability, and are excellent in mechanical properties of the cured film. In addition, no more manageable active hydrogen compounds that replace MOCA have been found so far.

  Also, as disclosed in Patent Documents 1 and 2, a polyurethane-based curable composition that is a two-component urethane waterproofing material using diethyltoluenediamine (hereinafter referred to as DETDA) and a large amount of plasticizer. There are some things, but this has a short pot life, is not suitable for summer use, and has insufficient adhesion to the top coat.

  Accordingly, an object of the present invention is to achieve both excellent curability at room temperature and sufficient pot life without using MOCA, which is a designated chemical substance, as a component of a polyurethane-based curable composition. Another object is to provide a polyurethane-based curable composition having excellent adhesion to the top coat.

  In solving the above-mentioned object, the polyurethane-based curable composition of the present invention is a polyurethane-based curable composition containing a polyisocyanate compound and an active hydrogen compound, and curable by reacting them. The active hydrogen compound is an aromatic polyamine compound having two or more primary amino groups and one or more aromatic rings, and 0.05 to 1 with respect to 1 mol of the primary amino group of the aromatic polyamine compound. It is characterized by containing 20% by mass or more of a modified aromatic polyamine which is a reaction product obtained by reacting a molar monoepoxide compound.

According to the present invention, by using an active hydrogen compound containing the above aromatic-modified polyamine as the active hydrogen compound, it is possible to ensure a sufficient pot life while maintaining excellent curability, and to adhere to the top coat. In the present invention, the aromatic polyamine compound used for obtaining the modified aromatic polyamine is toluenediamine, xylylenediamine, diethyltoluenediamine, 4, It should be one or more selected from the group consisting of 4'-methylenedianiline, 4,4'-methylenebis (2,6-dialkylaniline), and 4,4'-methylenebis (2-alkylaniline). Is preferred, and diethyltoluenediamine is more preferred.
The monoepoxide compound is preferably one or more selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, alkyl glycidyl ether, and alkyl glycidyl ester.

  The polyurethane curable composition of the present invention is preferably used as a two-component polyurethane coating material composition, more preferably as a two-component polyurethane coating waterproofing composition for hand coating. .

  Since the polyurethane-based curable composition of the present invention does not use MOCA or the like which is a designated chemical substance, it is favorable in terms of environment and hygiene, and has excellent curability at room temperature and sufficient Therefore, it can be used suitably as, for example, a paint or a waterproofing material because it can maintain both the usable life and the adhesiveness with the top coat. Particularly, it is suitably used as a two-component polyurethane coating waterproofing composition for hand coating.

  The polyurethane-based curable composition of the present invention is obtained by mixing a main agent containing a polyisocyanate compound and a curing agent containing an active hydrogen compound.

  Hereinafter, each component used for this invention is demonstrated in detail.

  The curing agent of the polyurethane-based curable composition of the present invention includes a modified aromatic polyamine that is a reaction product obtained by adding a monoepoxide compound to an aromatic polyamine compound as an active hydrogen compound.

  The aromatic polyamine compound has two or more primary amino groups and one or more aromatic rings. As this aromatic polyamine compound, a compound having excellent reactivity with isocyanate is preferably selected. Specifically, toluenediamine, xylylenediamine, DETDA, 4,4′-methylenedianiline, 4,4′-methylenebis (2,6-dialkylaniline), and 4,4′-methylenebis (2-alkylaniline) 1 type or 2 types or more selected from the group consisting of Among these, DETDA that is liquid at room temperature is particularly preferable from the viewpoints of workability and curability.

  DETDA preferably used in the present invention is 3,5-diethyltoluene-2,4-diamine (hereinafter referred to as 2,4-DETDA) and 3,5-diethyltoluene-2,6-diamine ( Hereinafter, it is at least one selected from 2,6-DETDA.

  Further, the mixing ratio of 2,4-DETDA and 2,6-DETDA in a diethyltoluenediamine mixture composed of 2,4-DETDA and 2,6-DETDA (hereinafter referred to as DETDA-mx) is particularly limited. Although not intended, 0.01 to 100 mol of 2,6-DETDA is suitable for 1 mol of 2,4-DETDA. In particular, DETDA-mx (hereinafter referred to as DETDA-mxs) in which 2,6-DETDA is 0.24 mole per mole of 2,4-DETDA is preferable, and this DETDA-mxs is Albemarle Corporation. It is available from the company under the trade name “Etacure 100”. Each of 2,4-DETDA and 2,6-DETDA can be obtained, for example, by separating both from “Ecure 100”.

  As the monoepoxide compound used for modification of the aromatic polyamine compound, one or more selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, alkyl glycidyl ether, and alkyl glycidyl ester are particularly preferably used.

  The modified aromatic polyamine of the present invention is a reaction product obtained by reacting the aromatic polyamine compound with a monoepoxide compound. In particular, a reaction product obtained by reacting (addition reaction) alkylene oxide (hereinafter referred to as AO) composed of ethylene oxide or propylene oxide with DETDA is preferable.

  For example, in the case of a reaction product obtained by reacting 1 mol of AO with 1 mol of DETDA, this reaction product is an adduct formed by reacting 1 molecule of AO with 1 molecule of DETDA ( 1A-1), (1A-2), and (1B), an adduct (2A) and (2B) produced by the reaction of two molecules of AO with one molecule of DETDA, unreacted DETDA, etc. It is a composition. In addition, in the case of a reaction product obtained by reacting N mole of AO with 1 mole of DETDA (hereinafter referred to as N mole adduct of DETDA AO), one molecule of DETDA is composed of N molecules. An adduct produced by reaction of AO as a main component, and optionally an adduct produced by reaction of less AO than N molecules, an adduct produced by reaction of more AO than N molecules, and unreacted Of DETDA and the like. Similar reaction products can also be obtained when other aromatic polyamine compounds and monoepoxide compounds are reacted.

(In the formula, R is a hydrogen atom or a methyl group.)
Thus, the modified aromatic polyamine which consists of a primary amine, a secondary amine, and a tertiary amine is obtained by adding a monoepoxide compound to an aromatic polyamine compound. Here, the secondary amino group is slower in reactivity with the isocyanate than the primary amino group. Therefore, even after reaction curing, the secondary amino group tends to remain as an unreacted amino group, and the adhesiveness with the urethane-based topcoat having an isocyanate group can be further improved. Furthermore, although a hydroxyl group is also produced, when a urethanization-promoting curing catalyst is used, crosslinking proceeds, so the heat resistance of the cured coating film can be improved.

  The active hydrogen-containing group of the modified aromatic polyamine has a primary amino group, a secondary amino group, and a hydroxyl group. And sclerosis | hardenability of a polyurethane curable composition can be adjusted by changing these ratio structures. However, since the hydroxyl group of the polyol in the curing agent and the hydroxyl group of the modified aromatic polyamine generated by adding the monoepoxide compound are extremely poor in reactivity, when the urethanization accelerated curing catalyst is not used, The contribution is low. This is because in the curing reaction of the curable composition at room temperature, the reaction between the isocyanate group and the hydroxyl group is unlikely to proceed unless the catalyst is used.

  Therefore, the addition amount of the monoepoxide compound to the aromatic polyamine compound is important for adjusting the ratio of the active hydrogen-containing group. In the present invention, 0.05 to 1 mol of monoepoxide compound is added to 1 mol of the primary amino group of the aromatic polyamine compound, preferably 0.1 to 0.4 mol. Is an additional amount.

  When the addition amount of the monoepoxide compound exceeds 1 mol per 1 mol of the primary amino group of the aromatic polyamine compound, the residual amount of the primary amino group decreases, so that the curability of the polyurethane curable composition is reduced. It is not preferable because it tends to decrease. On the other hand, when the amount is less than 0.05 mol, no significant modification effect is observed in the characteristics of the aromatic polyamine compound, and the reactivity with the isocyanate compound can hardly be alleviated, making it difficult to obtain a sufficient pot life. In addition, since amino groups are consumed in an almost total amount by reaction with isocyanate groups, unreacted amino groups hardly remain and it is difficult to obtain excellent adhesiveness with a top coating material.

  The modified aromatic polyamine added with the monoepoxide compound may be used alone as an active hydrogen compound, but may be used in combination with various polyols or unmodified aromatic polyamine compounds. The ratio of the modified aromatic polyamine in the active hydrogen compound is 20% by mass or more, but preferably 50 to 100% by mass.

  Examples of the polyol that may be used in the curing agent of the present invention include polyoxyalkylene polyol, polyoxytetramethylene glycol, castor oil, butadiene-based polyol, and the like, but polyoxypropylene polyol is preferable. Moreover, you may mix the polyol from which a functional group number and molecular weight differ. 2-4 are preferable and, as for the average functional group number of this polyol, 2-3 are more preferable. When the average functional group number of this polyol is less than 2, it is difficult to increase the molecular weight of the cured film, so that the curing rate is remarkably reduced, the curability is easily deteriorated, and the cured film is difficult to obtain sufficient mechanical strength. On the other hand, if it exceeds 4, the crosslink density becomes too high and the elongation performance of the cured film tends to deteriorate.

  Further, a curing catalyst may be used in order to complete the reaction so that the isocyanate group of the main agent does not remain in an unreacted state with a hydroxyl group based on the polyol or the like used for the curing agent.

  As the curing catalyst, a catalyst that promotes a known urethanization reaction can be used. 2-ethylhexanoic acid lead (lead octylate) or imidazole amine catalyst is particularly preferred. Further, when no polyol is used, no catalyst may be used. However, when further curing is desired, an organic acid catalyst such as octylic acid or oleic acid may be used. These catalysts can be mixed with a curing agent in advance.

  In addition, the curing agent may contain an additive selected from fillers, pigments, stabilizers, plasticizers, and solvents.

  Examples of the filler include calcium carbonate, talc, clay, silica, carbon and the like.

  Examples of the pigment include inorganic pigments such as chromium oxide and titanium oxide, and organic pigments such as phthalocyanine pigments.

  As the plasticizer, dioctyl phthalate (DOP), dibutyl phthalate, dinonyl phthalate, diisononyl phthalate (DINP), dioctyl adipate, diisononyl adipate (DINA), chlorinated paraffin, petroleum plasticizer, etc. can be used. . In addition, soybean oil fatty acid (analysis example: linoleic acid 54%, oleic acid 24%, palmitic acid 10%, linolenic acid 8%, stearic acid 4%), coconut oil fatty acid (analysis example: linoleic acid 38%, oleic acid 41%) Monocarboxylic acid methyl ester mixtures which are methanolic esters of fatty acids such as palmitic acid 17%, stearic acid 2%, linolenic acid 2%) can also be used.

  Furthermore, you may mix | blend stabilizers, such as antioxidant generally used with a polyurethane resin, a ultraviolet absorber, a dehydrating agent.

  As the polyisocyanate compound used as the main component of the polyurethane-based curable composition of the present invention, an isocyanate group-terminated polyurethane prepolymer prepolymerized with a polyoxyalkylene polyol is preferable.

  Examples of the polyisocyanate used as a raw material for such an isocyanate group-terminated polyurethane prepolymer include polyisocyanates such as aromatic, aliphatic and modified polyisocyanates having two or more isocyanate groups. However, 4,4'-diphenylmethane diisocyanate (MDI) or tolylene diisocyanate (TDI) is preferred from the viewpoint of the viscosity, curability of the resulting prepolymer and the mechanical strength of the cured coating film.

  The isocyanate group content of the isocyanate group-terminated polyurethane prepolymer is preferably 2 to 6% by mass. When the isocyanate group content exceeds 6% by mass, the curing rate of the polyurethane-based curable composition is increased, and the resulting film tends to be hard, so that it is difficult to obtain sufficient elongation performance. Moreover, since it is in the tendency for the mechanical strength of a cured film to become weak if it is less than 2 mass%, it becomes difficult to satisfy | fill the performance as a waterproofing material etc.

  On the other hand, it is preferable that the average functional group number of the polyol used for prepolymerization is 2-3. For example, polyoxypropylene polyols, polyoxypropylene polyoxyethylene polyols composed of diols alone or mixtures with triols, and the like can be mentioned. If the average number of functional groups is less than 2, it is difficult to increase the molecular weight of the cured film, so that the curing rate is remarkably reduced, and the cured film is difficult to obtain sufficient mechanical strength. On the other hand, if it exceeds 3, the crosslink density becomes too high and the elongation performance of the cured film tends to deteriorate.

  Furthermore, the hydroxyl value of the polyol used for prepolymerization is preferably 8 to 300 mgKOH / g, preferably 40 to 80 mgKOH / g, from the balance of the viscosity of the isocyanate group-terminated polyurethane prepolymer obtained, the strength of the cured coating film, and the elongation performance. More preferred.

In the polyurethane-based curable composition of the present invention, the mixing ratio of the main agent and the curing agent is the molar ratio (NCO / (NH ₂ + NH + OH)) (hereinafter referred to as isocyanate) of the isocyanate group of the main agent and the active hydrogen-containing group of the curing agent. It is preferable to mix so that it may become 1.0-1.3. However, when not using the urethanization-promoting curing catalyst, the hydroxyl groups of the polyol and the modified aromatic polyamine are not considered.

  In that case, it is preferable that the mixing mass ratio of a main ingredient and a hardening | curing agent is 1: 0.5-3, More preferably, it is 1: 1-2. If the mass ratio of the curing agent is less than 0.5, the absolute amount of the filler is small, so that appropriate thixotropy cannot be expressed, and if it exceeds 3, the blending amount of the active hydrogen compound component in the curing agent is small. Therefore, a plasticizer, a solvent, or a filler is used more than necessary, which is not preferable.

  The polyurethane-based curable composition having the above configuration can maintain a sufficient pot life while being excellent in curability. Further, the cured composition is excellent in adhesiveness with the top coat, and the mechanical strength, elongation performance, etc. can sufficiently satisfy the requirements for the use of waterproofing materials. Although it is preferably used as a waterproof material, it can be particularly preferably used as a waterproof material for hand coating.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these.

[Synthesis Example of Modified Aromatic Polyamine]
(Synthesis of modified polyamine A)
3375 g (18.93 mol) of DETDA (trade name; “Ecure 100”, manufactured by Albemarle Corporation) as an aromatic polyamine compound was charged into a 5 L stainless steel reaction vessel equipped with a stirrer, and the gas phase part was nitrogen gas. Replaced with.

  Thereafter, while maintaining the temperature of the reaction vessel at 135 ° C. and the pressure at 0.03 MPa (gauge pressure, the same applies hereinafter), propylene oxide as a monoepoxide compound is flowed at a flow rate of about 384 g / hr while stirring the inside of the reaction vessel. Introduced. The pressure in the reaction tank at the time of reaction with propion oxide was 0.3 to 0.5 MPa. After 1125 g (19.40 mol) of propylene oxide was introduced over 3 hours, the temperature of the reaction vessel was maintained at 135 ° C. and stirring was continued for 1 hour.

  Thereafter, the reaction vessel was cooled to 60 ° C. to obtain a brown transparent viscous oily liquid. The viscosity of the obtained liquid was 88300 mPa · s at 25 ° C. The modified aromatic polyamine thus obtained was designated as modified polyamine A.

  The obtained liquid was dissolved in chloroform to prepare a concentration of 5% by mass. The prepared sample was separated using a preparative gel permeation chromatogram (GPC) using chloroform as an eluent. The detector used RI. The separated sample was subjected to IR and NMR spectrum measurement after removing chloroform by air drying. As a result, the separated sample is referred to as a mixture of (i) unreacted DETDA, (ii) compound (11A-1), compound (11A-2), and compound (11B) (hereinafter referred to as PO1 molecule adduct). ), (Iii) a mixture of compound (21A) and compound (21B) (hereinafter referred to as PO2 molecule adduct).

Among the separated samples, the IR spectrum, ¹ H-NMR spectrum and ¹³ C-NMR spectrum of the PO1 molecule adduct are shown in FIGS. The IR spectrum, absorption by N-H bending to 1620 cm ^-1 is absorption by O-H stretching to 3360cm ^-1 were observed respectively. The NMR spectrum was assigned as follows as a result of analysis, and the compound was specified. The ratio of the amount of each compound represented by the formulas (11A-1), (11A-2) and (11B) was 1: 0.89: 0.48 in this order. .

Compound (11A-1)
¹³ C-NMR δppm: 13.3 (C-12), 13.4 (C-14), 18.0 (C-7), 19.5 (C-11), 20.8 (C-10), 24.2 (C-13), 57.5 ( C-8), 67.4 (C-9), 115.9 (C-1), 122.0 (C-3), 123.5 (C-5), 128.3 (C-6), 140.5 (C-4), 143.2 (C -2).

Compound (11A-2)
¹³ C-NMR δppm: 13.3 (C-9), 15.5 (C-14), 17.7 (C-7), 19.5 (C-8), 20.9 (C-12), 23.8 (C-13), 58.8 ( C-10), 67.4 (C-11), 118.0 (C-1), 122.2 (C-3), 127.5 (C-5), 128.4 (C-6), 141.0 (C-2), 142.8 (C -Four).

Compound (11B)
¹³ C-NMR δ ppm: 12.5 (C-7), 13.4 (C-14), 15.8 (C-12), 20.8 (C-10), 24.2 (C-13), 24.3 (C-11), 57.5 ( C-8), 67.4 (C-9), 121.2 (C-1), 123.0 (C-5), 126.0 (C-4), 126.5 (C-3), 141.2 (C-6), 143.3 (C -2).

Among the separated samples, the IR spectrum, ¹ H-NMR spectrum and ¹³ C-NMR spectrum of the PO2 molecule adduct are shown in FIGS. From these spectra, the PO2 molecule adduct was identified as a mixture of compounds represented by formulas (21A) and (21B).

(Synthesis of modified polyamine B)
The same method as modified polyamine A, except that 2512 g (14.11 mol) of DETDA was used as the aromatic polyamine compound, 1988 g (22.59 mol) of methyl glycidyl ether was used as the monoepoxide compound, and the temperature of the reaction vessel was 120 ° C. Was synthesized.

(Synthesis of modified polyamine C)
The same method as modified polyamine A, except that 3757 g (21.11 mol) of DETDA was used as the aromatic polyamine compound, 743 g (8.44 mol) of methyl glycidyl ether was used as the monoepoxide compound, and the temperature of the reaction vessel was 120 ° C. Was synthesized.

(Synthesis of modified polyamine D)
The compound was synthesized in the same manner as modified polyamine A, except that 2276 g (12.79 mol) of DETDA was used as the aromatic polyamine compound and 2224 g (38.34 mol) of propylene oxide was used as the monoepoxide compound.

(Synthesis of modified polyamine E)
The same as modified polyamine A, except that 3880 g (15.28 mol) of 4,4′-methylenebis (2-ethylaniline) was used as the aromatic polyamine compound and 620 g (10.69 mol) of propylene oxide was used as the monoepoxide compound. Synthesized by the method.

(Synthesis of modified polyamine F)
Synthesized in the same manner as modified polyamine A except that 4005 g (22.50 mol) of DETDA was used as the aromatic polyamine compound, 495 g (11.25 mol) of ethylene oxide was used as the monoepoxide compound, and the temperature of the reaction vessel was 120 ° C. did.

[Preparation of polyurethane-based curable composition]
Tables 1 and 2 below show the polyols A to D and the modified polyamines A to F used in Examples 1 to 6 and Comparative Examples 1 to 4 of the present invention.

[Example 1]
26.5 parts by mass of MDI was reacted with 7.3 parts by mass of polyol B and 66.2 parts by mass of polyol C (NCO / OH molar ratio = 3.0), and the isocyanate group content was 5. 9% by mass of an isocyanate group-terminated polyurethane prepolymer was obtained and used as a main agent.

  A solution obtained by mixing 19.2 parts by mass of modified polyamine B, 30.0 parts by mass of DINP, 47.8 parts by mass of calcium carbonate, and 3.0 parts by mass of pigment paste was used as a curing agent. The ratio of the main agent / curing agent was mixed at a mass ratio of 1/1 (isocyanate index is 1.2) and used as a polyurethane-based curable composition.

[Example 2]
17.3 parts by mass of polyol A and 69.2 parts by mass of polyol C were reacted with 13.5 parts by mass of 2,4-isomer 95% by mass of tolylene diisocyanate (TDI-100), and (NCO / OH molar ratio = 1.8) and an isocyanate group-terminated polyurethane prepolymer having an isocyanate group content of 2.8% by mass was obtained and used as a main agent.

  A liquid obtained by mixing 6.7 parts by mass of modified polyamine C, 30.3 parts by mass of DINP, 60.0 parts by mass of calcium carbonate, and 3.0 parts by mass of pigment paste was used as a curing agent. The ratio of the main agent / curing agent was mixed at a mass ratio of 1/1 (isocyanate index 1.1) and used as a polyurethane-based curable composition.

[Example 3]
17.0 parts by mass of polyol A and 68.0 parts by mass of polyol C were reacted with 15.0 parts by mass of tolylene diisocyanate (TDI-80) of 80% by mass of 2,4-isomer (NCO / OH molar ratio = 2.03) and an isocyanate group-terminated polyurethane prepolymer having an isocyanate group content of 3.6% by mass was obtained and used as a main agent.

  4.9 parts by weight of modified polyamine A, 15.6 parts by weight of polyol C, 16.1 parts by weight of DINA, 60.0 parts by weight of calcium carbonate, 3.0 parts by weight of pigment paste, 2-ethylhexane The liquid which mixed 0.4 mass part of lead acid (lead content 24 mass%) was used as a hardening | curing agent. The ratio of the main agent / curing agent is mixed as a mass ratio of 1/1 (isocyanate index is 1.1. However, since a urethanization-promoting curing catalyst is used, a hydroxyl group is taken into account), and a polyurethane-based curable composition is obtained. used.

[Example 4]
The same isocyanate group-terminated polyurethane prepolymer as in Example 2 was used as the main agent, 4.0 parts by mass of DETDA, 1.3 parts by mass of modified polyamine A, 31.7 parts by mass of DINP, 60.0 parts of calcium carbonate. A liquid obtained by mixing part by mass and 3.0 parts by mass of the pigment paste was used as a curing agent. The ratio of the main agent / curing agent was mixed at a mass ratio of 1/1 (isocyanate index is 1.2) and used as a polyurethane-based curable composition.

[Example 5]
An isocyanate group-terminated polyurethane prepolymer having the same prepolymer as that of Example 2 as a main ingredient was used as a main ingredient, 8.2 parts by mass of modified polyamine E, 28.8 parts by mass of DINP, 60.0 parts by mass of calcium carbonate, A liquid in which 3.0 parts by mass of the pigment paste was mixed was used as a curing agent. The ratio of the main agent / curing agent was mixed at a mass ratio of 1/1 (isocyanate index is 1.2) and used as a polyurethane-based curable composition.

[Example 6]
46.5 parts by mass of polyol C and 23.3 parts by mass of polyol D were reacted with 30.2 parts by mass of TDI-80 (NCO / OH molar ratio = 2.13), with an isocyanate group content of 7 .7% by mass of an isocyanate group-terminated polyurethane prepolymer was obtained and used as a main agent.

  A solution prepared by mixing 15.3 parts by mass of modified polyamine F, 31.7 parts by mass of DINP, 50.0 parts by mass of calcium carbonate, and 3.0 parts by mass of pigment paste was used as a curing agent. The ratio of the main agent / curing agent was mixed at a mass ratio of 1/1 (isocyanate index is 1.2) and used as a polyurethane-based curable composition.

[Comparative Example 1]
The same isocyanate group-terminated polyurethane prepolymer as in Example 1 was used as the main agent, DETDA 10.4 parts by mass, DINP 36.6 parts by mass, calcium carbonate 50.0 parts by mass, and pigment paste 3.0 parts by mass The liquid which mixed was used as a hardening | curing agent. The ratio of the main agent / curing agent was mixed at a mass ratio of 1/1 (isocyanate index is 1.2) and used as a polyurethane-based curable composition.

[Comparative Example 2]
The same isocyanate group-terminated polyurethane prepolymer as in Example 2 was used as the main agent, 4.9 parts by mass of DETDA, 32.1 parts by mass of DINP, 60.0 parts by mass of calcium carbonate, and 3.0 parts by mass of the pigment paste. The liquid which mixed was used as a hardening | curing agent. The ratio of the main agent / curing agent was mixed at a mass ratio of 1/1 (isocyanate index is 1.2) and used as a polyurethane-based curable composition.

[Comparative Example 3]
The same isocyanate group-terminated polyurethane prepolymer as in Example 3 was used as the main agent, 5.5 parts by mass of DETDA, 15.6 parts by mass of polyol C, 15.5 parts by mass of DINA, and 60.0 parts by mass of calcium carbonate. Part, 3.0 parts by mass of the pigment paste, and 0.4 parts by mass of lead 2-ethylhexanoate were used as a curing agent. The ratio of the main agent / curing agent was mixed at a mass ratio of 1/1 (isocyanate index 1.1) and used as a polyurethane-based curable composition.

[Comparative Example 4]
The same isocyanate group-terminated polyurethane prepolymer as in Example 1 was used as a main agent, 20.6 parts by mass of modified polyamine D, 30.0 parts by mass of DINP, 46.4 parts by mass of calcium carbonate, and 3.0 of pigment paste. A liquid in which parts by mass were mixed was used as a curing agent. The ratio of the main agent / curing agent was mixed at a mass ratio of 1/1 (isocyanate index is 1.2) and used as a polyurethane-based curable composition.

The raw materials of the main agents and the curing agents of Examples 1 to 6 and Comparative Examples 1 to 4 described above are summarized in Table 3 below.

(Performance evaluation items)
<Pot life>
In the laboratory at 23 ° C. and 50% RH, the main agent and the curing agent were mixed, and the time (pot life) (minute) to reach a viscosity of 100 Pa · s from the start of mixing was measured.

  If the pot life is 40 minutes or more, it can be sufficiently constructed even in the summer. Therefore, if the pot life is 40 minutes or more, it was judged that the pot life was sufficient.

<Curing property>
In a 23 ° C., 50% RH laboratory, coating was performed on a slate plate at a coating amount of ² kg / m ² and the state after 12 hours was observed.
If the coated surface was not sticky and could be walked, it was judged that the curability was good.

<Topcoat adhesiveness>
In a laboratory at 23 ° C. and 50% RH, a solvent-type acrylic urethane top coat was applied at a coating amount of 0.2 kg / m ² 24 hours after applying the waterproof material, and the adhesion of the top coat 24 hours later was It was evaluated by an eye test. On the surface of the top coat, 11 cuts were made vertically and horizontally at intervals of 1 mm using a razor to prepare a grid having 100 grids. After the cellophane tape was stuck on the grid, it was peeled off at a stretch in the vertical direction, and the number of squares remaining without peeling off the top coat was counted, 95-100 pieces ○, 50-94 △, 0-49 was set as x. If it was (circle), it judged that the adhesiveness with a topcoat was favorable.

<Physical properties of coating film>
According to JIS A 6021, the mechanical properties (tensile strength (T _B ) (unit: N / mm ² ) and elongation at break (E) (unit:%)) of the coating film were measured.

  About the polyurethane-type curable composition of Examples 1-6 and Comparative Examples 1-4, said item was evaluated and a result is shown in Table 4.

  From the above results, the polyurethane-based curable compositions of Comparative Examples 1 to 3 that do not use the modified aromatic polyamine added with the monoepoxide compound as the active hydrogen compound used as the curing agent have a very high curing speed and are sufficiently The pot life could not be secured. Also, the adhesion with the top coat could not be sufficiently satisfied.

  Moreover, the polyurethane-type curable composition of the comparative example 4 using the modified | denatured aromatic polyamine which added the monoepoxide compound exceeding 1 mol with respect to 1 mol of primary amino groups of an aromatic polyamine compound as an active hydrogen compound. The curability was remarkably lowered, and even after 12 hours, it was not possible to make it walkable.

  On the other hand, the polyurethane curable compositions of Examples 1 to 6 using the curing agent containing the active hydrogen compound of the present invention were excellent in curability and ensured sufficient pot life. Furthermore, the adhesiveness with the top coat could be excellent.

  Therefore, according to the present invention, it is possible to satisfy sufficient pot life and curability without using MOCA which is a designated chemical substance, and furthermore, polyurethane-based curing which is excellent in adhesiveness with a top coat. Sex compositions can be provided.

  The polyurethane-based curable composition of the present invention can be suitably used as, for example, a paint, a waterproof material, or a flooring material.

It is IR spectrum figure of PO1 molecule adduct. It is a ¹ H-NMR spectrum diagram of a PO1 molecule adduct. It is a ¹³ C-NMR spectrum diagram of a PO1 molecule adduct. It is IR spectrum figure of PO2 molecule adduct. It is a ¹ H-NMR spectrum diagram of a PO2 molecule adduct. It is a ¹³ C-NMR spectrum diagram of a PO2 molecule adduct.

Claims (6)

A polyurethane-based curable composition containing a polyisocyanate compound and an active hydrogen compound, and curable by reacting them,
The active hydrogen compound may be added to an aromatic polyamine compound having two or more primary amino groups and one or more aromatic rings in an amount of 0.05 to 1 mol of the primary amino group of the aromatic polyamine compound. A polyurethane-based curable composition comprising 20% by mass or more of a modified aromatic polyamine which is a reaction product obtained by reacting 1 mol of a monoepoxide compound.   The aromatic polyamine compound is toluenediamine, xylylenediamine, diethyltoluenediamine, 4,4′-methylenedianiline, 4,4′-methylenebis (2,6-dialkylaniline), and 4,4′-methylenebis (2 The polyurethane-based curable composition according to claim 1, which is one or more selected from the group consisting of -alkylaniline).   The polyurethane-based curability according to claim 1 or 2, wherein the monoepoxide compound is one or more selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, alkyl glycidyl ether, and alkyl glycidyl ester. Composition.   The polyurethane-based curable composition according to any one of claims 1 to 3, wherein the aromatic polyamine compound is diethyltoluenediamine.   The polyurethane-based curable composition according to any one of claims 1 to 4, which is used as a two-component polyurethane coating material composition.   The polyurethane curable composition according to claim 5, wherein the two-component polyurethane coating composition is a two-component polyurethane coating waterproofing composition for hand coating.