JP2003313265A - Polyurea resin composition, method for producing polyurea coating, curing agent for polyurea resin, and composition set for forming polyurea resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an extremely short curing time, a curing reaction catalyst is unnecessary, and it is possible to make a solvent unnecessary, which has excellent stability to light, high hardness, Provided is a polyurea resin composition capable of obtaining a tough cured film having good water resistance. SOLUTION: A compound represented by the following general formula (1):
A polyurea resin composition comprising a polyamine component containing a compound represented by the following general formula (2), a compound represented by the following general formula (3), and a polyisocyanate component. Embedded image

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polyurea resin composition, a method for producing a polyurea coating film using the composition, and a curing agent for polyurea resin. More specifically, a specific bis (N-alkylaminocyclohexyl)
The present invention relates to a polyurea resin composition using methanes, aminocyclohexyl (N-alkylaminocyclohexyl) methanes and aspartic acid esters, a method for producing a polyurea coating using the composition, and a curing agent for polyurea resins.

[0002]

2. Description of the Related Art Since the reactivity of active hydrogen with isocyanate is large, a polymer material can be easily obtained by reacting a polyfunctional active hydrogen-containing compound with a polyisocyanate compound.
By combining polyfunctional active hydrogen-containing compounds with various structures and polyisocyanate compounds, it is possible to synthesize polymer materials with various properties, and are widely used in paints, adhesives, elastomers, molding materials, etc. There is.

In the industrial field where these polyisocyanates are used, most of the other polyfunctional active hydrogen-containing compounds are mainly polyol compounds having a hydroxyl group, and they are aimed at the production of so-called polyurethanes. Since the reaction between the isocyanate group and the hydroxyl group proceeds relatively mildly, various catalysts such as tertiary amines and organometallics are used to increase the reactivity. Most of the polyol compounds are solid substances or high-viscosity substances, and thus are often used in a state of being dissolved in various solvents at the time of reaction with the polyisocyanate compound.

In some cases, these catalysts, solvents, etc. are volatilized into the atmosphere during preparation and subsequent film formation, which is a problem from the viewpoint of environment and safety.

Polyurethanes can be considerably different depending on the designing method, but they have good adhesion to various materials, high coating hardness, elasticity, and excellent abrasion resistance, chemical resistance, etc. It is a polymeric material that exhibits physical properties.
However, many of the polyurethanes currently used have the problem of yellowing due to light exposure.

On the other hand, as a polyfunctional active hydrogen-containing compound, a reaction with a polyamine having an amino group has been known for a long time. Cyclic diamines are also used in various urethane urea products, but they are mainly used to accelerate the reactivity with isocyanate and to control the physical properties by utilizing the hydrogen bonding property of the generated urea bond.

In recent years, there has been proposed a technique for improving various characteristics by using bis (N-alkylaminocyclohexyl) methane which is a diamine compound as a chain extender for polyurethane and polyurea (Japanese Patent No. 2759053). It is described that these diamine compounds have stability to light, that is, they are used as a curing agent or a chain extender for providing polyurethane and polyurea which are less yellowed by exposure to light.

However, when the above bis (N-alkylaminocyclohexyl) methanes are used as a curing agent or a chain extender for obtaining polyurethanes and polyureas, the stability to light is improved, but to sunlight. Further improvement is required in exposed applications. Further, in these reaction systems, it is necessary to substantially use a curing reaction catalyst or to use an organic solvent together, and further improvement is required from the viewpoint of environment and safety.

Further, Japanese Patent Publication No. 6-53871 discloses that
A method for forming a polyurethane coating using aspartic acid esters is disclosed, but the coating obtained by this method softens over time when immersed in water, and eventually the coating is damaged. There was a serious drawback:

[0010]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, that is, the curing time is extremely short, a curing reaction catalyst is unnecessary, and further, a solvent is unnecessary.
It has excellent stability to light, high hardness, toughness,
An object of the present invention is to provide a polyurea resin composition capable of obtaining a cured coating having good water resistance, a method for producing a polyurea coating using the composition, and a curing agent for a polyurea resin.

[0011]

Means for Solving the Problems As a result of intensive research and study to solve the above-mentioned problems, the present inventors have found that a specific bis (N-
Alkylaminocyclohexyl) methanes combined with specific aminocyclohexyl (N-alkylaminocyclohexyl) methanes and aspartic acid esters mainly reacts with polyisocyanate monomer to form polyurea. Equivalent to the polyol in the case of),
The resulting polyurea is more stable to light and has high hardness, toughness, and good water resistance,
The urea reaction rate is fast and the curing reaction catalyst is substantially unnecessary. Furthermore, when a specific polyisocyanate component is used, a cured film that is homogeneous and smooth even though the composition contains almost no volatile component. In addition, it was found that, in addition to exhibiting extremely high hardness, toughness, and physical properties excellent in water resistance, it was also extremely stable against light, and completed the present invention.

That is, in one embodiment of the polyurea resin composition according to the present invention, the compound represented by the following general formula (1), the compound represented by the following general formula (2) and the following general formula (3) And a polyamine component containing a compound represented by the formula (4) and a polyisocyanate component.

[0013]

[Chemical 12]

(In the formula, R ₁ and R ₂ are each an alkyl group having 1 to 10 carbon atoms and may be the same or different. R _{3 to} R ₆ are each a hydrogen atom or An alkyl group having 1 to 5 carbon atoms, which may be the same or different.)

[0015]

[Chemical 13]

(Wherein R ₇ is an alkyl group having 1 to 10 carbon atoms. R _{8 to} R ₁₁ are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
It may be the same or different. )

[0017]

[Chemical 14]

(In the formula, R ₁₂ and R ₁₃ are 1 to 10 respectively.
Are alkyl groups having carbon atoms, and may be the same or different. R ₁₄ and R ₁₅ are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be the same or different. X is an organic group that has an n-valent valence and is inactive with respect to the isocyanate group, and n represents an integer of 2 or more. )

An embodiment of the method for producing a polyurea coating film according to the present invention is characterized in that the polyamine component and the polyisocyanate component of the polyurea resin composition are reacted.

Further, one embodiment of the curing agent for polyurea resin according to the present invention is the compound represented by the above general formula (1), the compound represented by the above general formula (2), and the above general formula ( And a compound represented by 3).

Furthermore, one embodiment of the composition set for forming a polyurea resin according to the present invention is a composition for forming a polyurea resin, which independently comprises i) a polyisocyanate component and ii) a polyamine component. And the polyamine component contains a compound represented by the general formula (1), a compound represented by the general formula (2), and a compound represented by the general formula (3). It is characterized by doing.

Although the details of the action of the compound represented by the general formula (2) are not clear, a crosslinking reaction is induced due to its high reaction activity with the isocyanate component, resulting in the general formula (3). It is thought that this suppresses the water resistance deterioration property of the compound represented by.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The polyamine component (curing agent) comprises the compound represented by the general formula (1), the compound represented by the general formula (2) and the compound represented by the general formula (3). contains.

In the general formulas (1) and (2), R ₁ ,
R ₂ and R ₇ are each an alkyl group having 1 to 10 carbon atoms and may be linear or branched. In particular,
Methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, various isomers pentyl group, heptyl group, octyl group, nonyl group , Decyl group and the like, preferably an alkyl group having 3 to 10 carbon atoms, more preferably n-butyl group, iso-butyl group, sec-
Butyl group, tert-butyl group, most preferably sec
A butyl group. R ₁ and R ₂ may be the same or different, but are preferably the same.

R _{3 to} R ₆ and R _{8 to} R ₁₁ are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms and have 1 to 1 carbon atoms.
The alkyl group of 5 may be linear or branched.
R ₃ , R ₄ , R ₈ , and R ₉ are hydrogen atoms or methyl groups, R ₅ ,
R ₆ , R ₁₀ and R ₁₁ are preferably hydrogen atoms. R ₃
And R ₄ , R ₅ and R ₆ , R ₈ and R ₉ , and R ₁₀ and R ₁₁ may be the same or different, but are preferably the same.

Further, R ₂ and R ₇ , R ₃ and R ₈ , R ₄ and R ₉ , R
₅ and R ₁₀ , and R ₆ and R ₁₁ may be the same or different, but are preferably the same.

In the general formula (3), R ₁₂ , R ₁₃
Are each an alkyl group having 1 to 10 carbon atoms and may be linear or branched. Specifically, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group,
n-butyl group, iso-butyl group, sec-butyl group,
tert-butyl group, various isomeric pentyl groups, heptyl group, octyl group, nonyl group, decyl group and the like,
It is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, and most preferably an ethyl group. R ₁₂ and R ₁₃ may be the same or different, but are preferably the same.

R ₁₄ and R ₁₅ are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the alkyl group having 1 to 5 carbon atoms may be linear or branched and is a hydrogen atom. Preferably there is. R ₁₄ and R ₁₅ may be the same or different, but are preferably the same.

X is an organic group having a valence of n, which is inactive to an isocyanate group, and is preferably a divalent hydrocarbon group having a linear, branched or alicyclic chain.
Specifically, 1-ethyltrimethylene group, tetramethylene group, pentamethylene group, 2-methylpentamethylene group, hexamethylene group, 2,2,4-trimethylhexamethylene group, 2,4,4-trimethylhexamethyl group Methylene group, methylene (3,5,5-trimethyl-3,1-cyclohexylene) group, methylenebis (4,4′-cyclohexylene) group, methylenebis (3,3′-dimethyl-)
4,4′-cyclohexylene) group, undecamethylene group, dodecamethylene group, 1,4-cyclohexylene group,
1,2-cyclohexylene group and the like can be mentioned.

Although n is an integer of 2 or more, aspartic acid esters in which n is 2 are particularly preferable.

The mixing ratio of the compound represented by the general formula (1) and the compound represented by the general formula (2) is 100 parts by weight of the compound represented by the general formula (1). 4 to 20 parts by weight of the compound represented by

The mixing ratio of the compounds represented by the general formulas (1) to (3) is 40% by weight of the compound represented by the general formula (1).
To 80 parts by weight, compounds 3 to 13 represented by the general formula (2)
By weight, 60 to 20 parts by weight of the compound represented by the general formula (3) is preferable.

Examples of the polyisocyanate component include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate. , 2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,4-naphthalene diisocyanate,
1,5-naphthalene diisocyanate, chlorophenylene-2,4-diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 3,3'-
Dimethoxydiphenyl-4,4'-diisocyanate,
Aromatic diisocyanates such as o-xylene diisocyanate and m-xylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 2, -methyl-1,5-pentamethylene diisocyanate, 2,2,4- Trimethyl-1,
6-hexamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate,
Aliphatic diisocyanates such as decamethylene diisocyanate and lysine diisocyanate, 1,4-cyclohexyl diisocyanate, isophorone diisocyanate,
Examples thereof include alicyclic diisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate.

Further, a modified polyisocyanate containing one or more of uretdione bond, isocyanurate bond, allophanate bond, biuret bond, uretonimine bond, carbodiimide bond, urethane bond, urea bond and the like obtained by modifying these polyisocyanates is also available. Can be used. Furthermore, polyisocyanates such as polyphenylene polymethylene polyisocyanate and crude toluene diisocyanate can also be used. Further, a terminal isocyanate prepolymer which is a reaction product of a polyol and / or a polyamine in a maximum amount of 0.5 equivalent with respect to 1 equivalent of a monomer polyisocyanate can also be used.

These polyisocyanates may be used alone or in combination of two or more kinds.

Among them, a composition containing almost no volatile component can be obtained and more excellent weather resistance can be obtained. Therefore, the compound represented by the following general formula (a) and the following general formula (b) To (c) are preferably mixed with at least one compound selected from the compounds represented by the formulas (c) to (c), more preferably 50 to 80 mol% of the compound represented by the formula (a) and represented by the formula (b). It is a mixture comprising 50 to 20 mol% of a compound and / or a compound represented by the general formula (c). These may be used in combination with the above polyisocyanates such as aromatic diisocyanates, polyphenylene polymethylene polyisocyanates, and crude toluene diisocyanates.

[0038]

[Chemical 15]

(In the formula, R _{21 to} R ₂₃ are 4 to 10 respectively.
Represents an alkylene group having a carbon atom, a cycloalkylene group, preferably an n-hexylene group, and R ₂₄ is 1 to 1.
It represents an alkyl group having 0 carbon atoms, preferably an n-butyl group. )

For the same reason, 1,6-hexamethylene diisocyanate (HDI) derivative can also be preferably used, and examples thereof include oligomers obtained by isocyanurate bond, uretdione bond, allophanate bond, biuret bond, and the like. It is more preferable that the isocyanurate bond is in the range of 50 to 80 mol% and the uretdione bond and / or the allophanate bond is in the range of 50 to 20 mol%. In this case, the compounds represented by the general formulas (a) to (c) may be mixed, or an isocyanurate bond,
Two or more kinds of uretdione bond and allophanate bond are 1
Those linked in one molecule may be used. These may be used in combination with the above polyisocyanates such as aromatic diisocyanates, polyphenylene polymethylene polyisocyanates, and crude toluene diisocyanates.

The ratio of the polyamine component to the polyisocyanate component is preferably such that the isocyanate equivalent ratio in the polyisocyanate component is 0.9 to 1.25 with respect to 1 equivalent of active hydrogen in the polyamine component. By setting this equivalent ratio, the curing reaction becomes sufficient and sufficient coating film physical properties can be exhibited. Furthermore, since it is possible to effectively prevent the excess isocyanate from remaining in the coating, it is possible to eliminate or alleviate the change in the physical properties of the coating which is considered to be caused by the decomposition reaction with water.

In the present invention, if necessary, a coloring agent,
Additives such as a stabilizer, a dispersant, an anti-hydrolysis agent, a filler, a lubricant, an ultraviolet absorber, a leveling agent, an antioxidant, a flame retardant, and a defoaming agent can be appropriately added depending on the application and purpose. .

The polyurea resin composition of the present invention can be preferably used as a two-pack type coating composition of a polyamine component and a polyisocyanate component, and is applied by a known coating method using a two-component type high pressure spray, a quantitative mixing dispenser, a static mixer or the like. can do. However, in the present invention, the reaction starts immediately after mixing the polyamine component and the polyisocyanate component, and the liquid viscosity increases accordingly. In addition, the reaction rate of the polyamine component and the organic polyisocyanate component is essentially high, and at the same time,
When a specific polyisocyanate is used, the solvent does not coexist in the reaction solution, and the time from mixing to coating and coating film formation is short, so a two-component high pressure spray is used. The coating method is preferred.

The composition according to the present invention can be applied to various substrates such as various plastics, organic substrates such as rubber, wood and paper, various metals, inorganic substrates such as concrete and ceramics. In particular, since the curing speed is very fast, it can be suitably used for coating vertical surfaces such as walls and ceilings.

The polyurea resin composition according to the present invention may be sold and distributed in the form of a composition set in which a polyisocyanate component and a polyamine component are placed in independent containers.

[0046]

The present invention will be described in more detail with reference to the following examples.

<Synthesis Example 1> Synthesis of compound represented by the following formula (1-b): Alumina-supported platinum catalyst and bis (4-
Aminocyclohexyl) methane (10 g) and methyl ethyl ketone (27.4 g) were added, and the mixture was stirred and reacted at 120 ° C. for 8 hours in the presence of hydrogen and a pressure of 8 MPa. After the reaction was completed, excess methyl ethyl ketone and water produced were separated from the reaction mixture and purified to obtain a nearly colorless and transparent viscous liquid. The elemental analysis values of the obtained compound are shown below together with the calculated values. [Elemental analysis value] C: 78.11%, H: 13.20%,
N: 8.69% [Calculated value] C: 78.19%, H: 13.12%, N:
8.68%

<Synthesis Example 2> Bis (4-
A compound represented by the following formula (1-d) was obtained in the same manner as in Synthesis Example 1 except that bis (4-amino-3methylcyclohexyl) methane was used instead of aminocyclohexyl) methane.

In the same manner, a compound represented by the following formula (1-a) and a compound represented by the following formula (1-c) were obtained.

[0050]

[Chemical 16]

<Synthesis Example 3> Synthesis of compound represented by the following formula (2-b) 10 g of bis (4-aminocyclohexyl) methane was placed in a three-necked flask equipped with a condenser, a dropping funnel, a thermometer and a stirrer, and methyl ethyl ketone was added. After 10.74 g was added dropwise, the mixture was refluxed for 6 hours to obtain 8.9 g of a pale brown liquid. Then, it is purified by column chromatography, and N- {4-[(4-aminocyclohexyl) methyl] cyclohexyl} -N-
2.7 g of (1-methylpropylidene) amine was obtained. After dissolving in 40 ml of dry methanol, cooling to 5-10 ° C.
0.19 g of aBH ₄ was added, and the temperature was raised to 35 ° C. in 24 hours. The mixture was further cooled to 10 ° C. or lower, excess dilute hydrochloric acid was added, and after dissolution, 15% ammonia water was added dropwise until the reaction liquid became cloudy. After extraction with ethyl acetate, washing with water, and drying with a general-purpose desiccant, the solvent was distilled off to obtain 1.0 g of a pale yellow viscous liquid. The elemental analysis values of the obtained compound are shown below together with the calculated values. [Elemental analysis value] C: 76.57%, H: 12.89%,
N: 10.54% [Calculated value] C: 76.63%, H: 12.86%, N:
10.51%

<Synthesis Example 4> A compound represented by the following formula (2-a) was obtained in the same manner as in Synthesis Example 3 except that acetone was used in place of methyl ethyl ketone as the raw material ketones.

In the same manner, a compound represented by the following formula (2-c) and a compound represented by the following formula (2-d) were obtained.

[0054]

[Chemical 17]

<Synthesis Example 5> 1.00 parts by weight of 2-methyl-pentamethylenediamine was placed under a nitrogen atmosphere in a three-necked round bottom flask equipped with a mechanical stirrer, a thermometer, and a dropping funnel and kept at 15 ° C. It was Diethyl maleate 2.9
6 parts by weight was added dropwise with stirring for 5 hours. After the dropping was completed, the reaction was completed by heating to 50 ° C. After purification, a pale yellow and transparent compound represented by the following formula (3-a) was obtained. The elemental analysis values of the obtained compound are shown below together with the calculated values. [Elemental analysis value] C: 57.34%, H: 8.72%,
N: 6.11%, O: 27.83% [Calculated value] C: 57.37%, H: 8.75%, N:
6.08%, O: 27.79%

In the same manner as above, compounds represented by the following formula (3-b) to compounds represented by the following formula (3-g) were obtained.

[0057]

[Chemical 18]

Example 1 Liquids A-1 and B-1 having the following compositions were mixed at 23 ° C. using a static mixer to prepare a polyurea resin composition.

Liquid A-1 (Polyamine Component) Compound represented by Formula (1-b) 57 parts by weight Compound represented by Formula (2-b) 8 parts by weight Compound represented by Formula (3-a) 35 parts by weight B-1 liquid (polyisocyanate component) 65 mol% of a compound represented by the general formula (a) (R ₂₁ is n-hexylene group), a compound represented by the general formula (b) (R ₂₂ is n -Hexylene group) 15 mol%, a compound represented by the general formula (c) (R ₂₃ is n-hexylene group, R ₂₄ is n-butyl group) 20 mol%, 100 parts by weight of a mixture.

Using the polyurea resin composition obtained,
The following evaluation was performed. The results are shown in Table 1.

(Measurement of Gel Time) After the polyurea resin composition was discharged onto a glass plate, it was immediately pulled upward while stirring with a spatula, and the time until the composition stopped pulling a thread was measured and used as the gel time.

(Measurement of Hardness) After the polyurea resin composition was prepared, it was immediately poured into a Teflon (registered trademark) mold of 150 mm × 150 mm × 3 mm and left at 23 ° C. for 24 hours,
Room temperature hardness was measured with a Shore hardness meter.

(Weather resistance) Immediately after preparing the polyurea resin composition, the polyurea resin composition was poured into a Teflon (registered trademark) mold of 150 mm × 10 mm × 3 mm, left standing for 24 hours for curing, and then released to prepare strip-shaped test pieces. This test piece was subjected to an exposure test under the following conditions to visually observe the state of yellowing, and evaluated according to the following criteria.

Exposure conditions: Xenon arc lamp, irradiation illuminance; 340 W / mm ² , exposure time; 1000 hours, 1 cycle; 120 minutes, watering; 18 minutes, temperature; 63 ° C. ◎: excellent (no change) ○: good ( Slightly cloudy) △: Slightly bad (slightly yellowing) ×: Bad (yellowing)

(Water resistance) A test piece prepared by the same method as the weather resistance test was immersed in warm water at 60 ° C. for 168 hours, and the condition of the test piece was visually observed and evaluated according to the following criteria. ◎: Excellent (no change) ○: Good (slightly elastic) △: Slightly poor (elastic) ×: Poor (the surface is eroded and the original shape is not retained)

(Flexibility) Tin plate (150 mm × 50 m)
m × 0.3 mm), the polyurea resin composition was applied to a thickness of about 0.5 mm using a spray device. After being left for 24 hours for curing, the test piece was bent by a simple bending tester, the state of the coating film was visually observed, and evaluated according to the following criteria. ⊚: Excellent (no change) ○: Good (slightly cracks are observed) Δ: Slightly bad (cracks are not generated, no film peeling) ×: Bad (coating is destroyed and peeled)

Example 2 A polyurea resin composition was prepared and evaluated in the same manner as in Example 1 except that the solution A-2 shown below was used in place of the solution A-1. The results are shown in Table 1.

[0068]   Liquid A-2 (polyamine component) 50 parts by weight of the compound represented by formula (1-d) 7 parts by weight of the compound represented by formula (2-d) 43 parts by weight of the compound represented by formula (3-b)

Example 3 With the composition shown below, Solution A-3 and Solution B-2 were mixed at 50 ° C. using a static mixer to prepare a polyurea resin composition, and the same procedure as in Example 1 was carried out. evaluated. The results are shown in Table 1.

Liquid A-3 (polyamine component) Compound represented by the formula (1-c) 70 parts by weight Compound represented by the formula (2-c) 9 parts by weight Compound represented by the formula (3-c) 21 parts by weight Liquid B-2 (polyisocyanate component) Compound represented by the general formula (a) (R ₂₁ is n-hexylene group) 70 mol%, Compound represented by the general formula (b) (R ₂₂ is n -Hexylene group) 30 mol% mixture 100 parts by weight

Example 4 Liquids A-4 and B-3 having the compositions shown below were mixed at 60 ° C. using a static mixer to prepare a polyurea resin composition, and the same procedure as in Example 1 was carried out. evaluated. The results are shown in Table 1.

Liquid A-4 (polyamine component) Compound represented by the formula (1-a) 65 parts by weight Compound represented by the formula (2-a) 10 parts by weight Compound represented by the formula (3-c) 25 parts by weight B-3 liquid (polyisocyanate component) 75 mol% of the compound represented by the general formula (a) (R ₂₁ is n-hexylene group), the compound represented by the general formula (c) (R ₂₃ is n -Hexylene group, R ₂₄ is n-butyl group) 25 mol% mixture 100 parts by weight

<Comparative Example 1> As the polyamine component, the compound represented by the formula (1
A polyurea resin composition was prepared and evaluated in the same manner as in Example 1 except that only the compound represented by -b) was used.
The results are shown in Table 1.

<Comparative Example 2> As the polyamine component, the compound of the formula (3
A polyurea resin composition was prepared and evaluated in the same manner as in Example 1 except that only the compound represented by -a) was used.
The results are shown in Table 1.

[0075]

[Table 1]

[0076]

As described above, the composition of the present invention is
It can be cured at room temperature, and since the curing time is extremely short, a curing reaction catalyst is unnecessary, and when a specific polyisocyanate is used, it does not substantially contain a volatile organic component. Moreover, the cured film obtained by the present invention has excellent weather resistance, high hardness, toughness, and good water resistance,
It can be suitably used as a coating composition.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Naoki Fueki             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Motokazu Kobayashi             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Jun Kubota             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F-term (reference) 4D075 CA02 CA03 CA32 CA38 CA44                       DB01 DB12 DB14 DB18 DB21                       DB31 DC02 EA07 EA27 EB38                       EB39 EB45 EB56 EC07 EC37                       EC54                 4J034 AA03 AA04 CA15 CA17 CA23                       CB03 CB04 CC03 CC05 CC23                       CC26 CC45 CC52 CC62 CC67                       HA07 HB09 HC03 HC12 HC13                       HC17 HC46 HC53 HC61 HC64                       HC67 HC70 HC71 RA07

Claims (15)

[Claims] 1. A compound represented by the following general formula (1):
A polyurea resin composition comprising a polyamine component containing a compound represented by the following general formula (2), a compound represented by the following general formula (3), and a polyisocyanate component. [Chemical 1] (In the formula, R ₁ and R ₂ are each an alkyl group having 1 to 10 carbon atoms and may be the same or different. R _{3 to} R ₆ are each a hydrogen atom or 1 to 5). An alkyl group having a carbon atom of, which may be the same or different.) (In the formula, R ₇ is an alkyl group having 1 to 10 carbon atoms. R _{8 to} R ₁₁ are each a hydrogen atom or 1 to
An alkyl group having 5 carbon atoms, which may be the same or different. ) [Chemical 3] (In the formula, R ₁₂ and R ₁₃ are alkyl groups each having 1 to 10 carbon atoms and may be the same or different. R ₁₄ and R ₁₅ are each a hydrogen atom or 1 to 5).
Are alkyl groups having carbon atoms, and may be the same or different. X is an organic group that has an n-valent valence and is inactive with respect to the isocyanate group, and n represents an integer of 2 or more. ) 2. The method according to claim 1, wherein R ₂ and R ₇ , R ₃ and R ₈ , R ₄ and R ₉ , R ₅ and R ₁₀ , R ₆ and R ₁₁ are the same. Polyurea resin composition. 3. R ₁ , R ₂ and R ₇ are alkyl groups having 3 to 10 carbon atoms.
Alternatively, the polyurea resin composition according to item 2. 4. R ₁ and R ₂ are butyl groups, R ₃ and R ₄ are hydrogen atoms or methyl groups, and R ₅ and R ₆ are hydrogen atoms. The polyurea resin composition described in 1. Wherein R ₇ is butyl group, according to any one of claims 1 to 4 R _8, R ₉ is hydrogen atom or a methyl group, and R _{1 0,} R ₁₁ is characterized in that it is a hydrogen atom Polyurea resin composition of. 6. The polyurea resin composition according to claim 1, wherein R ₁₂ and R ₁₃ are ethyl groups and R ₁₄ and R ₁₅ are hydrogen atoms. 7. A compound represented by the general formula (1)
0 to 80 parts by weight, 3 to 13 parts by weight of the compound represented by the general formula (2), and 60 to 20 parts by weight of the compound represented by the general formula (3) are contained. 1 to
The polyurea resin composition according to any one of 5 above. 8. The compound 10 represented by the general formula (1).
The compound represented by the general formula (2) is contained in an amount of 4 to 20 parts by weight based on 0 part by weight.
The polyurea resin composition according to any one of 1. 9. The polyurea according to claim 1, wherein the equivalent ratio of isocyanate in the polyisocyanate component to 1 equivalent of active hydrogen in the polyamine component is 0.9 to 1.25. Resin composition. 10. The polyisocyanate component comprises a compound represented by the following general formula (a) and the following general formula (b):
The polyurea resin composition according to any one of claims 1 to 9, which is a mixture with at least one selected from the compounds represented by (c). [Chemical 4] (In the formula, R _{21 to} R ₂₃ each represent an alkylene group or a cycloalkylene group having 4 to 10 carbon atoms, and R ₂₄
Represents an alkyl group having 1 to 10 carbon atoms. ) 11. The polyurea resin composition according to claim 1, wherein the polyisocyanate component is a hexamethylene diisocyanate derivative. 12. A method for producing a polyurea coating, which comprises reacting a polyamine component and a polyisocyanate component of the polyurea resin composition according to any one of claims 1 to 11. 13. A compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (3). Hardening agent for polyurea resin. [Chemical 5] (In the formula, R ₁ and R ₂ are each an alkyl group having 1 to 10 carbon atoms and may be the same or different. R _{3 to} R ₆ are each a hydrogen atom or 1 to 5). An alkyl group having carbon atoms, which may be the same or different.) (In the formula, R ₇ is an alkyl group having 1 to 10 carbon atoms. R _{8 to} R ₁₁ are each a hydrogen atom or 1 to
An alkyl group having 5 carbon atoms, which may be the same or different. ) [Chemical 7] (In the formula, R ₁₂ and R ₁₃ are alkyl groups each having 1 to 10 carbon atoms and may be the same or different. R ₁₄ and R ₁₅ are each a hydrogen atom or 1 to 5).
Are alkyl groups having carbon atoms, and may be the same or different. X is an organic group that has an n-valent valence and is inactive with respect to the isocyanate group, and n represents an integer of 2 or more. ) 14. A set of compositions for forming a polyurea resin, which independently comprises i) a polyisocyanate component and ii) a polyamine component, wherein the polyamine component is represented by the following general formula (1): And a compound represented by the following general formula (2), and a compound represented by the following general formula (3). [Chemical 8] (In the formula, R ₁ and R ₂ are each an alkyl group having 1 to 10 carbon atoms, and may be the same or different. R _{3 to} R ₆ are each a hydrogen atom or 1 to 5). An alkyl group having a carbon atom of, which may be the same or different.) (In the formula, R ₇ is an alkyl group having 1 to 10 carbon atoms. R _{8 to} R ₁₁ are each a hydrogen atom or 1 to
An alkyl group having 5 carbon atoms, which may be the same or different. ) [Chemical 10] (In the formula, R ₁₂ and R ₁₃ are each an alkyl group having 1 to 10 carbon atoms and may be the same or different. R ₁₄ and R ₁₅ are each a hydrogen atom or 1 to 5;
Are alkyl groups having carbon atoms, and may be the same or different. X is an organic group that has an n-valent valence and is inactive with respect to the isocyanate group, and n represents an integer of 2 or more. ) 15. The isocyanate component comprises a compound represented by the following general formula (a) and a compound represented by the following general formula (b):
The composition set for forming a polyurea resin according to claim 14, which is a mixture with at least one selected from the compounds represented by (c). [Chemical 11] (In the formula, R _{21 to} R ₂₃ each represent an alkylene group or a cycloalkylene group having 4 to 10 carbon atoms, and R ₂₄
Represents an alkyl group having 1 to 10 carbon atoms).