JP2003096154A - Two-pack curable resin composition and two-pack curable coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a two-pack curable resin composition which excels in adhesion, has quick drying properties, excels in water resistance, alkali resistance, and corrosion resistance such as cathodic peeling properties, has good impact resistance, and is suitable as the resin composition for a solventless two-pack effective type coating material, and a two-pack curable coating material composed of this composition. SOLUTION: The two-pack curable resin composition comprises (A1) an amino compound having two or more secondary amino groups to be obtained by reacting (a1) a compound having a primary amino group directly bonded to a tertiary alkyl group with (a2) a compound having two or more unsaturated double bonds and (B) a polyisocyanate compound. The two-pack curable resin composition further comprises (A2) a polyol compound. The two-pack curable coating material comprises this composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a two-part curable resin composition and a two-part curable coating composition using the composition. More specifically, steel sheet piles, steel pipe sheet piles, steel pipe piles, civil engineering such as steel, construction materials such as steel materials, water resistance at the time of cathodic protection in a long-term corrosive environment, alkali resistance,
Excellent in corrosion resistance such as cathode peeling resistance and adhesion, quick drying,
TECHNICAL FIELD The present invention relates to a two-component curable urethane resin composition having good impact resistance in a low temperature environment and suitable as a resin composition for a solventless two-component curable coating, and a two-component curable coating using the composition. It is a thing.

[0002]

2. Description of the Related Art Conventionally, as a resin for industrial machines, vehicles, anticorrosion, woodworking, inorganic building materials, floors, etc., alkyd resin paints, urethane resin paints, etc. have a relatively high molecular weight and are excellent in appearance. General-purpose paint is used. However, many of them contain a large amount of organic solvent for the purpose of improving coating workability although they are unnecessary for essential coating film formation. This does not meet today's resource saving requirements, has the risk of flammable explosion, and is also a source of air pollution when it is volatilized into the atmosphere during the drying process.

In the case of a solvent-free paint, it is preferable that the paint viscosity is low in consideration of coating workability. Therefore, it is considered that a relatively low molecular weight material effective for lowering the viscosity is also effective as a resin constituent component. It is considered that a two-component curing type urethane resin coating having a low molecular weight and high reactivity is most suitable for this. However, since the conventional urethane resin paint has too strong cohesive force, the adhesion to metal is poor. Therefore, a primer must be used together, and the coating work process is complicated.

In order to improve these drawbacks, a solventless type two-component curing type urethane resin paint has been developed in recent years. The simplest solvent-free two-component curable urethane resin composition is a two-component curable urethane resin composition composed of two components, castor oil and polyisocyanate. However, the cured coating film is not practical because it remains tacky, has low hardness, and is inferior in corrosion resistance such as water resistance and alkali resistance.

To improve the drawbacks of these castor oil-based two-component curable urethane resin compositions, a polyester polyether polyol comprising a polyester polyol such as castor oil and a polyhydric alcohol (JP-A-49-110724).
Japanese Patent Publication No. 1-29389), a polyol blended with an epoxy modified product (JP-A-51-41737), and a polyester polyol composed of castor oil polyol and amine polyol (JP-B-63-17304, JP-B-63-304). 28474), a polyol obtained by adding a xylene resin thereto (Japanese Patent Publication No. 1-38666, Japanese Patent Publication No. 1-36867), and a polyester polyether polyol composed of castor oil and polyether polyol (Japanese Patent Publication No. 1-11234, Japanese Patent Publication No. There is a two-component curable urethane resin composition using, for example, Japanese Patent Publication No. 1-11235).

However, even a two-component curable urethane resin composition using these polyester polyols is inferior in quick-drying property, and the effect of improving corrosion resistance such as water resistance, alkali resistance, water resistance, and cathode peeling property is not sufficient. I was not satisfied.

[0007]

The problem to be solved by the present invention is that it has excellent adhesion to materials, especially metal materials, has fast drying property, has excellent corrosion resistance such as water resistance, alkali resistance, and cathode peeling property, and also has impact resistance. (EN) It is intended to provide a two-component curable resin composition which is good and is suitable as a resin composition for a solventless two-component effect type paint, and a two-component curable coating composition comprising this composition.

[0008]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a compound (a1) having a primary amino group directly bonded to a tertiary alkyl and an unsaturated double bond are used. An amino compound (A1) having two or more secondary amino groups obtained by reacting with a compound (a2) having two or more of is used together with a polyol compound (A2),
A two-component curable urethane urea resin composition containing a polyisocyanate compound is suitable as a resin composition for a solventless two-component curable coating material, and a two-component curable coating material using this composition is adhered. Excellent, fast drying, water resistance, alkali resistance, corrosion resistance such as cathode peelability is equal to or more than the conventionally known paint, and also excellent in impact resistance, without using the polyol compound (A2), Even a two-component curable urea resin composition prepared by blending the amino compound (A1) and the polyisocyanate compound (B) is suitable as a resin composition for a solvent-free two-component curable coating material. The two-component curing type coating composition containing the composition has excellent adhesion, quick drying property, water resistance, alkali resistance, cathode peeling resistance and other corrosion resistance equivalent to or better than conventionally known coating materials and impact resistance is also compared. To find that it is good This has led to the completion of the present invention.

That is, the present invention is obtained by reacting a compound (a1) having a primary amino group directly bonded to a tertiary alkyl with a compound (a2) having two or more unsaturated double bonds. A two-component curable resin composition comprising an amino compound (A1) having two or more secondary amino groups and a polyisocyanate compound (B) as essential components. Is provided.

The present invention also provides a compound obtained by reacting a compound (a1) having a primary amino group directly bonded to a tertiary alkyl with a compound (a2) having two or more unsaturated double bonds. A two-component curable resin characterized by comprising an amino compound (A1) having two or more secondary amino groups, a polyol compound (A2) and a polyisocyanate compound (B) as essential components. A composition is provided.

Further, the present invention provides a two-component curable coating material containing the above-mentioned two-component curable resin composition.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The amino compound (A) used in the present invention includes a compound (a1) having a primary amino group directly bonded to a tertiary alkyl and a compound (a) having two or more unsaturated double bonds.
It is not particularly limited as long as it is an amino compound having two or more secondary amino groups obtained by reacting with 2), and among them, an amino compound having 2 to 6 secondary amino groups is preferable, and Particularly preferred are amino compounds having 2 to 4 secondary amino groups.

The compound (a1) having a primary amino group directly bonded to a tertiary alkyl used herein is not particularly limited, but is reacted with a compound (a2) having two or more unsaturated double bonds. A monovalent amine compound is desirable because it does not gel during the synthesis of the amino compound (A). The number of carbon atoms of the alkyl group of the compound (a1) having a primary amino group directly bonded to a tertiary alkyl is obtained by reacting with a compound (a2) having two or more unsaturated double bonds. Since it is possible to prevent the reactivity of the secondary amino group of the amino compound (A) having two or more amino groups to be reduced, it is preferably 4 to 40, and particularly preferably 4 to 22.

A specific example of the compound (a1) having a primary amino group directly linked to a tertiary alkyl is tert-
Butylamine, tert-octylamine (1,1-dimethylhexylamine), tert-nonylamine (1,1-dimethylheptylamine), tert-decylamine (1,1-dimethyloctylamine), ter
Examples thereof include t-dodecylamine (1,1-dimethyldecylamine) and tert-stearylamine (1,1-dimethylhexadecylamine). Examples of the commercially available compound (a1) having a primary amino group directly linked to a tertiary alkyl include Rohm and Haas.
Primene TOA (alkyl group having 8 carbon atoms), Primene 81-R (alkyl group having 12 carbon atoms), and Primary Ami manufactured by Japan Ltd.
ne (the number of carbon atoms in the alkyl group is 12), Primene
JM-T (alkyl group has 18 carbon atoms), Prim
ary Amine (18 carbon atoms in the alkyl group),
Primene MD (alkyl group has 1 carbon atom)
0); United States National Chemical In
Amines, C _16-22 manufactured by Ventories.
-Tert-alkyl (alkyl group having 16 carbon atoms
22), Amines, C _12-14 -tert-a.
lkyllauryl (the number of carbon atoms of the alkyl group is 12 to
14) and the like.

The compound (a2) having two or more unsaturated double bonds used in the present invention may be any compound having two or more unsaturated double bonds and is not particularly limited, but may be a tertiary alkyl group. A compound having 2 to 20 (meth) acryloyl groups is preferable, and particularly 2 to 6 because it is less likely to gel during the reaction with the compound (a1) having a directly linked primary amino group. Compounds having are particularly preferred.

Specific examples of the compound (a2) having two or more unsaturated double bonds include acrylates having two or more acryloyl groups, and 1,4-butanediol diacrylate and 1,6-hexanediol diacrylate. Acrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate,
1,3-butylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane ethylene oxide modified triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate Examples thereof include acrylate and methoxylated cyclohexyl diacrylate. Examples of commercially available acrylates include diacrylate type light ester 1,6HX (1,6-hexanediol diacrylate) manufactured by Kyoeisha Chemical Co., Ltd., light ester 1,9ND (1,9-nonanediol diacrylate), Viscoat 25 (neopentyl glycol diacrylate) manufactured by Osaka Organic Chemical Industry Co., Ltd., SR- manufactured by SARTOMER Company
212 (1,3-butylene glycol diacrylate)
And the like, and as a triacrylate type and a tetraacrylate type, Kyoeisha Chemical Co., Ltd. light acrylate TMP-A (trimethylolpropane triacrylate), SARTOMER Company SR-.
454 (trimethylolpropane ethylene oxide modified triacrylate), Aronix M-305 (pentaerythritol triacrylate) manufactured by Toagosei Co., Ltd., NK ester A-TM manufactured by Shin Nakamura Chemical Co., Ltd.
MT (pentaerythritol tetraacrylate), S
SR-355 manufactured by ARTOMER Company
(Ditrimethylolpropane tetraacrylate) and the like.

Further, among the methacrylates having two or more methacryloyl groups, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate. , Neopentyl glycol dimethacrylate, glycerol dimethacrylate, bisphenol A dimethacrylate, ethylene oxide modified bisphenol A dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate and the like. Examples of commercially available methacrylates are BD (1,3-butylene glycol dimethacrylate) manufactured by Mitsubishi Rayon Co., Ltd., ED (ethylene glycol dimethacrylate) manufactured by Mitsubishi Rayon Co., Ltd., and Daihachi Chemical Industry Co., Ltd. as dimethacrylate type. Examples include MR-N (neopentyl glycol dimethacrylate) manufactured by Nippon Oil & Fats Co., Ltd., Blemmer GMR (glycerol dimethacrylate) manufactured by NOF CORPORATION, and the like. NK Ester TMPT (Trimethylolpropane Trimethacrylate), SARTOMER
SR-367 (pentaerythritol tetramethacrylate) manufactured by Company is mentioned.

A compound (a1) having a primary amino group directly bonded to a tertiary alkyl is reacted with a compound (a2) having two or more unsaturated double bonds to form two secondary amino groups. The reaction temperature when synthesizing the amino compound (A) contained above is preferably 50 to 200 ° C., but other side reactions are unlikely to occur, and therefore 50 to 150 ° C.
Is desirable. As the ratio of these used in this reaction, the reaction activity is high, and the compound (a1) having a primary amino group directly linked to a free tertiary alkyl does not remain, so that The molar ratio (n _a2 ) / (n _a1 ) of the unsaturated double bond in the compound (a2) having two or more unsaturated double bonds to the amino group in the compound (a1) having a primary amino group is 0. The range of 8 to 1.2 is desirable, and more desirably 0.95 to 1.0.
The range is 5.

Polyol compound (A2) used in the present invention
Is not particularly limited, for example, various polyester polyols and polyester polyethers,
Among them, polyester polyol is preferable.

As the polyester polyol, any of various polyester polyols can be used and is not particularly limited. For example, castor oil; an alkylene oxide adduct of castor oil, an epoxidized product of castor oil, a halide of castor oil, and castor oil as raw materials. Castor oil derivative such as transesterified product with polyhydric alcohol or hydroxyl group-containing epoxy resin; castor oil is transesterified with hydroxyl group-containing compound such as polyol at 200 to 250 ° C. in the presence of a basic catalyst such as lithium hydroxide. A castor oil derivative having a molecular weight of 300 to 700, which is obtained by reacting a rosin having a molecular weight of 300 to 700, a polymerized rosin such as hydrogenated rosin and dimer rosin, with a terminal of the castor oil or a castor oil derivative. Derivative; the castor oil The end of castor oil derivatives, molecular weight 400 to 900 having a carboxyl group or a hydroxyl group at a terminal obtained by reacting a compound having a carboxyl group
Polyester resin having a molecular weight of 400 to 900 and having a hydroxyl group at the terminal obtained by esterification of the following polybasic acid and polyhydric alcohol.

As the compound having a carboxyl group, a monobasic acid can be used, but a polybasic acid is preferably used. Examples of the polybasic acid include tetrachlorophthalic anhydride, het acid, tetrabromophthalic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic acid, fumaric acid, malonic acid. , Succinic acid, glutamic acid, adipic acid, pimelic acid, sebacic acid, trimellitic acid, maleic anhydride and the like.

Examples of monobasic acids include propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid. Saturated monobasic acids such as acids; Unsaturated monobasic acids such as oleic acid, linoleic acid, linolenic acid; benzoic acid, toleyric acid, t-butylbenzoic acid, chloro or bromobenzoic acid, aminated benzoic acid, hydroxybenzoic acid And the like, such as aromatic monobasic acids. These monobasic acids are preferably used in combination with polybasic acids rather than used alone.

Molecular weight 400-90 having a hydroxyl group at the terminal
Examples of the polyhydric alcohol used to obtain the polyester resin of 0 include ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, pentanediol, hexanediol, neopentyl guicol, and hydrogenated bisphenol. , Glycerin, pentaerythritol, trimethylolpropane, trimethylolethane and the like.

The polyisocyanate compound (B) used in the present invention is an amino compound (A) having two or more amino groups.
1) and a curing agent for the polyol compound (A2), and various aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates or a mixture thereof can be used.

Specific examples of the polyisocyanate compound (B) include aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), and alicyclic polyisocyanates such as isophorone diisocyanate (IPDI) and hydrogenated diphenylmethane. Diisocyanate (H ₁₂ MDI), cyclohexane diisocyanate (H ₆ XDI) and the like are aromatic polyisocyanates such as tolylene diisocyanate (T
DI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (crude MDI), and the like, and further, dimer compounds of these polyisocyanates and trimers of these polyisocyanates. Examples thereof include compounds having a buret structure or an isocyanurate structure, polyol adducts of these polyisocyanates, polycarbonate-modified isocyanates obtained by modifying these polyisocyanates with CO ₂ or the like, and various other modified products.

Among these polyisocyanates, when the yellowing resistance is not particularly emphasized, the crude MDI and the polyol adduct of MDI, which are inexpensive, have excellent coating workability, curability, and physical properties of the cured coating film, MDI to CO ₂
Aromatic polyisocyanates such as polycarbonate-modified MDI modified with, for example, are preferable. On the other hand, when high weather resistance such as outdoors is required, aliphatic polyisocyanates and alicyclic polyisocyanates are preferable.

In the present invention, when the amino compound (A1) and the polyol compound (A2) are used in combination, the weight ratio (A1) / (A2) of these compounds is
Since a cured coating film with excellent corrosion resistance and toughness can be obtained, 2
It is preferably 0/80 to 90/10, and particularly preferably 20/80 to 60/40.

In the present invention, the amino compound (A1) and the polyisocyanate compound (B) are combined, or the amino compound (A1) and the polyol compound (A2) are combined.
And a polyisocyanate compound (B) are combined,
Although each is used, a cured coating film having good curability and excellent corrosion resistance and toughness can be obtained. Therefore, in the case of the former, the ratio of these used is, in the case of the former, a polyamine based on the secondary amino group in the amino compound (A1). Isocyanate compound (B)
Equivalent ratio of isocyanate groups in (NCO) / (NH)
However, in the latter case, the equivalent ratio (NCO) / (NH + OH) of the isocyanate groups in the polyisocyanate compound (B) to the total of the amino groups in the amino compound (A1) and the hydroxyl groups in the polyol compound (A2) is Each,
The range of 0.7 to 1.3 is preferable, and 0.8 is especially preferable.
A range of up to 1.2 is particularly preferred.

The two-component curable coating composition of the present invention uses the two-component curable resin composition of the present invention as it is as a two-component curable coating composition, or the amino compound (A1) and polyisocyanate compound (B). Or an amino compound (A1), a polyol compound (A2) and a polyisocyanate compound (B), and a curing catalyst for organic metal compounds such as dibutyltin dilaurate and dibutyltin diacetate and various amines; azo pigments , Copper phthalocyanine-based pigments, red iron oxide, yellow lead, titanium oxide, zinc white, carbon black and other organic or inorganic color pigments; red lead, lead white,
Basic lead chromate, basic lead sulfate, zinc chromate,
Anticorrosive pigments such as zinc dust and MIO; extender pigments such as precipitated barium sulfate, clay, silica, talc, calcium carbonate, mica; various auxiliaries such as leveling agents, hygroscopic agents, silane-based or titanate-based coupling agents, etc. Can be obtained by appropriately adding

In the two-component curable coating material of the present invention, plasticizer components such as dioctyl phthalate, asphalt and tar, petroleum-based diluents such as heavy oil A and aromatic hydrocarbons also impair the effects of the present invention. It can be added in the range not present.

When coating the two-component curable coating material of the present invention, it is preferable to heat the coating material at room temperature or at 50 to 80 ° C. and spray-coat it. It is preferable to use it.

The two-component curable coating material of the present invention is excellent in adhesion to the coating material, especially to metal, and can form a coating film having a thickness of 0.005 to 10 mm on the metal surface. In order to exhibit the original performance, a thick coating film corresponding thereto can be formed.

[0033]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention should not be limited to these.

Example 1 1 having a thermometer, a condenser and a nitrogen gas inlet tube
A liter 4-necked flask was charged with 336 parts by weight of trimethylolpropane triacrylate (Kyoeisha Chemical Co., Ltd., light acrylate TMP-A) and a tertiary alkylamine having an average carbon number of 12 (Rohm and Haas Japan Co., Ltd.). Manufactured by PRIMENE @ 81-R) 664 parts by weight and reacted at 90 ° C. for 9 hours, and the disappearance of the peak due to the double bond was confirmed by IR measurement, and the molecular weight was 881 and the active hydrogen equivalent was the end point of the reaction. An amino compound (A1-1) having three secondary amino groups and having a viscosity (Gardner: 25 ° C.) QR of 294 g / equivalent was obtained.

The obtained amino compound (A1-1) 100
0 g and crude MDI (polyphenylmethane polyisocyanate) 426 g [second amino compound (A1-1)]
A two-component curable coating composition (P1) comprising the two-component curable resin composition of the present invention was obtained by mixing and stirring a primary amino group and an equivalent ratio of the isocyanate group of crude MDI of 1.0].

Example 2 1 having a thermometer, a condenser and a nitrogen gas introducing tube
In a 4-liter four-necked flask, 302 parts by weight of 1,6-hexanediol diacrylate (Kyoeisha Chemical Co., Ltd. light ester 1,6HX) and a tertiary alkylamine having an average carbon number of 12 (Rohm and Haas Japan (PRIMENE @ 81-R manufactured by Co., Ltd.) 698 parts by weight was added, and the mixture was reacted at 90 ° C. for 9 hours, and the disappearance of the peak due to the double bond was confirmed by IR measurement, and the molecular weight of 616, activity was determined as the end point of the reaction. An amino compound (A1-2) having two secondary amino groups and having a hydrogen equivalent of 308 g / equivalent and a viscosity (Gardner: 25 ° C.) O was obtained.

Obtained amino compound (A1-2) 100
0 g and crude MDI447 g [amino compound (A1-
The secondary amino group of 2) and the equivalent ratio of the isocyanate group of crude MDI of 1.0] are mixed and stirred to obtain a two-component curable coating composition (P2) comprising the two-component curable resin composition of the present invention. It was

Example 3 1 having a thermometer, a condenser and a nitrogen gas introducing tube
In a liter four-necked flask, 366 parts by weight of trimethylolpropane trimethacrylate (Kyoeisha Chemical Co., Ltd. light ester TMP) and a tertiary alkylamine having an average carbon number of 12 (PRIMENE @ manufactured by Rohm and Haas Japan Co., Ltd.) 81-R) 634 parts by weight was added and reacted at 90 ° C. for 9 hours, and the disappearance of the peak due to the double bond was confirmed by IR measurement, and the molecular weight was 923 and active hydrogen equivalent was 308 g / equivalent as the end point of the reaction. Then, an ammono compound (A1-3) having three secondary amino groups and having a viscosity (25 ° C.) RS was obtained.

Obtained amino compound (A1-3) 100
0 g and crude MDI 406 g [amino compound (A1-
The secondary amino group of 3) and an equivalent ratio of the isocyanate group of crude MDI of 1.0] are mixed and stirred to obtain a two-component curable coating composition (P3) comprising the two-component curable resin composition of the present invention. It was

Example 4 1 having a thermometer, a condenser and a nitrogen gas introducing tube
In a liter four-necked flask, 234 parts by weight of trimethylolpropane triacrylate (Kyoeisha Chemical Co., Ltd. light acrylate TMP-A) and a tertiary alkylamine having an average carbon number of 18 (made by Rohm and Haas Japan Co., Ltd. PRIMONE @ JM-T) 766 parts by weight was added, and the mixture was reacted at 90 ° C. for 9 hours, the disappearance of the peak due to the double bond was confirmed by IR measurement, and the end point of the reaction was molecular weight 1271, active hydrogen equivalent 424 g. An amino compound (A1-4) having three secondary amino groups and having an equivalent weight and viscosity (Gardner: 25 ° C.) W-X was obtained.

Obtained amino compound (A1-4) 100
0 g and crude MDI 295 g [amino compound (A1-
The secondary amino group of 4) and the equivalent ratio of the isocyanate group of crude MDI of 1.0] are mixed and stirred to obtain a two-component curable coating composition (P4) comprising the two-component curable resin composition of the present invention. It was

Example 5 500 g of the amino compound (A1-1) obtained in Example 1
And 500 g of castor oil and 374 g of crude MDI [the total of the secondary amino groups of the amino compound (A1-1) and the hydroxyl groups of castor oil, and the equivalent ratio of the isocyanate groups of crude MDI of 1.0] were mixed and stirred to give a mixture of the present invention. A two-component curable coating material (P5) composed of the two-component curable resin composition was obtained.

Example 6 300 g of the amino compound (A1-1) obtained in Example 1
And 700 g of castor oil and 354 g of crude MDI [the total of the secondary amino groups of the amino compound (A1-1) and the hydroxyl groups of castor oil, and the equivalent ratio of the isocyanate groups of crude MDI of 1.0] were mixed and stirred to give a mixture of the present invention. A two-component curable coating material (P6) composed of the two-component curable resin composition was obtained.

Example 7 1 having a thermometer, a condenser and a nitrogen gas introducing tube
To a liter four-necked flask, 800 parts by weight of castor oil, 200 parts by weight of trimethylolpropane and 0.02 part by weight of lithium hydroxide were added, and transesterified at 250 ° C. for 1 hour to give a molecular weight of 730 and a hydroxyl value. 367 mgK
A castor oil derivative (A2-1) having OH / g, an acid value of 2.0 mgKOH / g, and a viscosity (Gardner: 25 ° C.) V was obtained.

The amino compound (A1-
1) 500 g and the castor oil derivative (A2-1) 500
g and crude MDI 513 g [amino compound (A1-
The two-part curable resin composition of the present invention, which is obtained by mixing and stirring the total of the secondary amino group of 1) and the hydroxyl group of the castor oil derivative (A2-1) and the equivalent ratio of the isocyanate group of crude MDI of 1.0]. A two-component curable coating material (P7) was obtained.

Example 8 500 g of the amino compound (A1-4) obtained in Example 4
And castor oil 500 g and crude MDI 309 g [the secondary amino group of the amino compound (A1-4) and the total hydroxyl group of castor oil, and the equivalent ratio of the isocyanate group of crude MDI 1.0] were mixed and stirred, A two-component curable coating material (P8) composed of the two-component curable resin composition was obtained.

Comparative Example 1 1000 g of castor oil and 323 g of crude MDI (equivalent ratio of hydroxyl group of castor oil to isocyanate group of crude MDI of 1.0) were mixed and stirred to prepare a two-part curable resin composition for comparison and control. A curable coating material (p1) was obtained.

Comparative Example 2 Castor oil derivative (A2-1) 100 obtained in Example 7
0 g and crude MDI 818 g [castor oil derivative (A2
The hydroxyl group of -1) and the equivalent ratio of the isocyanate group of crude MDI of 1.0] were mixed and stirred to obtain a two-component curable coating composition (p2) composed of a two-component curable resin composition for comparison.

Comparative Example 3 1 having a thermometer, a condenser and a nitrogen gas introducing tube
600 parts by weight of castor oil, 200 parts by weight of bisphenol A type epoxy resin having an epoxy equivalent of 480, and 0.08 parts by weight of lithium hydroxide were added to a liter four-necked flask and reacted at 220 ° C. for 3 hours. Then, 200 parts by weight of hydrogenated rosin was added and reacted to obtain a molecular weight of 720, a hydroxyl value of 143 mgKOH / g, and an acid value of 26.0 mgKOH /.
g, viscosity (Gardner: 25 ° C.) V-W 2 castor oil derivative (A2-2) was obtained.

Obtained castor oil derivative (A2-2) 10
00g and crude MDI 318g [castor oil derivative (A
The hydroxyl group of 2-2) and an equivalent ratio of isocyanate groups of crude MDI of 1.0] were mixed and stirred to obtain a two-component curable coating composition (p3) made of a two-component curable resin composition for comparison. .

Comparative Example 4 1000 g of polyalkylene oxide polyol (DIOL-1000 manufactured by Mitsui Polyol Co.) and crude MDI2
50 g (equivalent ratio of hydroxyl group of polyalkylene oxide polyol and isocyanate group of crude MDI 1.0) was mixed and stirred to give a two-component curable coating composition (p4) composed of a two-component curable resin composition for comparison. Obtained.

Test Examples The following tests were conducted on the two-component curable coating materials (P1 to P8 and p1 to p4) obtained in Examples 1 to 8 and Comparative Examples 1 to 4. The results are shown in Tables 1 to 3.

(Test Method and Judgment Method) (1) Gel Time Test: Time (minutes) until 200 μl of each two-component curable coating material is weighed and stirred with a glass rod and the poly cup does not flow even if tilted. Was measured and used as gel time.

(2) Finger touch test: On a sandblasted steel plate (thickness of 75 × 150 × 3.2 mm) at 25 ° C., 22.5 g of a two-component curable coating material well stirred with a glass rod was coated with a bar coater to a film thickness of 2 mm. The time (minutes) until the coating film does not cause stringing when the sample was applied as described above after being brought into contact with the coating film with fingers wearing protective gloves and then separated was taken as the finger touch time.

(3) Curability test: 22.5 g of a two-component curable coating material well stirred with a glass rod on a sandblasted steel plate (thickness of 75 × 150 × 3.2 mm) at 25 ° C. to a film thickness of 2 mm with a bar coater. After being strongly pressed against the coating film with a finger with protective gloves, the curing time is defined as the time when no dents or finger marks on the coating film can be formed.

(4) Appearance of coating film: Sandblasted steel plate (7
(5 × 150 × 3.2 mm thick), and 22.5 g of a two-component curable coating material that was well stirred with a glass rod was coated with a bar coater to give a film thickness of 2
A sample coated so as to have a thickness of 8 mm and cured by standing at 25 ° C. for 1 week was visually evaluated, and a sample having a smooth coating surface and gloss was regarded as good.

(5) Pencil hardness test: On a sandblasted steel plate (75 × 150 × 3.2 mm thick), 22.5 g of a two-component curable coating material well stirred with a glass rod was applied with a bar coater to a film thickness of 2 mm. The pencil hardness was measured according to JIS-K5400 using a sample which was applied and allowed to stand and cure at 25 ° C. for 1 week. The load was 1 kg.

(6) Hardness measurement: Sandblasted steel plate (7
(5 × 150 × 3.2 mm thick), and 22.5 g of a two-component curable coating material that was well stirred with a glass rod was coated with a bar coater to give a film thickness of 2
The sample was applied so as to have a thickness of mm and allowed to stand and cure at 25 ° C. for 1 week, and the sample was measured by a JIS-A Shore hardness meter-D.

(7) Water resistance test: On a sandblasted steel plate (75 × 150 × 3.2 mm thick), 22.5 g of a two-component curable coating, which was well stirred with a glass rod, was applied with a bar coater to a film thickness of 2 mm. The sample, which was applied and allowed to stand and cure at 25 ° C. for 1 week, was immersed in seawater at a depth of 20 cm and left for 2 months, and the state of the coating film was visually observed and evaluated according to the following criteria. ○: No blister, tear, or peeling. Δ: Blisters are recognized. X: What is seen to be broken or peeled.

(8) Alkali resistance test: On a sandblasted steel plate (75 × 150 × 3.2 mm thick), 22.5 g of a two-component curable coating, which was well stirred with a glass rod, was applied with a bar coater to a film thickness of 2 mm. The sample, which was applied and allowed to stand and cure at 25 ° C. for 1 week, was visually observed for the state of the coating film after being immersed in an aqueous sodium hydroxide solution having a concentration of 5% by weight, and evaluated according to the following criteria. ○: No blister, tear, or peeling. Δ: Blisters are recognized. X: What is seen to be broken or peeled.

(9) Impact resistance test: On a sandblasted steel plate (75 × 150 × 3.2 mm thick), 22.5 g of a two-component curable coating material that was well stirred with a glass rod was coated with a bar coater to a film thickness of 2 mm. The sample was left standing at 20 ° C. for 1 day after being left to cure for 1 week at 25 ° C., and then a steel ball (diameter: 10.7 c
m) was dropped and cracking and peeling of the coating film were evaluated according to the following criteria. ◯: No crack or peeling is observed in the coating film. Δ: A slight crack or peeling of the coating film is recognized. X: The coating film has cracks or peeling of 1 cm or more.

(10) Cathodic delamination resistance: 22.5 g of a two-component curable coating material well stirred with a glass rod on a sandblasted steel plate (thickness of 75 × 150 × 3.2 mm) with a bar coater to a film thickness of 2 mm. The sample is applied to and cured by standing at 25 ° C. for 1 week, and the electrode is connected to serve as a cathode. This sample was immersed in a 5 wt% saline solution in which a metal anode was set,
The surface state of the coating film was observed after 1 month at 20 ° C. after applying a current of 1.5 volts and evaluated according to the following criteria. ◯: No peeling or swelling of the coating film. Δ: Peeling or swelling of the coating film is slightly observed. X: Peeling or swelling was observed.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

The two-component curable resin composition of the present invention and the two-component curable coating composition using the same are excellent in adhesion to materials, particularly metal materials, have fast drying property, water resistance, alkali resistance, and cathode. It has excellent corrosion resistance such as peelability and good impact resistance.

Continued front page    F-term (reference) 4J034 BA02 BA08 CA14 CA15 CA16                       CA17 CB02 CB03 CB04 CB05                       CB07 CC03 CC08 CC26 CC45                       CC52 CC62 DA01 DB03 DB07                       DF01 EA12 HA01 HA02 HA07                       HC03 HC12 HC17 HC22 HC34                       HC35 HC46 HC52 HC61 HC64                       HC67 HC71 HC73 KA01 KB02                       KC17 KD12 KE02 QB13 RA07                 4J038 DG051 DG061 DG101 DG111                       DG131 GA06 NA03 NA04                       NA11

Claims (12)

[Claims] 1. A secondary amino group obtained by reacting a compound (a1) having a primary amino group directly bonded to a tertiary alkyl with a compound (a2) having two or more unsaturated double bonds. A two-component curable resin composition comprising an amino compound (A1) having two or more of the above and an polyisocyanate compound (B) as essential components. 2. The two-part curable resin according to claim 1, wherein the compound (a1) having a primary amino group directly linked to a tertiary alkyl has a tertiary alkyl group having 4 to 22 carbon atoms. Composition. 3. The two-part curable resin according to claim 2, wherein the compound (a2) having two or more unsaturated double bonds is a (meth) acrylate having 2 to 4 (meth) acryloyl groups. Composition. 4. The two-component curable resin composition according to claim 1, wherein the amino compound (A1) having two or more secondary amino groups is an amino compound having 2 to 6 secondary amino groups. . 5. A secondary amino group obtained by reacting a compound (a1) having a primary amino group directly bonded to a tertiary alkyl with a compound (a2) having two or more unsaturated double bonds. A two-component curable resin composition comprising an amino compound (A1) having two or more of the above, a polyol compound (A2), and a polyisocyanate compound (B) as essential components. 6. The two-part curable resin composition according to claim 5, wherein the polyol compound (A2) is a polyester polyol. 7. The two-component curable resin composition according to claim 5, wherein the polyol compound (A2) is one or more polyols selected from the group consisting of castor oil, castor oil fatty acid and castor oil modified polyol. 8. The compound according to claim 5, 6 or 7, wherein the tertiary alkyl group of the compound (a1) having a primary amino group directly linked to a tertiary alkyl has 4 to 22 carbon atoms.
Liquid curable resin composition. 9. The seven-component curable resin according to claim 8, wherein the compound (a2) having two or more unsaturated double bonds is a (meth) acrylate having 2 to 4 (meth) acryloyl groups. Composition. 10. The two-component curing method according to claim 5, wherein the amino compound (A1) having two or more secondary amino groups is an amino compound having 2 to 6 secondary amino groups. Type resin composition. 11. The weight ratio (A1) / (A2) of the amino compound (A1) and the polyol compound (A2) is 2/8.
The two-part curable resin composition according to any one of claims 5 to 10, wherein the two-component curable resin composition is from 9 to 1. 12. A two-component curable coating material comprising the two-component curable resin composition according to any one of claims 1 to 11.