JP2018030997A - Urethan-modified epoxy resin and one-pack lacquer type paint - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an urethan-modified epoxy resin which is excellent in rust preventive property, primary adhesion and water resistant adhesion possessed by a modified epoxy resin and can materialize high solids of a paint.SOLUTION: The urethan-modified epoxy resin is provided which is a reactant of an amine-modified epoxy resin (A) composed of an epoxy resin (a1) containing a bisphenol type epoxy resin (a1-1) and amines (a2), and a polyisocyanate (B), and in which an epoxy group concentration of the component (a1) is 1.2×10to 4.5×10eq/g, the component (a2) contains 0.1-50 wt.% of alkanol amines (a2-1), and an amine value of the component (A) is 40 to 90 mgKOH/g.SELECTED DRAWING: None

Description

  The present invention relates to a urethane-modified epoxy resin and a one-component lacquer-type paint.

  The bisphenol A type epoxy resin obtained by reacting bisphenol A with epichlorohydrin has excellent rust prevention, adhesion, chemical resistance, etc. due to the reactivity of the epoxy group and hydroxyl group in the resin. Therefore, it is widely used as a paint resin.

  By the way, since an epoxy resin generally does not have self-curing property, when the epoxy resin coating is cured at room temperature, it is used as a two-component reaction type coating in which a curing agent such as polyamine or polyamide is blended in the coating.

  However, two-component reactive paints must be mixed with a curing agent just before being applied to the substrate, which is inconvenient to handle and has various practical limitations in terms of pot life (pot life). Cheap. Therefore, there has been a strong demand for a one-pack, lacquer-type coating resin that can be dried at room temperature without blending a curing agent while maintaining adhesion as an epoxy resin, rust prevention, and the like.

  As a solution to this problem, for example, a coating resin containing a urethane-modified epoxy resin obtained by reacting a polyisocyanate compound with an epoxy resin obtained from a bisphenol-type epoxy resin and amines is known (Patent Literature). 1). Moreover, it is obtained by reacting a bisphenol type epoxy resin, a secondary alkanolamine and a C8 or higher alkylamine as a lacquer type coating resin excellent in long-term rust and corrosion resistance while maintaining high hardness. A reaction product of an amine-modified epoxy resin and a polyisocyanate compound is also known (Patent Document 2).

  By the way, in recent years, one-component, lacquer-type paints can be modified to reduce the solvent and achieve high solids (high solidification) while maintaining various properties such as rust prevention properties of the coating film. Development of an epoxy resin has been desired.

Japanese Patent Publication No. 6-89289 JP 2010-235919 A

  An object of the present invention is to solve the above-described problems, and to provide a urethane-modified epoxy resin that is excellent in rust prevention, primary adhesion, and water-resistant adhesion, and that can achieve high solidification of a paint.

  As a raw material, the present inventors react an amine-modified epoxy resin having a relatively high amine value with an epoxy resin having a predetermined epoxy group concentration and a predetermined amount of alkanolamines, and a polyisocyanate. It has been found that the above problems can be solved by the urethane-modified epoxy resin. That is, the present invention relates to the following urethane-modified epoxy resin and one-pack / lacquer type paint.

1. A reaction product of an epoxy resin (a1) containing a bisphenol-type epoxy resin (a1-1), an amine-modified epoxy resin (A) comprising an amine (a2), and a polyisocyanate (B),
The epoxy group concentration of the component (a1) is 1.2 × 10 ^{−3 to} 4.5 × 10 ⁻³ eq / g,
The component (a2) contains 0.1 to 50% by weight of alkanolamines (a2-1),
The amine value of the component (A) is 40 to 90 mgKOH / g,
Urethane modified epoxy resin.

2. The use ratio of the component (a1) and the component (a2) is {number of epoxy groups in the component (a1)} / {number of active hydrogens in the amino group of the component (a2)} = 100/120 to 100/80 Urethane modified epoxy resin.

3. The urethane-modified epoxy resin according to item 1 or 2, wherein the ratio of component (A) and component (B) is {number of isocyanate groups in (B) / number of hydroxyl groups in (A)} is 0.001 to 0.40. .

4). One-pack lacquer type paint using the urethane-modified epoxy resin according to any one of Items 1 to 3.

5. The one-component lacquer-type paint according to item 4, wherein the non-volatile content of the paint is 50% by weight or more.

  The urethane-modified epoxy resin of the present invention is a coating film by using, as a raw material, an amine-modified epoxy resin having a relatively high amine value using an epoxy resin having a predetermined number of epoxy groups and a predetermined amount of alkanolamines. While maintaining the hardness and flexibility of the coating, it is excellent in rust prevention, primary adhesion and water-resistant adhesion, and can achieve a high solid state coating. Moreover, since the one-component lacquer type paint obtained by using the urethane-modified epoxy resin of the present invention can reduce the solvent content, it is also suitable from the viewpoint of environmental suitability.

  The urethane-modified epoxy resin of the present invention comprises an amine-modified epoxy resin (a1) (hereinafter referred to as component (a1)) and an amine-modified epoxy resin (hereinafter referred to as component (a2)) composed of a predetermined amine (a2) (hereinafter referred to as component (a2)). A) (hereinafter referred to as component (A)) and polyisocyanate (B) (hereinafter referred to as component (B)).

  The component (a1) is an epoxy resin containing a bisphenol type epoxy resin (a1-1) (hereinafter referred to as the component (a1-1)).

  As the component (a1-1), various known bisphenol type epoxy resins can be used without any particular limitation. For example, a reaction product of bisphenols and a haloepoxide such as epichlorohydrin or β-methylepichlorohydrin can be mentioned. Bisphenols include a reaction product of phenol or 2,6-dihalophenol with aldehydes or ketones such as formaldehyde, acetaldehyde, acetone, acetophenone, cyclohexanone, benzophenone, an oxidation reaction product of dihydroxyphenyl sulfide with a peracid, And etherification reaction products of hydroquinones. Specific examples of bisphenols include 2,2-bis (4-hydroxyphenyl) propane (bisphenolΑ), bis (4-hydroxyphenyl) methane (bisphenol F), and the like, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferred from the viewpoint of rust prevention. These (a1-1) components are each used individually or in combination of 2 or more types as appropriate.

  The component (a1) includes other epoxy resins (a1-2) (hereinafter referred to as the component (a1-2)) other than (a1-1) as long as the rust prevention property of the coating film can be maintained. Good. Although it does not specifically limit as (a1-2) component, For example, an aliphatic epoxy resin, an aromatic epoxy resin, etc. are mentioned. These may be used alone or in combination of two or more.

  Although it does not specifically limit as an aliphatic epoxy resin, For example, resin containing the glycidyl ester of a long-chain aliphatic dibasic acid, the glycidyl ether of a long-chain aliphatic polyol, the glycidyl ether of a polyether polyol, etc. are mentioned. Examples of the long-chain aliphatic dibasic acid include sebacic acid, azelaic acid, dodecanoic acid, malonic acid, succinic acid, glutaric acid, adipic acid, 8,11-dimethyl-7,11-octadecadien-1,18 -Dicarboxylic acid, 7-ethyloctadecanedicarboxylic acid, 1,4-cyclohexenecarboxylic acid and the like. Examples of long-chain aliphatic polyols include 1,4-butanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decane. Diol etc. are mentioned. Examples of the polyether polyol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, Examples include tetrapropylene glycol, pentapropylene glycol, hexapropylene glycol, polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene glycol, and polybutylene glycol.

  Although it does not specifically limit as an aromatic epoxy resin, A cresol novolak type epoxy resin, a phenol novolak type epoxy resin, a triphenol methane type epoxy resin, a triphenol ethane type epoxy resin, a trisphenol type epoxy resin, a dicyclopentadiene type epoxy resin , Diphenyl ether type epoxy resin, biphenyl type epoxy resin and the like.

  In the present invention, in order to obtain the component (A) having a predetermined amine value, the final coating film has good rust prevention, primary adhesion, water-resistant adhesion, and also realizes high solidification. The epoxy group concentration of the component (a1) is an important parameter. The epoxy group concentration of the component (a1) is represented by the number of epoxy groups per gram in the component (a1). Hereinafter, the calculation method will be described by taking the (a1-1) component and the (a1-2) component as examples.

  When one type of component (a1-1) is used, the epoxy group concentration of component (a1) is calculated from (Equation 1) using the epoxy equivalent of component (a1-1).

(Formula 1)

  When one type of (a1-1) component and one type of (a1-2) component are used, the epoxy group concentration of the (a1) component is calculated from (Formula 2).

(Formula 2)

  When a plurality of components (a1-1) are used, the epoxy group concentration of the component (a1) is calculated from (Equation 3). Here, a plurality of (a1-1) components are represented as (a1-1-1), (a1-1-2),..., (A1-1-n).

(Formula 3)

(A1) an epoxy group concentration of the component, usually ^{1.2 × 10 -3 ~4.5 × 10 -3} eq / g. When the epoxy group concentration is lower than 1.2 × 10 ⁻³ eq / g, the amine value of the component (A) is lowered, and the rust prevention property of the coating film is lowered. Moreover, when an epoxy group density | concentration exceeds 4.5 * 10 < ^-3 > eq / g, the amine value of (A) component will become high and the water-proof adhesiveness and rust prevention property of a coating film will fall. From these viewpoints, it is preferably 1.5 × 10 ⁻³ to 4 × 10 ⁻³ eq / g.
Assuming that the epoxy group concentration of the component (a1) satisfies the above range, individual epoxy resins belonging to the component (a1) (for example, the component (a1-1), the component (a1-2), ( As for the epoxy group concentration of the component a1-1-1) etc., those outside the above range can be used freely.

  Component (a2) is an amine containing a predetermined amount of alkanolamines (a2-1) (hereinafter referred to as component (a2-1)) from the viewpoint of adhesion to the substrate.

  As the component (a2-1), various known alkanolamines can be used without particular limitation. For example, primary alkanolamines such as monoethanolamine and monoisopropanolamine; diethanolamine, diisopropanolamine, di-2-hydroxybutylamine, N-methylethanolamine, N-ethylethanolamine, N-benzylethanolamine and the like Tertiary alkanolamines such as secondary alkanolamines, triethanolamines, tripropanolamines and the like can be mentioned. Among these, from the viewpoint of adhesion to the substrate, primary alkanolamines and / or secondary alkanolamines are preferable, and monoethanolamine and / or diethanolamine are more preferable.

  Content of (a2-1) component is 0.1 to 50 weight% in (a2) component, Preferably it is 5 to 30 weight%. When the content is less than 0.1% by weight, the primary adhesion and rust resistance of the coating film are inferior, and when it exceeds 50% by weight, the water adhesion and rust resistance of the coating film are inferior.

  The component (a2) may include non-alkanolamines (a2-2) (hereinafter referred to as (a2-2) component). The component (a2-2) is not particularly limited, and examples thereof include ethylamine, propylamine, butylamine, hexylamine, octylamine, laurylamine, stearylamine, n-palmitylamine, oleylamine, 2-ethylhexylamine and the like. Primary aliphatic monoamines; secondary aliphatic monoamines such as diethylamine, dipropylamine, dibutylamine; ethylenediamine, propylenediamine, hexamethylenediamine, 2,2,4-trimethylhexanediamine, 2,4,4-trimethylhexane Aliphatic diamines such as diamine and isophoronediamine; aromatic amines such as toluidine, xylidine, cumidine (isopropylaniline), hexylaniline, nonylaniline, dodecylaniline; cyclopentylamine, cycline Hexylamine, alicyclic amines such as Noruboniruamin; benzylamine, aromatic nucleus-substituted aliphatic amines such as phenethylamine, such as a dimer diamine. These amines are used individually or in combination of 2 or more types as appropriate. Among these, from the viewpoint of water-resistant adhesion of the coating film, aliphatic amines are preferable, and primary aliphatic monoamines and / or secondary aliphatic monoamines are more preferable.

  Although the usage-amount of a (a2-2) component is not specifically limited, It is about 50 to 99.9 weight%, Preferably it is about 70 to 95 weight%. When the content is less than 50% by weight, the water adhesion and rust resistance of the coating film are inferior. When the content exceeds 99.9% by weight, the primary adhesion and rust resistance of the coating film are inferior.

  As the use ratio of the component (a1) and the component (a2), {the number of epoxy groups in the component (a1)} / {the number of active hydrogens in the amino group of the component (a2)} is about 100/120 to 100/80, preferably It is about 100/110 to 100/90, more preferably about 100/105 to 100/95. By setting it as the said range, (a1) component and (a2) component are consumed, and it becomes easy to obtain (A) component which has a predetermined amine value.

The number of epoxy groups in the component (a1) is a value obtained by dividing the charged weight of the component (a1) by the epoxy equivalent of the component (a1). When there are a plurality of components (a1), the number of epoxy groups is calculated from (Equation 4).

(Formula 4)

The number of active hydrogens in the amino group of the component (a2) is a value obtained by dividing the charged weight of the component (a2) by the amine equivalent of the component (a2). When there are a plurality of components (a2), the number of active hydrogens is calculated from (Equation 5).

(Formula 5)

  The component (A) is produced by reacting the components (a1-1) and (a2-1), and if necessary, the components (a1-2) and (a2-2) under the following conditions. Can do. Although manufacturing conditions are not specifically limited, Reaction temperature is about 50-250 degreeC normally, Preferably it is about 80-150 degreeC. The reaction time is not particularly limited because it depends on the reaction temperature, but is usually about 3 to 10 hours, preferably 3 to 6 hours from the viewpoint of production efficiency.

  As the physical properties of the component (A), the amine value is important in terms of satisfying the high solidification of the paint and the rust prevention, primary adhesion and water-resistant adhesion of the coating film. The amine value is measured according to JIS K-7237. (A) As an amine value of a component, it is 40-90 mgKOH / g, Preferably it is 50-85 mgKOH / g, More preferably, it is 60-80 mgKOH / g. When the amine value is less than 40 mgKOH / g, the rust prevention property of the coating film tends to be lowered, and when it exceeds 90 mgKOH / g, the water-resistant adhesion property of the coating film tends to be lowered.

  (B) It does not specifically limit as a component, Various well-known things can be used. For example, aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates and the like may be mentioned, and these may be used alone or in combination of two or more.

  Examples of aromatic polyisocyanates include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetra Examples thereof include alkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, orthotoluidine diisocyanate, and polyphenyl polyisocyanate. Two or more of these can be used in combination.

  Examples of the aliphatic polyisocyanates include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. . Two or more of these can be used in combination.

  Examples of the alicyclic polyisocyanates include cyclohexane-1,4-diisocyanate, xylylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, and isophorone diisocyanate. Etc. Two or more of these can be used in combination.

  In the production of the urethane-modified epoxy resin of the present invention, the amount of the component (A) and the component (B) used is not particularly limited, but usually {number of isocyanate groups in the component (B)} / {number of hydroxyl groups in the component (A) } Is about 0.001 to 0.4, preferably about 0.005 to 0.3, and more preferably about 0.01 to 0.2. When it is 0.001 or more, the molecular weight of the urethane-modified epoxy resin obtained is appropriately high, and it is suitable as a resin for a one-pack / lacquer type paint that can be dried at room temperature. On the other hand, if it is 0.4 or less, an excessive increase in the molecular weight can be suppressed, which is suitable as a high solid paint.

  The number of hydroxyl groups in component (A) is the sum of the number of hydroxyl groups in component (a1) and the number of hydroxyl groups in component (a2).

  (I): The number of hydroxyl groups of the component (a1) is calculated by multiplying the charged molar amount of the component (a1) by the number of hydroxyl groups per molecule including the hydroxyl group generated when the epoxy group of the component (a1) is opened. it can. When the component (a1) includes a plurality of components, the number of hydroxyl groups in the component (a1) is the total number of hydroxyl groups in each component.

  (Ii): The number of hydroxyl groups in the component (a2) can be calculated by multiplying the charged molar amount of the component (a2) by the number of hydroxyl groups per molecule of the component (a2). When the component (a2) includes a plurality of components, the number of hydroxyl groups in the component (a2) is the total number of hydroxyl groups in each component.

  The number of isocyanate groups in component (B) is a value obtained by multiplying the charged molar amount of component (B) by the number of isocyanate groups per molecule of component (B). When there are a plurality of components (B), the number of isocyanate groups is the total number of isocyanate groups in each component.

  The reaction conditions for the component (A) and the component (B) are not particularly limited, but the reaction temperature is usually about 20 to 200 ° C, preferably about 50 to 150 ° C. Moreover, reaction time is about 3 to 10 hours normally, Preferably it is about 3 to 6 hours.

  In the reaction, a solvent can be used. For example, it has active hydrogen such as hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, and cellosolv acetates such as methyl cellosolve acetate and cellosolve acetate. Those that are not used are mentioned, and each can be used alone or in combination of two or more. In addition, after the production of the urethane-modified epoxy resin of the present invention, a solvent having active hydrogen such as cellosolves such as methyl cellosolve and ethyl cellosolve; alcohols such as isopropyl alcohol and n-butyl alcohol may be used as a diluent solvent. It can be used without.

  The weight average molecular weight (polystyrene conversion value by gel permeation chromatography) of the urethane-modified epoxy resin of the present invention is not particularly limited and is preferably in the range of about 10,000 to 100,000, more preferably 20,000. About 50,000. By setting the weight average molecular weight to 10,000 or more, it is possible to obtain a resin suitable for a one-pack lacquer type paint having a long-term high antirust property and water-resistant adhesion, and to 100,000 or less. As a result, it is easy to obtain a resin suitable for a high-solids type paint with suppressed viscosity increase.

The solid content concentration of the urethane-modified epoxy resin of the present invention is not particularly limited, and may be appropriately determined in consideration of the viscosity when formed into a paint, but is usually about 30 to 80% by weight. . Moreover, from the point of the handleability of the coating material obtained, the viscosity of the resin solution is adjusted to about R to Z ₇ (Gardner method, 25 ° C.).

  The one-component lacquer type paint (hereinafter referred to as the present paint) using the modified epoxy resin for urethane of the present invention will be described below. This paint can be used as a normal temperature drying paint, and is also suitable as a forced drying paint or a baking paint. Further, the present paint is not particularly limited to the object to be coated and uses, and can be widely applied. However, considering the performance such as rust prevention and adhesion of the coating film, it is suitable for undercoating.

  In the preparation of this paint, coloring pigments such as carbon black and titanium oxide, moisture-resistant pigments such as talc, calcium carbonate, and barium sulfate, rust preventive pigments such as aluminum phosphomolybdate and zinc phosphate, and the like can be appropriately blended. . Moreover, you may mix | blend suitably with hardeners, such as a melamine resin, urea resin, isocyanate, blocked isocyanate, various well-known solvents, and another additive as needed to this coating material. When this paint is made into a high solid, the nonvolatile content is usually 50% by weight or more, preferably about 55 to 80% by weight, more preferably 60 to 80% by weight.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Moreover, in each Example and a comparative example, a part or% is shown on a weight basis.

Example 1
In a reaction vessel equipped with a stirrer, a cooler, a thermometer and a nitrogen gas introduction pipe,
As component (a1-1), 150 g of jER1001 (Mitsubishi Chemical Corporation, epoxy equivalent 475 g / eq), 52 g of YD-128 (manufactured by Nippon Steel & Sumikin Co., Ltd., epoxy equivalent 189 g / eq) are charged, and component (a1) Was prepared. The epoxy group concentration of the component (a1) was 2.9 × 10 ⁻³ eq / g.
Next, 10 g of diethanolamine and 0.1 g of monoethanolamine were added as the component (a2-1), and 28 g of stearylamine and 18.5 g of 2-ethylhexylamine and 128 g of xylene were added as the component (a2-2). The reaction was carried out at 5 ° C. for 5 hours to obtain an amine-modified epoxy resin (A1) having an amine value of 70 mgKOH / g.
Next, 8.0 g of isophorone diisocyanate and 90 g of cyclohexanone were charged in the same reaction vessel as component (B), and these were reacted at 100 ° C. for 4 hours under a nitrogen stream to obtain a urethane-modified epoxy resin. The weight average molecular weight of the obtained epoxy resin was measured under the following conditions and shown in Table 1 (the same applies hereinafter).

[Weight average molecular weight of urethane-modified epoxy resin]
Apparatus: HLC-8220 (manufactured by Tosoh Corporation)
Column: TSKgel α-2500 × 1, α-3000 × 1
Separation solvent: DMF (containing 5 mmol / kg of LiBr),
Flow rate: 1ml / min
Temperature: 40 ° C
Standard: Polystyrene

Examples 2-6, Comparative Examples 1-4
The composition shown in Table 1 was synthesized according to the same method as in Example 1 to obtain a urethane-modified epoxy resin.

(Preparation of various paints and test coatings)
Mixtures having the compositions shown below were kneaded with a paint shaker to prepare a one-pack / lacquer type paint. The obtained paint was applied to a degreased dull steel plate (SPCC-SD, 0.8 × 70 × 150 mm) with a bar coater so that the film thickness after drying was 25 μm, and forced drying (80 ° C. × 20 Minutes) and then allowed to stand at room temperature (20 ° C., 60% RH) for 6 days to prepare a test coating film, which was subjected to the following tests.

(composition)
Each lacquer type coating resin obtained in Examples 1 to 6 and Comparative Examples 1 to 4 200 parts Titanium oxide 80 parts Carbon black 4 parts Sedimented barium sulfate 80 parts Aluminum phosphate anticorrosive pigment 16 parts Xylene 35 parts Cyclohexanone 35 copies

(Evaluation test of coating film)
(1) Pencil hardness Conforms to JIS K5600-5-4.

(2) Flexibility (bending test)
Each paint was applied by a bar coater on a chin-free steel plate (0.3 × 120 × 200 mm) so that the film thickness after drying was 25 μm, forcedly dried (80 ° C. × 20 minutes), (20 ° C., 60% RH) and left for 6 days to obtain a test piece. Each test piece was bent with a vise and the presence or absence of cracks in the bent portion was confirmed. Flexibility was evaluated by the number of plates (chin-free steel plates) sandwiched between them (2T indicates that there are two plates to be sandwiched and there is no cracking).

(3) Primary adhesion Performed according to JIS K5600-5-6, after coating, 23 ° C., 50% R.D. H. The cross-cut adhesion when the test coating film cured for 6 days under the above conditions was peeled was evaluated as 100.

(4) Water-resistant adhesion The cross-cut adhesion when the test coating film immersed in warm water of 40 ° C. for 10 days was peeled was evaluated as 100, according to JIS K5600-6-2.

(5) Rust prevention property It was carried out according to JIS K5600-7-9, and indicated by the cellophane tape peeling width (mm) after 10 days and 20 days of the salt spray test.
These evaluation results are shown in Table 1.

In Table 1, the numerical values relating to the component (a1), the component (a2), and the component (B) all indicate the charged parts by weight. Moreover, each symbol means the following.
jER1001 (manufactured by Mitsubishi Chemical Corporation, trade name “jER1001”, epoxy equivalent 475 g / eq, number of hydroxyl groups per molecule when the epoxy group is ring-opened: 4)
YD-128 (manufactured by Nippon Steel & Sumikin Co., Ltd., trade name “Epototo YD-128”, epoxy equivalent 189 g / eq, number of hydroxyl groups per molecule when epoxy group is ring-opened: 2)
YD-014 (manufactured by Nippon Steel & Sumikin Co., Ltd., trade name “Epototo YD-014”, epoxy equivalent 950 g / eq, number of hydroxyl groups per molecule when epoxy group is ring-opened: 6)
YDF-2001 (manufactured by Nippon Steel & Sumikin Co., Ltd., trade name “Epototo YDF-2001”, epoxy equivalent 470 g / eq, number of hydroxyl groups per molecule when the epoxy group is opened: 4)
YDF-170 (manufactured by Nippon Steel & Sumikin Co., Ltd., trade name “Epototo YDF-170”, epoxy equivalent 170 g / eq, number of hydroxyl groups per molecule when epoxy group is opened: 2)
SA: Stearylamine (amine equivalent: 134.75, number of hydroxyl groups per molecule: 0)
DEA: Diethanolamine (amine equivalent: 105, number of hydroxyl groups per molecule: 2)
MEA: monoethanolamine (amine equivalent: 30.5, number of hydroxyl groups per molecule: 1)
2EHA: 2-ethylhexylamine (amine equivalent: 64.6, number of hydroxyl groups per molecule: 0)
DBA: dibutylamine (amine equivalent: 129.2, number of hydroxyl groups per molecule: 0)
IPDI: Isophorone diisocyanate (manufactured by Sumitomo Bayer Urethane Co., Ltd., number of isocyanate groups per molecule: 2)
NV (%): solid content concentration Mw: weight average molecular weight Vis: Gardner viscosity (25 ° C.)

Claims (5)

A reaction product of an epoxy resin (a1) containing a bisphenol-type epoxy resin (a1-1), an amine-modified epoxy resin (A) comprising an amine (a2), and a polyisocyanate (B),
The epoxy group concentration of the component (a1) is 1.2 × 10 ^{−3 to} 4.5 × 10 ⁻³ eq / g,
The component (a2) contains 0.1 to 50% by weight of alkanolamines (a2-1),
The amine value of the component (A) is 40 to 90 mgKOH / g,
Urethane modified epoxy resin. The use ratio of the component (a1) and the component (a2) is {number of epoxy groups in the component (a1)} / {number of active hydrogens in the amino group of the component (a2)} = 100/120 to 100/80. 1. Urethane-modified epoxy resin. The urethane-modified epoxy resin according to claim 1 or 2, wherein the use ratio of the component (A) and the component (B) is {number of isocyanate groups of (B) / number of hydroxyl groups of (A)} = 0.001 to 0.4. . One-pack lacquer type paint containing the urethane-modified epoxy resin according to claim 1. The one-component lacquer-type paint having a nonvolatile content of 50% by weight or more.