JP2003165821A - Curable resin composition and paint - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition capable of suppressing development of blisters even in the existence of water, and to provide a paint using the same. <P>SOLUTION: The resin composition is obtained by mixing a curable composition comprising (A) a polyol and (B) a polyisocyanate compound with a (C) an amine compound having a dimmer acid skeleton. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel curable resin composition and a coating material containing the curable resin composition.

[0002]

Urethane resin compositions utilizing the curing reaction of polyols and polyisocyanates show excellent coating film properties in terms of durability, chemical resistance, extensibility, impact resistance, etc. It is widely used as a sealing material or adhesive in various fields such as the construction field and the civil engineering field. However, the urethane-based resin composition is
It has a property of generating carbon dioxide gas when water intervenes in the curing process. For example, when using a material in which moisture is taken in during storage, when performing a coating operation under high humidity conditions such as in summer, or when performing coating on a substrate containing a large amount of moisture, The carbon dioxide gas may swell the coating film, greatly impairing the physical properties and aesthetics of the coating film. Therefore, when using such a urethane-based resin composition, it is necessary to pay sufficient attention to storage management, weather conditions at the time of application, the condition of the base, etc., and the use is restricted in some cases. There was an occasion.

[0003]

As a method for solving such a problem, for example, Japanese Patent Laid-Open No. 62-148557.
In the publication, it is proposed to mix an inorganic hygroscopic material such as zeolite with the polyol component. However,
The method of this publication is effective when the material is stored, but there is a problem that foaming cannot always be suppressed when the polyol and the isocyanate compound are mixed at the time of use. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin composition capable of suppressing the occurrence of swelling even under conditions in which water is present, and a coating material using the same. It is a thing.

[0004]

In order to solve these problems, the inventor of the present invention has made earnest studies, and arrived at the idea of mixing a specific amine compound with a polyol or a polyisocyanate compound, and completed the present invention. did.

That is, the present invention has the following features. 1. A curable resin composition comprising (A) a polyol, (B) a polyisocyanate compound, and (C) an amine compound having a dimer acid skeleton. 2.1. A coating material containing the curable resin composition described in 1.

[0006]

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

(A) Polyol The polyol in the present invention may be any as long as it has reactivity with the polyisocyanate compound and can serve as a binder. Such polyols include, for example, polyether polyols, polyester polyols, acrylic polyols and the like. Each polyol is illustrated below.

(1) Polyether polyol As the polyether polyol, one of polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, glucose, sorbitol and sucrose. Or polyols obtained by adding one or more of propylene oxide, ethylene oxide, butylene oxide, styrene oxide and the like to two or more thereof; obtained by adding tetrahydrofuran to the polyhydric alcohol by ring-opening polymerization And polyoxytetramethylene polyols; and the like.

(2) Polyester Polyol Polyester polyol is one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, trimethylolpropane, pentaerythritol and other low molecular weight polyhydric alcohols. One or more, and one or two of glutaric acid, adipic acid, pimelic acid, speric acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, hydrogenated dimer acid or other low molecular weight dicarboxylic acid or oligomer acid. Condensation polymers with at least one species; ring-opening polymers of ring-opening esters such as propiolactone, caprolactone, valerolactone;
And other polyols.

(3) Acrylic polyol In the acrylic copolymer, as a monomer component thereof,
Β-hydroxyethyl (meth) acrylate, β-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, β-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (Meth) acrylic acid β-hydroxypentyl and other (meth) acrylic acid hydroxyalkyl esters; glycerin, trimethylolpropane and other polyhydric alcohol (meth) acrylic acid monoesters, N-methylol (meth) acrylamide and other hydroxyl groups A monoethylenically unsaturated monomer having 1 or more kinds selected from the following can be used.

(4) Other polyols Other than these, phenol resin polyol, epoxy polyol, polybutadiene polyol, polyisoprene polyol, polyester-polyether polyol, polymer polyol obtained by vinyl addition or dispersion of polymers such as acrylonitrile and styrene, and urea dispersion. Examples thereof include polyols and carbonate polyols.

(B) Polyisocyanate Compound The polyisocyanate compound may be any one that can be crosslinked and cured by reacting with the above-mentioned polyol. For example, tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (pure-MDI), polymeric MDI, xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), hydrogenated XDI, hydrogenated M
Allophanate conversion of isocyanate monomer such as DI,
Those which are derivatized by biuretization, dimerization (uretidione formation), trimerization (isocyanurate formation), adduct formation, carbodiimidization reaction, and the like, and a mixture thereof can be used. Particularly, considering the yellowing of the formed coating film, it is desirable to use an aliphatic or alicyclic polyisocyanate, or a mixture thereof.
Furthermore, these polyisocyanate compounds can also be used in the form of blocked isocyanates using a blocking agent such as alcohols, phenols, ε-caprolactam, oximes and active methylene compounds. The mixing ratio of these polyisocyanate compound and polyol is not particularly limited, but is usually 0.2 to NCO / OH equivalent ratio.
2.0, preferably 0.7 to 1.3.

(C) Amine compound having a dimer acid skeleton In the composition of the present invention, an amine compound having a (C) dimer acid skeleton (hereinafter referred to as a component (C)) is an essential component. In the present invention, by mixing the component (C), it is possible to suppress the occurrence of swelling even under the condition that water is present.

The component (C) is a compound in which an amino group is introduced into dimer acid, and in particular, one or more selected from dimer diamine and dimer acid polyamidoamine are preferable. Dimer acid is a polymerized fatty acid generally produced by a polymerization reaction of unsaturated fatty acids obtained from a drying oil or a semi-drying oil, and has a fatty acid dimer as an effective main component. Usually, the main component is a C ₃₆ dibasic acid or the like obtained by polymerization of a C ₁₈ unsaturated fatty acid. However, since this dimer acid is a polymerized fatty acid,
The structure is not a single but a mixture of acyclic, monocyclic and polycyclic and may contain a small amount of monomeric acid, trimeric acid and the like. As a fatty acid as a raw material of dimer acid,
Examples thereof include tall oil-based, soybean oil, coconut oil, castor oil, vegetable oil-based fatty acids such as rice bran oil, and beef tallow-based fatty acids.

The dimer diamine is obtained by converting the carboxyl group of the above dimer acid into an amino group. This dimer diamine can be obtained, for example, by amidating and reducing dimer acid. Dimer acid polyamidoamine is a polycondensation product of dimer acid and polyethylene polyamine and alkylene dicarboxylic acid or fatty acid. Here, as the polyethylene polyamine,
For example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and the like can be mentioned. Examples of the alkylenedicarboxylic acid include adipic acid, sebacic acid, dodecadioic acid and the like. Examples of the fatty acid include butyric acid, isobutyric acid, octylic acid, cyclohexanecarboxylic acid, propionic acid and the like.

The component (C) is usually mixed in a proportion of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the solid content of the (A) polyol. (C)
When the amount of the component is less than 0.01 part by weight, the formed coating film tends to swell. If the amount is more than 10 parts by weight, the weather resistance, discoloration resistance and the like tend to decrease.

In the composition of the present invention, a known and commonly used curing catalyst can be used in combination unless the effects of the present invention are impaired. Examples of such curing catalysts include tin carboxylates such as dibutyltin dilaurate, dibutyltin diacetate and dibutyltin dioctate; iron, cobalt,
Metal carboxylates such as naphthenic acid or octylate of metals such as manganese and zinc; aluminum compounds such as aluminum trisacetylacetate; tri-n-butylamine, N, N-dimethylcyclohexylamine,
Dimethylbenzylamine, dimethyloctylamine, diethanolamine, 1,4-diazabicyclo- (2,
2,2) -amine compounds such as octane; and the like.

The composition of the present invention may be used as it is as a clear composition or as a coloring composition. When used as a coloring composition, inorganic pigments such as titanium oxide, red iron oxide and oxide yellow; organic pigments such as phthalocyanine, quinacridone and azo pigments;
Metallic pigments such as aluminum powder and mica powder; aggregates such as colored silica sand and colored beads; and the like can be used.

In addition, the composition of the present invention may optionally contain
Various resins such as acrylic resin, silicon resin, alkyd resin, and epoxy resin can be mixed. In addition, for example, fillers, fibers, leveling agents, rheology control agents, defoaming agents, antioxidants, light stabilizers,
UV absorber, pigment dispersant, antiseptic, antifungal agent, antibacterial agent,
Known additives such as anti-algal agents can also be used.

The composition of the present invention can be used as a coating material, a sealing material, an adhesive agent and the like. Examples of applications include construction, building materials, civil engineering, woodworking, plastic products, metal products, non-ferrous metal products, and the like. The temperature at which the composition of the present invention is cured is not particularly limited and can be appropriately set depending on the application. The composition of the present invention can be normally cured even in a natural environment where it is difficult to adjust the temperature / humidity and the water content of the underlying substrate, and thus is particularly suitable for use as a room temperature curable paint.

[0021]

EXAMPLES Examples and comparative examples will be shown below to further clarify the characteristics of the present invention. The following raw materials were used in Examples and Comparative Examples.

Polyol 1: acrylic polyol resin, solid content 100% by weight, hydroxyl value 100 KOHmg /
g, average molecular weight 2500-Polyol 2: dimer acid diol resin, solid content 10
0% by weight, hydroxyl value 200 KOHmg / g, average molecular weight 550-Polyol 3: epoxy polyol resin, solid content 10
0 wt%, hydroxyl value 300 KOHmg / g, average molecular weight 5000-Polyisocyanate compound: hexamethylene diisocyanate derivative, NCO content 24 wt% -Compound 1: Dimer diamine (50 wt% mineral spirit solution) -Compound 2: Triethylenediamine ( 50% by weight mineral spirit solution) -Compound 3: dibutyltin dilaurate (1% by weight mineral spirit solution)

Blistering resistance test 1 Standard mortar with a water content of 15% (70 × 70 × 20 mm)
The back surface and the side surface of (1) were completely sealed with an epoxy resin to prepare a test base material. Next, the above raw materials were mixed at the ratio shown in Table 1 to prepare a resin composition. The raw materials were mixed at a temperature of 20 ° C. and a relative humidity of 65%. The obtained resin composition was applied to the surface of the test substrate at a thickness of 1 mm and cured at a temperature of 20 ° C and a relative humidity of 65% for 7 days, and then immersed in water (20 ° C) for 18 hours → -20 ° C. A heating / cooling repeating test in which one cycle consists of 3 hours → 80 ° C. and 3 hours was performed 30 cycles in total. The surface condition of the coating film after the test was visually observed, and the evaluation was made by ◯ when no swelling was observed, Δ when slightly swelling was observed, and x when clearly swelling was observed.

Blistering resistance test 2 A resin composition was prepared by mixing the above raw materials in the ratio shown in Table 1 at a temperature of 30 ° C. and a relative humidity of 95%. Then, the obtained resin composition was applied to a slate plate (300 × 30).
(0 × 6 mm) with a thickness of 1 mm and then cured for 24 hours. Coating and curing are at a temperature of 30 ℃ and relative humidity of 95.
% Went down. The surface state of the coating film after curing was visually observed, and the evaluation was made such that no swelling was observed, ◯, slight swelling was observed, Δ, and clearly swelling was observed, x.

The test results are shown in Table 1. In a resin composition obtained by mixing a polyol, a polyisocyanate compound, and a dimer diamine, swelling is not observed even when applied to a substrate having a high water content or even when used under high humidity. It was

[0026]

[Table 1]

[0027]

EFFECTS OF THE INVENTION According to the present invention, it is possible to obtain a resin composition capable of suppressing the occurrence of swelling even under the condition where water is present, and a coating material using the resin composition.

Continued front page    F-term (reference) 4J034 BA05 BA08 CA03 CB02 CB03                       DA01 DA03 DB03 DC02 DC35                       DF01 DF14 DF16 DG02 DP02                       DP06 DP18 DQ15 GA54 HA07                       HD02 HD03 HD04 HD05 HD12                       RA07 RA08                 4J038 DG111 DG131 DG191 DG271                       DG281 DG291 DG301 DG321                       JB04 NA04

Claims (2)

[Claims] 1. A curable resin composition comprising (A) a polyol, (B) a polyisocyanate compound, and (C) an amine compound having a dimer acid skeleton. 2. A coating material containing the curable resin composition according to claim 1.