JP2662966B2 - Polyurethane synthetic resin paint - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyurethane-based synthetic resin paint. In particular, the present invention relates to a polyurethane-based synthetic resin paint having good interlayer adhesion between an undercoat film and an overcoat film.

(Prior Art) Polyurethane-based synthetic resin paints include those obtained by combining (1) an acrylic polyol, a polyester polyol or a polyether polyol with a polyisocyanate, and (2) a photocurable paint or an electron beam as urethane acrylate. Some are used for cured coatings.
In recent years, a combination of a fluorine-based polyol and a polyisocyanate has been used.

In many cases, in the case of recoating, the vehicle of the undercoat and the vehicle of the topcoat are often the same in order to improve the interlayer adhesion between the undercoat and the overcoat. Even in this case, since it is a thermosetting resin paint, adjustment of the degree of crosslinking between the undercoating film and the topcoating film, slowing down of the curing speed, the type and amount of added pigments and other additives, and appropriate coating It is often solved by selecting conditions.

(Problems to be Solved by the Invention) When a polyurethane-based synthetic resin paint is applied, interlayer adhesion between the undercoat film and the top coat film often becomes a problem.

For example, at the contact surface between a coating film composed of a vehicle in which an acrylic polyol and a polyisocyanate are combined and an unsaturated polyester resin coating film, regardless of which is an undercoat or which is an overcoat, interlayer adhesion Is not good. In particular, it is remarkable in the case of a clear state where the pigment does not enter or in the case where the contact surface is a smooth surface.

Further, the interlayer adhesion between a coating composition containing a vehicle in which an acrylic polyol, a polyester polyol, a fluorine-based polyol, or the like is combined with a polyisocyanate as a component, and a photopolymerizable acrylate-based resin coating are not good.

If the interlayer adhesion is not good as a coating film, it causes peeling of the top coating film, and a film having excellent water resistance, chemical resistance and weather resistance cannot be obtained.

An object of the present invention is to improve the interlayer adhesion to a polyurethane-based synthetic resin paint having strong adhesion. Of course,
That is, not only when the undercoat paint and the overcoat paint are different but also when they are the same kind, the adhesion with the base material, the interlayer adhesion between the undercoat and the topcoat,
The coating must have good physical and chemical properties.

(Means for Solving the Problems) The present invention is intended to improve the above-mentioned interlayer adhesion and to study a paint which does not impair various properties as a coating film. Could be obtained.

In a polyurethane-based synthetic resin coating, (1) an addition reaction product of acrylic acid or methacrylic acid with an aliphatic monoglycidic ester compound, or glycidyl acrylate or glycidyl methacrylate and neoacid with respect to the isocyanate group equivalent of polyisocyanate. (2) a polymerizable isocyanate group-containing urethane compound obtained by adding an addition reaction product of the above with a polymerizable compound having another hydroxyl group, if necessary, so that the total hydroxyl group equivalent is reduced; A polyurethane-based synthetic resin coating comprising a monofunctional monomer and / or a polyfunctional monomer, (3) a photopolymerization initiator, and, if necessary, (4) a thermosetting unsaturated polyester resin. The polymerizable isocyanate group-containing urethane compound used is subjected to radical polymerization A compound having an unsaturated group, an isocyanate group, and a urethane group formed by the reaction of an isocyanate group with a hydroxyl group, and urethanizing a part of the isocyanate group of the polyisocyanate with a polymerizable compound having a hydroxyl group. Can be made by Accordingly, the obtained urethane compound containing a polymerizable isocyanate group has both the properties as a polymerizable compound and the properties as an isocyanate compound. It is good to use.

In other words, the obtained polymerizable isocyanate group-containing urethane compound or a polyurethane-based synthetic resin coating containing the same has unreacted isocyanate groups, and when left in the air, reacts with moisture in the air to gradually increase the viscosity. It rises and finally turns into a gel from candy. For this reason, when stored in a container, the air in the container is preferably sealed by replacing the air in the container with an inert gas such as nitrogen gas, as in the case of a commercially available curing agent for a two-component polyurethane resin paint. Further, the obtained polymerizable isocyanate group-containing urethane compound or a polyurethane-based synthetic resin coating containing the same has an unsaturated group that undergoes radical polymerization, and therefore, it is necessary to avoid prolonged exposure to high temperatures for a long time. In addition, when the obtained polyurethane-based synthetic resin paint containing a polymerizable isocyanate group-containing urethane compound is used together with a pigment having moisture and a synthetic resin having a free hydroxyl group in the composition, A two-pack type based on a polymerizable isocyanate group-containing urethane compound containing a pigment with moisture and a synthetic resin with a free hydroxyl group.The curing agent and base are mixed when used. To use. Such examples will be shown in Examples 4 and 7. Alternatively, in the composition of the polyurethane-based synthetic resin coatings I, II and III for ultraviolet curing in Examples 1, 2 and 3, the unsaturated polyester resin component of EPORAC 2101-70 and other components are separated. Liquid type,
If they are mixed at the time of use, the storage stability is further improved.

The polymerizable isocyanate group-containing urethane compound used in the present invention may be an addition reaction product of methacrylic acid acrylate and an aliphatic monoglycidic ester compound with respect to the isocyanate group equivalent of polyisocyanate, or glycidyl acrylate or glycidyl. It can be produced by adding an addition reaction product of methacrylate and neo acid and, if necessary, another polymerizable compound having a hydroxyl group so as to reduce the total hydroxyl group equivalent, followed by an addition reaction. In order to accelerate this addition reaction, tertiary amines such as triethylamine, triethanolamine and diethylaminoethyl methacrylate and tin compounds such as dibutyltin dilaurate and stannous octoate may be added in known amounts. It is known that an addition reaction product of a polyisocyanate and a polymerizable compound having a hydroxyl group is used as a coating material for ultraviolet curing. According to JP-A-57-119904, entitled "Radiation-curable acrylate esters containing urethane groups and their use" (Applicant, Bayer Actchengesellschaft), 1 NCO gram of polyisocyanate is described. The addition reaction is performed by adding an OH gram equivalent of 1 to 1.2 of a polymerizable compound having a hydroxyl group with respect to the equivalent, and Example 2 describes that the reaction is performed until the NCO value becomes 0.1% by weight or less. Japanese Patent Application Laid-Open No. 54-130633, entitled "UV curable coating composition" (applicant, Nippon Synthetic Chemical Industry Co., Ltd.) includes, in its examples, tolylene diisocyanate, β-hydroxyethyl acrylate and pentane. It is described that after reacting erythritol triacrylate, 1,6-hexanediol or the like, if a non-reacted free NCO group is present, the stability is impaired, so that a small amount of methanol is added.

In addition, generally commercially available UV curable synthetic resin NC
O value is often 0.3% by weight or less.

The polyisocyanate used here is well known to those skilled in the art, and includes known aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates. Examples of these are tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, o-, m- and p-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane 4,4'- Diisocyanate, lysine diisocyanate, m- and p
Phenylene diisocyanate, diphenyl ether diisocyanate, di (2-isocyanatoethyl) -bicyclo [2.2.1] -hept-5-ene-2,3-dicarboxylate, dicyclohexyl-4,4'-methane diisocyanate, 1,5- Naphthylene diisocyanate, 2,4,
6-triisocyanate toluene, polymethylene polyphenyl isocyanate and the like. Also, there are adducts obtained by urethanizing an excess of these polyisocyanates with a polyhydric alcohol, polyisocyanates containing an isocyanurate ring, polyisocyanates containing a burette group, polyisocyanates containing an allophanate group, and the like.

Next, as an essential component that reacts with polyisocyanate to obtain a polymerizable isocyanate group-containing urethane compound,
An addition reaction product of acrylic acid or methacrylic acid with an aliphatic monoglycide ester compound such as Kajura E10 (product of Yuka Shell Chemical) or an addition reaction product of glycidyl acrylate or glycidyl methacrylate with neo acid is used. .

Here, Kajura E10 is an aliphatic monoglycide ester having a molecular formula of C ₁₂ H ₂₂ O _{3 to} C ₁₄ H ₂₆ O ₃ and an epoxy equivalent of 250, which is known from Japanese Patent Publication No. 45-38807, and represented by the following formula.

R ', R ", and R are aliphatic groups. Neo acids are aliphatic tertiary carboxylic acids represented by the following formula known in JP-B-45-6254.

R _1, R _2, R ₃ are both alkyl groups, the total number of carbon atoms in the alkyl group is 3 to 25. Suitable neo acids include neopentanoic acid, neoheptanoic acid,
Neodecanoic acid, neotridecanoic acid (above,
Esso Standard Oil Co., Ltd.), Versatic acid “9”, Versatic acid “911”, Versatic acid “SR”
S120 "(these are Ciel Chemical Industry Limited products).

Further, examples of the polymerizable compound having another hydroxyl group used as needed include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, glycerin diallyl ether, and trimethylol. Propane diallyl ether, pentaerythritol triallyl ether, addition reaction product of glycidyl acrylate and acrylic acid, addition reaction product of glycidyl acrylate and methacrylic acid, addition reaction product of glycidyl methacrylate and acrylic acid, glycidyl methacrylate and methacrylic acid There are addition reactants and the like.

The reaction between the polyisocyanate and the polymerizable compound having a hydroxyl group for obtaining the polymerizable isocyanate group-containing urethane compound used in the present invention may be performed by adding a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether to 0.001 to 0.1% by weight as necessary. It can be easily completed under the condition of room temperature to 160 ° C. The reaction is carried out without solvent or in an organic solvent such as toluene, xylene, ethyl acetate, butyl acetate, methyl isobutyl ketone, or in the presence of a polymerization inhibitor, styrene, α-methylstyrene, methyl methacrylate, butyl methacrylate. ,
The reaction can also be performed in a reactive solvent such as 2-ethylhexyl acrylate and diallyl phthalate.

In the polyurethane-based synthetic resin paint of the present invention, a thermosetting unsaturated polyester resin can be used as necessary.

Thermosetting unsaturated polyester resins include unsaturated dibasic acids such as maleic anhydride and fumaric acid and alcohols such as ethylene glycol, propylene glycol, butylene glycol, glycerin monoallyl ether, trimethylolpropane diallyl ether, and pentaerythritol diallyl ether. To a compound, a saturated dibasic acid such as phthalic anhydride or adipic acid is added such that the carboxyl group equivalent of the dibasic acid is larger than the hydroxyl group equivalent of the alcohol, and the polycondensate obtained by the reaction is converted to styrene. ,
Dissolved in a polymerizable monomer such as α-methylstyrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, diallyl phthalate, benzoin, benzoin alkyl ether, benzophenone, isopropylthioxanthone, benzyldimethyl ketal, acetophenone diethyl ketal, 2-hydroxy It is a non-solvent or a resin having a curing component of 80% by weight or more of an organic solvent of 20% by weight or less which can be cured by irradiation with ultraviolet light by adding a photopolymerization initiator such as -2-methylphenylpropane.

Further, a tertiary amine such as triethylamine and triethanolamine and a photosensitizer such as triphenylphosphine and β-thiodiglycol are used in combination with the photopolymerization initiator to promote the photopolymerization reaction. Can also.

When mixing a polymerizable isocyanate group-containing urethane compound with an unsaturated polyester resin, the unsaturated group that undergoes radical polymerization acts in the same manner as the polymerizable monomer to introduce a urethane bond into the cured resin to form a polyurethane-based resin. A resin coating film can be formed.

Examples of the monofunctional monomer and / or polyfunctional monomer used in the present invention include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, phenoxyethyl acrylate, 1,3-dioxolan acrylate, diethylaminoethyl methacrylate, and the like. Examples include glycidyl methacrylate, N-vinylpyrrolidone, diethylene glycol diacrylate, neopentyl glycol diacrylate, butanediol diacrylate, trimethylolpropane trimethacrylate, and styrene, α-methylstyrene, ethyl acrylate, methyl methacrylate, and the like.

Since the polymerizable isocyanate group-containing urethane compound used in the present invention is also a synthetic resin having a polymerizable unsaturated group, a polymerizable isocyanate group-containing urethane compound and a monofunctional monomer or a polyfunctional monomer are mainly used. Vehicle-based paints are also included as polyurethane-based synthetic resin paints of the present invention and can be used. Also,
The same photopolymerization initiator as used in the thermosetting unsaturated polyester resin is used in the present invention.

The polyurethane-based synthetic resin coating of the present invention contains various cellulose derivatives, urethane-based oils, conventional organic solvents, various coloring pigments, and constitutions, in addition to the essential vehicle components described above, as long as the characteristics of the coating of the present invention are not impaired. Pigments, metal powders, plasticizers,
A known amount of a leveling agent, various fragrances and the like can be mixed and used. Further, the photopolymerization initiator and the photosensitizer are used in the range of 0.01 to 10% by weight, respectively, based on the total amount of the unsaturated polyester resin or the photopolymerizable acrylic resin and the polymerizable isocyanate group-containing urethane compound. be able to.

The polyurethane-based synthetic resin coating of the present invention can be produced by kneading each selected composition by a conventional method.

The polyurethane-based synthetic resin paint of the present invention can be finished with a single coat on the substrate, or can be overcoated such as undercoat and overcoat, or undercoat, intermediate coat and overcoat. The undercoat paint at the time of recoating is not limited to the polyurethane-based synthetic resin paint of the present invention, and may be another kind. Similarly, another type of top coat or middle coat may be used for recoating. As a coating method, it is applied by a conventional means such as roll coating, curtain flow coating, dipping coating, spraying, ironing coating, and brush coating, and is naturally dried or heated dried, or is irradiated with ultraviolet light by a mercury lamp or electron beam irradiation. Hardening and drying can be performed by a known method.

The polyurethane-based synthetic resin paint of the present invention can be used, for example, in wooden products of any shape such as panels, coils, molded products, sheets, films, and tubes, secondary processed products, metals, plastics, paper, leather, glass, fibers, and textiles. Can be applied to any acceptable substrate.

Hereinafter, the present invention will be described with reference to examples. However, all figures indicate parts by weight.

Examples, 1,2 a) 75% polyisocyanate, 25% ethyl acetate solution obtained by reacting 3 mol of tolylene diisocyanate with 1 mol of trimethylolpropane (Nippon Polyurethane Industry, trade name "Coronate L", NCO Content 13.2%) and 2
-Hydroxyethyl methacrylate and hydroquinone monomethyl ether in 1% ethyl acetate
Put into a reaction vessel at the mixing ratio shown in the table, and raise the temperature while stirring to keep it at about 80 ° C. The value of OH / NCO at this time is 0.32 / 1 in the case of “A” in Table 1 and 0.64 / 1 in the case of “B” in Table 1. The reaction between the isocyanate groups of the polyisocyanate and the hydroxyl groups of 2-hydroxyethyl methacrylate is followed by quantifying the amount of remaining hydroxyl groups. The reaction is completed in about 3 hours, and a urethane compound having a polymerizable unsaturated group and an unreacted isocyanate group, that is, a polymerizable isocyanate group-containing urethane compound "A" or "B" is obtained. These “A” and “B” may be used after isolation and purification, but may be used as they are.

The NCO content of “I” and “B” obtained here is
They are 7.70% and 3.45%, respectively.

b) The polymerizable isocyanate group-containing urethane compounds "a" and "b" obtained in a) were combined with an unsaturated polyester resin "Epolac 2101-70 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., viscosity 9 poise)" in Table 2 below. By kneading into the compounding, ultraviolet curable polyurethane-based synthetic resin paints I and II are obtained.

Example 3 c) Acrylic acid 72 Cardura E-10 250 Hydroquinone monomethyl ether 0.16 A total of 322.16 was charged into a reaction vessel, and the temperature was gradually raised with stirring to about 85.
Keep between ° C and 95 ° C. The reaction between the carboxyl group of acrylic acid and the epoxy group of Cardura E-10 is followed by quantifying the amount of the remaining carboxyl group. The reaction is completed in 5 hours to obtain an adduct AE having one hydroxyl group and one polymerizable unsaturated group.

d) A total of 900 of the adduct AE 302 coronate L598 obtained in c) is placed in a reaction vessel, and a polymerizable isocyanate group-containing urethane compound "c" is obtained by the same operation as in a).
The NCO content of this "c" is 4.38%. In this case, the value of OH / NCO is 0.5 / 1.

e) Using "c" obtained in d) and the unsaturated polyester resin, mixing with the following composition to obtain an ultraviolet-curable polyurethane-based synthetic resin paint III.

"c" obtained in d) 480 Epolac 2101-70 320 Styrene 200 Benzoin-isobutyl ether 30 Total 1030 Example 4 The acrylic polyol "Dianal PS (manufactured by Mitsubishi Rayon, nonvolatile content 48%, viscosity: P, OH value 3
A two-pack type polyurethane synthetic resin paint is obtained by combining the composition using 2) with a paint base and the polymerizable isocyanate group-containing urethane compound "i" obtained in a) as a curing agent.
Create an IV.

Base Dianal PS 450 Toluene 70 Calcium carbonate 250 Talc 180 Rutile type titanium white 20 Iron oxide yellow 30 Total 1000 Curing agent “I” obtained in a) 130 Ethyl acetate 20 Total 150 Base: Mixing ratio of curing agent 100: Set to 15 and use.

In comparison with Examples 1 to 4 described above, the case where no polymerizable isocyanate group-containing urethane compound is used is described below as a comparative example.

Comparative Examples 1, 2, 3 The hydroxyl groups of 2-hydroxyethyl methacrylate and the hydroxyl groups of the adduct AE obtained in Example 3c were equivalent to the isocyanate groups of Coronate L having an NCO content of 13.2%. Was mixed as shown in Table 3 below, and the same operation as described in a) of Examples 1 and 2 was carried out.
A polymerizable urethane compound 3M having no unreacted isocyanate groups is obtained. This is a type of urethane acrylate.

In Comparative Examples 1, 2, and 3, including those using the polymerizable urethane compound 3M, the components are mixed according to the formulation shown in Table 4 below to prepare an ultraviolet curing resin.

As can be seen from the above table, Comparative Example 1 is only an unsaturated polyester resin. Comparative Example 2 is a composition obtained by adding a polyisocyanate having no polymerizable unsaturated group to an unsaturated polyester resin, and Comparative Example 3 is a composition obtained by adding a polymerizable urethane compound having no isocyanate group. .

Comparative Example 4 In the two-pack type polyurethane synthetic resin coating material of Example 4, a polyisocyanate having no polymerizable unsaturated group is used as a curing agent, and the composition is shown below.

Base Same as described in Example 4. Hardener Coronate L 76 ethyl acetate 24 total 100 base: hardener = 100: 10 used in mixing ratio.

A coated plate is prepared using each coating material of the above Examples and Comparative Examples, and a coating film performance test is performed.

First, a coated board is prepared using the polyurethane-based synthetic resin paints I, II, III and IV obtained in Examples 1 to 4.

A mixture of the base of Example IV and the curing agent at a predetermined mixing ratio is applied twice to the surfaces of three 12 mm-thick plywood sheets for formwork. 7 g./R ^{2 in} the first coating, dried at room temperature for 15 minutes, 5 g./R ^{2 in the second} coating, a total of 12 g./R ² applied, 50-60
Forcibly dry in a hot air drying oven maintained at ℃ for 16 minutes.

The paints I, II and II of Examples 1, 2 and 3
When the coating amount of I in roller coating, each was coated so as to 6G./R ^2, irradiates 15cm apart 9 seconds from a mercury lamp at an ultraviolet irradiation device installed mercury lamp 80W / cm to painted surfaces, paint The surfaces of I, II and III are hardened and dried.

Next, using the paints obtained in Comparative Examples 1 to 4, a coated plate is prepared according to the method for preparing a coated plate of the example.

Table 5 shows the results of the following coating film performance tests performed on the obtained coated plates.

Test items and test methods Hardness: Measured by pencil hardness.

Adhesion: 100 pieces of 1mm-wide goban eyes are made with a cutter knife, a cellophane tape is adhered from above, and it is vigorously peeled off. The larger the number of peeled eyes, the better the adhesion.

Alkali resistance: The entire coated plate is immersed in a 3% sodium carbonate solution, pulled up 48 hours later, washed with water, and dried. If there is no abnormality on the painted surface, it is judged to be acceptable.

Example 5 A polyurethane synthetic resin paint V having the following composition was prepared.

Base "I" obtained in a) 40 Epolak 2101-70 40 Styrene 19 Cobalt octate 1 Total 100 Curing agent Methyl ethyl ketone peroxide 55% dimethyl phthalate solution 2 Total 2 Base: Curing agent mixing ratio = 100: 2 The obtained polyurethane-based synthetic resin paint V was obtained in Example 1.
The polyurethane-based synthetic resin paint I is an ultraviolet-curable paint, whereas a two-part type paint of a base and a curing agent which is cured at room temperature and dried.

 The coating film performance test using this will be described below.

After a two-pack type acrylic polyurethane paint of Comparative Example 4 was coated ironing twice the surface of the mold for the plywood coated plate creation method described above, applied so that the polyurethane synthetic resin paint V to 6G./R ² Then after one hour at room temperature it dries dry,
After two days, it is cured and dried. Its hardness is H and adhesion is 100 /
100, the alkali resistance was also acceptable and good.

In the above Examples and Comparative Examples, the case where the plywood was painted was described. The coated formwork plywood is strictly required as the practical use conditions, such as the adhesion of the coating film to the plywood substrate and the interlayer adhesion when overcoated.

Example 6 A UV-curable polyurethane-based synthetic resin paint VI having the following composition is prepared.

"B" obtained in a) 30 "B" obtained in a) 30 Styrene 40 Benzoin ethyl ether 3 Total 103 This is used for undercoating and topcoating on a 12 mm thick birch plywood.

First, 3 g./R ^{2 is} applied for undercoating, and is irradiated with ultraviolet rays for 9 seconds with an 80 W / cm mercury lamp at a distance of 15 cm from the lamp and cured and dried.

Next, the cured similarly 9 seconds UV irradiation and when applying the 3.g / R ² of the undercoat on as a top coat.

The obtained coating film was subjected to the same coating film performance test as in the above-mentioned example. As a result, the pencil hardness was 5H and the adhesion was good.

Example 7 A two-pack type polyurethane-based synthetic resin paint VII is prepared according to the following formulation.

Base Dianal PS 770 Dioctyl phthalate 10 Ethyl acetate 110 Toluene 110 Total 1000 Curing agent “I” obtained in a) 220 Ethyl acetate 30 Total 250 Base: Used with a mixing ratio of curing agent of 100: 25.

This polyurethane synthetic resin paint VII and the polyurethane synthetic resin paint I of Example 1 were applied to a 12 mm thick birch plywood.
Are alternately used for top coat and undercoat, respectively, and as a comparative example, the unsaturated polyester resin paint of Comparative Example 1 is used, and the coated plates (a), (b),
Create (c).

The results of surface hardness and adhesion test of the obtained cured dried coating film are shown in the lower part of Table 7.

The coated plate (c) of the comparative example results in leaving some problems in interlayer adhesion as compared with the coated plates (a) and (b) using the polyurethane synthetic resin paint of the present invention.

Embodiments 6 and 7 can be applied to the fields of floor building materials, interior wall materials, furniture, decorative boards and the like.

Alternatively, as an example of the coating formwork plywood in Examples 1 to 4, a two-component polyurethane synthetic resin paint composed of a base and a curing agent is applied to the undercoat, and a UV-curable polyurethane synthetic resin paint is applied to the top coat. However, the present invention is not limited to this. For example, on the contrary, a two-pack type polyurethane composed of a base and a curing agent, which is a semi-transparent ultraviolet-curable polyurethane-based synthetic resin paint containing an extender pigment in an undercoat, and a top pigment in a top coat, is used as an overcoat. It can also be finished by painting a semi-transparent colored ultraviolet-curable polyurethane-based synthetic resin paint to which a small amount of a synthetic resin paint or a lake pigment is added.

Examples 8 to 13 g) methacrylic acid 786 Cardura E-10 2,214 hydroquinone monomethyl ether 0.6 A total of 3,000.6 was placed in a reaction vessel, and the temperature was gradually increased while stirring, and about 90
Maintain between ° C and 112 ° C. The reaction between the carboxyl group of methacrylic acid and the epoxy group of Cardura E-10 is followed by quantifying the amount of the remaining carboxyl group. The reaction is completed in about 5 hours to obtain an adduct MAE having one hydroxyl group and one polymerizable unsaturated group. Its OH content is 5.0
% By weight.

Next, using the components used for the addition reaction described in Table 8 including the adduct MAE, the addition reaction is carried out according to the procedure described in a) of Examples 1 and 2 to obtain an addition reaction product. At this time, the value of OH / NCO is 0.83 / 1 in any of these six Examples 8 to 13. Each of these addition reaction products is a urethane compound containing a polymerizable isocyanate group, and a polyurethane-based synthetic resin coating VIII, I for ultraviolet curing can be obtained by mixing these with other coating components.
X, X, XI, XII and XIII can be obtained. The conditions for UV irradiation are 80 W / cm when the film thickness is 30-200 μm.
15cm distance between the mercury lamp and the object to be coated, conveyor speed 10m /
In a minute, if the mercury lamp is four, it is hardened when it passes two or three times. Also, these paints have a storage stability of 3 months or more at room temperature.

The application areas of these paints are not limited, but VIII, IX and X are mainly for wood products, X, XI,
XII and XIII can be used for metals, plastics, paper, leather, glass, braids, textiles, etc., which require weather resistance.

In addition, although all of these polyurethane-based synthetic resin paints for ultraviolet curing have been described as clear, they can also be used by adding a coloring pigment.

If you want to add a small amount of easily dispersible color pigments, you only have to mix and disperse in these polyurethane synthetic resin paints,
If you want to add a large amount of color pigment, make the composition used for the addition reaction OH / NCO = 1 to 1.05 / 1, and make a synthetic resin with almost no free NCO groups under the same reaction conditions. A large amount of color pigment is kneaded with this to make a colored paste,
This can be used by appropriately mixing it with the clear of the above-mentioned polyurethane-based synthetic resin paint for ultraviolet curing.

Claims (2)

(57) [Claims] 1. A polyurethane synthetic resin paint,
(1) an addition reaction product of acrylic acid or methacrylic acid with an aliphatic monoglycidic ester compound, or an addition reaction product of glycidyl acrylate or glycidyl methacrylate with neo acid with respect to isocyanate group equivalent of polyisocyanate; Further, if necessary, the total hydroxyl group equivalent to the polymerizable compound having another hydroxyl group is reduced, and the polymerizable isocyanate group-containing urethane compound obtained by the addition reaction is mixed with (2) a monofunctional monomer or a polyfunctional monomer. A polyurethane-based synthetic resin coating comprising a functional monomer, (3) a photopolymerization initiator, and, if necessary, (4) a thermosetting unsaturated polyester resin. 2. The method according to claim 1, wherein the polymerizable compound having another hydroxyl group is at least one of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate. The polyurethane-based synthetic resin paint according to claim 1,