JP2017066214A - Coating composition excellent in migration resistance and adhesiveness and manufacturing method of coating product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylic urethane coating for forming a coated film hardly migrating a component of a packaging material to a coated film, good in migration resistance and excellent in adhesiveness to a substrate (especially adhesiveness to a metal film) or the like and a coating method.SOLUTION: The acrylic urethane coating is a two-liquid type acrylic urethane coating containing acrylic polyol as a main resin and a polyisocyanate compound as a curing agent and can form a coated film good in migration resistance because solid hydroxyl value of the acrylic polyol is 30 mgKOH/g or more and mass average molecular weight of the acrylic polyol is 30000 or more.SELECTED DRAWING: None

Description

  The present invention is capable of forming a coating film having good coating properties such as adhesion, which prevents components contained in the packaging material from transferring to the coating film on the surface when the coated product is transferred. The present invention relates to a method for producing an acrylic urethane-based paint and a coated product excellent in the above.

Various methods are used to give a desired appearance to the plastic. For example, by applying a metal film to the surface using a method such as plating, vapor deposition, or sputtering, a metallic appearance is imparted to the plastic. Acrylic urethane paints are often used to protect the surface of the metal film. Acrylic urethane paints are excellent in characteristics such as fleshiness, glossiness, weather resistance, etc., and are also used to color plastic surfaces and the above metal films by coating them with colorants. .
As an acrylic urethane-based paint, for example, in Patent Document 1, when a coating film is formed on the surface of a plastic molded product, a weight average molecular weight of 5,000 to 30,000 is provided for the purpose of providing a coating film with high gloss and good appearance. A coating material containing an acrylic polyol having a number, a polycarbonate diol having a number average molecular weight of 300 to 1500, and a polyisocyanate compound in an amount of 0.6 to 1.5 molar equivalents relative to the total of hydroxyl groups in the acrylic polyol and the polycarbonate diol. A composition is described.

JP 2011-207953 A

When the product (painted product) after painting is wrapped in a mirror mat or resin packaging material, and shipped and transported, components such as plasticizers contained in the packaging material are transferred to the coating film on the product surface. Doing so may affect the appearance. Especially for products with short cycles such as game machines, it is necessary to manufacture and deliver a predetermined amount of coated product at a time on a predetermined date, so it is shipped before sufficient curing time has elapsed after painting. Necessary. In such a case, it can be said that the problem that the appearance of the product is adversely affected by the transfer of the components of the packaging material described above to the coating film is likely to occur.
However, the coating composition described in Patent Document 1 is intended to recover scars on the surface of the cured coating film, and the effect on the appearance of the coated product due to the transfer of components of the packing material to the coating film Has not been studied at all. If the component of the packaging material is suppressed from moving to the coating film, the adhesion of the coating film to the substrate deteriorates, so an acrylic urethane paint that can form a coating film that achieves both migration resistance and adhesion is desired. It is rare.
Therefore, the present invention forms a coating film in which the components of the packing material are not easily transferred to the coating film, the migration resistance is good, and the adhesion to the substrate (particularly the adhesion to the metal film) is good. It is an object of the present invention to provide a method for producing an acrylic urethane-based paint and a coated product.

[1] The acrylic urethane paint of the present invention is a two-component acrylic urethane paint containing an acrylic polyol as a main resin and a polyisocyanate compound as a curing agent, and the solid hydroxyl value of the acrylic polyol. Is 30 mg KOH / g or more, and the mass average molecular weight of the acrylic polyol is 30000 or more.

[2] The acrylic urethane paint according to [1], wherein the polyisocyanate compound is an aromatic polyisocyanate compound having an aromatic ring.
[3] The acrylic urethane paint according to [2], wherein the polyisocyanate group of the polyisocyanate compound is 0.7 mole equivalent or more and 3.0 mole equivalent or less with respect to 1 mole equivalent of the hydroxyl group of the acrylic polyol.
[4] The acrylic urethane coating according to [2], wherein the polyisocyanate group of the polyisocyanate compound is 1.1 to 1.3 molar equivalents relative to 1 molar equivalent of the hydroxyl group of the acrylic polyol.
[5] The acrylic urethane paint according to any one of [1] to [4], further including a hydroxyl group-containing resin having a smaller mass average molecular weight than that of the acrylic polyol.
[6] The acrylic urethane paint according to [5], wherein the secondary resin is polycarbonate diol.
[7] The acrylic urethane paint according to [7], wherein the polycarbonate diol has a number average molecular weight of 500 or more and 2000 or less and a solid hydroxyl value of 50 mgKOH / g or more and 250 mg / KOH or less.
[8] The acrylic urethane paint according to any one of [1] to [7], further containing a solvent.
[9] The acrylic urethane paint according to any one of [1] to [8], further including a colorant.
[10] A method for producing a coated product, comprising a step of forming a coating film on the surface of the product or a member constituting the product using the paint according to any one of [1] to [9].
[11] The method for manufacturing a painted product according to [10], wherein the painted product is a gaming machine.

The acrylic urethane coating of the present invention contains an acrylic polyol having a hydroxyl value and a weight average molecular weight within a specific range as a main agent, and thus has good migration resistance and adhesion to a substrate (particularly adhesion to a metal film). A good coating film can be formed. Therefore, it is possible to form a coating film in which the appearance of the product is hardly deteriorated due to the migration of the components of the packaging material at the time of shipment, transportation and the like.
For this reason, a coating product with good migration resistance can be provided by the step of forming a coating film using the acrylic urethane paint of the present invention.

Embodiments of the acrylic urethane paint of the present invention will be described below.
The acrylic urethane paint of this embodiment is a two-component acrylic urethane paint containing an acrylic polyol as a main resin and a polyisocyanate compound as a curing agent.

(Acrylic polyol)
The acrylic polyol is an acrylic resin having two or more hydroxyl groups in one molecule, and is, for example, a polymer of a hydroxyl group-containing acrylic monomer. Hydroxyl group-containing acrylic monomers include, for example, monomers having a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate. A ring-opening adduct of γ-butyrolactone to 2-hydroxyethyl methacrylate, and a ring-opening adduct of ε-caprolactone to 2-hydroxyethyl acrylate. Any one hydroxyl group-containing acrylic monomer can be used alone, or two or more hydroxyl groups can be used in appropriate combination. This embodiment is not limited to the type of monomer and polymerization method.

  In the present embodiment, the acrylic polyol includes a copolymer of a hydroxyl group-containing acrylic monomer and another ethylenically unsaturated monomer. The hydroxyl group-containing acrylic monomers are those exemplified above, and any one of them can be used alone, or two or more of them can be used in appropriate combination. This embodiment is not limited to the type of monomer and polymerization method. Other ethylenically unsaturated monomers are, for example, monomers similar to the acrylic acid esters, methacrylic acid esters, styrene derivatives, vinyl esters, halogenated vinyl monomers, and nitrogen-containing vinyl monomers exemplified above. Other ethylenically unsaturated monomers can be used alone or in appropriate combination of two or more. This embodiment is not limited to the type of monomer and polymerization method.

  Commercially available acrylic polyols include, for example, Mitsubishi Rayon Co., Ltd. dialnal; LR2713, LR-1718, LR2571, LR-2679, DIC Corporation acridick; 57-773, KU-220, 50- 598-K, WEU-926 and the like.

  The hydroxyl value of the acrylic polyol is a viewpoint that improves the migration resistance (hereinafter simply referred to as “migration resistance”) to the packaging material in the initial stage after coating by increasing the crosslink density of the coating film of the acrylic urethane paint. Therefore, it is preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, and further preferably 50 mgKOH / g or more. Further, from the viewpoint of preventing the adhesiveness to the substrate from being lowered due to excessive curing shrinkage of the coating film, it is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less. More preferably, it is 80 mgKOH / g or less.

  The hydroxyl value is the amount of potassium hydroxide required to neutralize the acetic acid required for acetylation by acetylating the hydroxyl group in the sample, expressed in mg per 1.0 g of the sample. This is a scale indicating the content of hydroxyl groups. As a method for testing the hydroxyl value, the neutralization titration method defined in JIS0070-1992 is used.

As the acrylic polyol, it is desirable to blend an acrylic polyol having a high molecular weight from the viewpoint of relaxing the shrinkage of the coating film upon curing and improving the adhesion. Specifically, the mass average molecular weight is preferably 30000 or more, more preferably 40000 or more, and further preferably 50000 or more. From the viewpoint of improving migration resistance, it is desirable that the hydroxyl value is 30 mgKOH / g or more as described above. However, when the hydroxyl value is high, the shrinkage of the coating film during curing is increased and the adhesion to the substrate is reduced. Often to do. Therefore, the above-mentioned hydroxyl value and blending with a high molecular weight acrylic polyol as described above can alleviate the shrinkage of the coating film during curing while obtaining a higher crosslinking density, and therefore has good migration resistance. In addition, a coating film having good adhesion to a substrate (particularly adhesion to a metal film) can be obtained.
Further, from the viewpoint of increasing the smoothness of the coating film and obtaining a beautiful appearance, the mass average molecular weight is preferably 150,000 or less, more preferably 120,000 or less, and even more preferably 100,000 or less.

(Polyisocyanate compound)
The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. For example, 2,4-toluene diisocyanate, diphenylmethane-4,4′-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate , Methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, n-pentane-1,4-diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate. Any of these may be used alone or in appropriate combination of two or more.

As the polyisocyanate compound, an aromatic polyisocyanate compound having an aromatic ring is preferable. Since the polyisocyanate compound has an aromatic ring that is an electron-withdrawing group, the reaction activity of the isocyanate group is increased, so that the migration resistance of the coating film formed by the acrylic urethane paint containing the polyisocyanate compound is improved.
Moreover, since the polarity of a polyisocyanate compound becomes high by having an aromatic ring, when the metal layer is formed adjacent to the coating film formed with an acrylic urethane coating, the adhesiveness of a metal layer and a coating film is It becomes good.

  Examples of aromatic polyisocyanate compounds include 2,4-toluene diisocyanate (TDI), diphenylmethane-4,4'-diisocyanate (MDI), and xylylene diisocyanate (XDI) isocyanates. Among these, xylylene diisocyanate isocyanate is preferable. Examples of commercially available products include Takenate D-110 manufactured by Mitsui Chemicals, Inc., m-Xylylene Diisocyanate manufactured by Tokyo Chemical Industry Co., Ltd., and the like.

  The ratio of the acrylic polyol and polyisocyanate compound contained in the acrylic urethane paint increases the curability of the paint film to increase migration resistance, and increases the paint film strength to improve various physical properties of the paint film. In view of the above, it is preferable that the polyisocyanate group of the polyisocyanate compound is 0.7 mole equivalent or more and 3.0 mole equivalent or less with respect to 1 mole equivalent of the hydroxyl group of the acrylic polyol, and 0.7 mole equivalent or less and 2.0 mole equivalent or less. The molar equivalent is more preferably 1 mol equivalent or less, and even more preferably 1.1 mol equivalent or more and 1.3 mol equivalent or less. The more the polyisocyanate group of the polyisocyanate compound is present with respect to the hydroxyl group of the acrylic polyol, the more the reactivity (reaction rate) of the acrylic urethane paint is increased, and the migration resistance of the coating film is improved. Further, the presence of many polyisocyanate groups is suitable for blending a secondary resin having a high hydroxyl value.

  From the viewpoint of improving the adhesion by preventing the coating film from curing and shrinking, and from the viewpoint of increasing the pot life, the polyisocyanate group of the polyisocyanate compound is 3.0 mol relative to 1 mol equivalent of the hydroxyl group of the acrylic polyol. It is preferably no greater than the equivalent, more preferably no greater than 2.0 molar equivalent, and even more preferably no greater than 1.5 molar equivalent.

(Sub resin)
From the viewpoint of adjusting the adhesion of the coating film to the substrate, the acrylic urethane paint preferably further contains a secondary resin in addition to the acrylic polyol and the polyisocyanate compound. As the secondary resin, a soft resin or a soft monomer is used. When an appropriate amount of these is used as a secondary resin, it is incorporated into the coating film after the reaction between the acrylic polyol and the polyisocyanate compound. Therefore, the coating film is not excessively softened, and the adhesion to the substrate can be adjusted while maintaining good migration resistance.

  As the soft resin, a resin having a hydroxyl group whose number average molecular weight is smaller than that of acrylic polyol is preferable. An example of such a resin is polycarbonate diol (PCD). As a commercial item of polycarbonate diol, Asahi Kasei Co., Ltd. Duranol; T5650E, T5650J, T5651, T5652, ETERNACOLL made by Ube Industries, Ltd .; UM-90, PH-50, PH-100, PH200, etc. are mentioned, for example. .

  The blending amount of the soft resin may be an appropriate amount in order to obtain the effect of improving the adhesion while maintaining good migration resistance. The appropriate blending amount varies depending on the type of the soft resin, but is usually about 1 to 10% by mass in 100% by mass of the acrylic polyol as the main agent.

  The number average molecular weight of the soft resin is preferably 500 or more, more preferably 600 or more, and further preferably 700 or more, from the viewpoint of increasing the adhesion of the coating film. Moreover, from a viewpoint of making compatibility with a main ingredient favorable, it is preferable that it is 2000 or less, It is more preferable that it is 1000 or less, It is further more preferable that it is 900 or less.

  If the solid hydroxyl value of the soft resin is too low, the curing may be insufficient and the migration resistance may be lowered, and if it is too high, the shrinkage of the curing may become strong and affect the adhesion. Therefore, from the viewpoint of forming a coating film having good migration resistance and adhesion, it is preferably 50 mgKOH / g or more and 250 mg / KOH or less, more preferably 100 mgKOH / g or more and 200 mg / KOH or less, and 130 mgKOH / It is more preferable that it is g or more and 150 mg / KOH or less.

  Examples of the soft monomer blended in the acrylic urethane coating as the auxiliary resin include 2-hydroxy-3-phenoxypropyl acrylate, nonylphenol ethylene oxide (EO) -modified acrylate, caprolactone derivatives, and the like. Examples of these commercially available soft monomers include Aronix manufactured by Toa Gosei Co., Ltd .; M-5700, M-111, Placel (PCL) manufactured by Daicel Corporation; 205, 208, 205U, 305, 308, and the like. It is done.

  An appropriate amount of the soft monomer is blended in order to obtain an effect of improving adhesion while maintaining good migration resistance. The appropriate blending amount varies depending on the type of the soft monomer, but is usually in the range of 1 to 5% by mass in 100% by mass of the acrylic polyol as the main agent. Although the soft monomer is good in compatibility with the main agent in comparison with the soft resin, it is easy to lower the migration resistance by a small amount of blending, so that the blend amount is generally smaller than that of the soft resin.

(solvent)
The acrylic urethane paint may further contain a solvent. By including a solvent, even when an acrylic polyol having a high mass average molecular weight is used, the viscosity of the acrylic urethane coating can be adjusted to a range suitable for spray coating work. However, the method of applying the acrylic urethane coating is not limited to spray coating, and an acrylic urethane coating that does not contain a solvent may be used.

  Solvents include, for example, diethyl ketone (3-pentanone), methyl propyl ketone (2-pentanone), methyl isobutyl ketone (4-methyl-2-pentanone), 2-hexanone, 5-methyl-2-hexanone, 2-to Ketones such as butanone, 3-heptanone, 4-heptanone, cyclopentanone, cyclohexanone, ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, methyl propionate, propionic acid Organic solvents such as esters such as ethyl, diethyl carbonate, γ-butyrolactone, isophorone and butyl isobutyrate, hydrocarbons such as heptane, hexane and cyclohexane, and aromatic hydrocarbons such as toluene and xylene can be used. . Furthermore, ethers such as tetrahydrofuran, 1,4-dioxane, ketones such as acetone and methyl ethyl ketone, and esters such as methyl acetate, n-propyl acetate, isopropyl acetate, methyl propionate, ethyl propionate, and dimethyl carbonate . In this embodiment, it is not restricted to the kind of solvent, Arbitrary 1 type can be used individually or in combination of 2 or more types as appropriate.

(Coloring agent)
The acrylic urethane paint may further contain colorants such as dyes, pigments (colored pigments, bright materials, extender pigments, and other design-imparting pigments). With a colorant, the coating film can be colored, the gloss of the coating film can be adjusted, and the texture of the coating film can be adjusted. However, when a clear (colorless) coating film is formed, the acrylic urethane paint is carried out in a form that does not contain a colorant.

(catalyst)
For the purpose of accelerating curing, a catalyst such as a metal catalyst may be added to the acrylic urethane paint. Since the curing of the acrylic urethane paint is promoted by adding the catalyst, in general, the addition of the catalyst is effective for improving the migration resistance. However, when the curing is accelerated, the pot life of the acrylic urethane paint tends to be shortened.
The acrylic urethane paint of this embodiment uses a polyisocyanate compound having a solid hydroxyl value and a mass average molecular weight within a predetermined range as a main resin, and therefore, a coating having good migration resistance without blending a catalyst. A film can be formed. The acrylic urethane paint of this embodiment has a feature that the pot life is long because it does not contain a catalyst in order to improve the migration resistance of the coating film.
In this embodiment, a catalyst means the compound containing the metal added for the purpose of hardening acceleration, and about 0.001-0.1 mass% is normally mix | blended in 100 mass% of acrylic urethane coatings. Examples of the catalyst include zinc neodecanoate (CAS 27253-29-8).

(Optional component)
The acrylic urethane paint may further contain a kind and amount of an auxiliary agent that does not impair the effects of the present invention, if necessary. Examples of such auxiliary agents include dispersants, fluidity modifiers, ultraviolet absorbers, and light stabilizers. Moreover, in order to improve the abrasion resistance of the coating film, a polyethylene wax may be blended.

(Manufacturing method of painted products)
This invention can also be implemented as a manufacturing method of the coated product including the process of forming a coating film on the surface of a product using the polyacryl urethane paint of embodiment mentioned above. This process can form a coating film with good migration resistance. For example, it is necessary to manufacture a predetermined amount of product at a time on a predetermined date. Can be manufactured efficiently and with high reliability.

  The coating film of the polyacryl urethane coating is, for example, an acrylic urethane resin prepared by mixing an acrylic polyol and a polyisocyanate compound at a certain ratio when forming the coating film, and further adding a solvent to a solid content concentration suitable for coating. It is obtained by applying and drying the coating material on a substrate within a predetermined time and further performing a curing treatment. As the solvent, any one of the above solvents may be used alone, or two or more may be used in appropriate combination.

  In the step of forming the coating film, a known coating method such as a roll coating method, a spray method, a dip method, or a brush coating method can be selected as the coating method. The thickness of the coating film is preferably 1 to 100 μm. More preferably, it is 10-50 micrometers, Most preferably, it is 15-25 micrometers. If it is less than 1 μm, it is difficult to manage the process of forming a coating film, and if it exceeds 100 μm, workability is deteriorated, which is not economically preferable. A coating film having a desired thickness may be formed by one application, or a coating film having a desired thickness may be formed by applying a plurality of times.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the examples.

[Preparation method of coating film]
The acrylic polyol as the main agent and the polyisocyanate compound as the curing agent are mixed in such a ratio that the polyisocyanate group of the latter polyisocyanate compound is 1.2 molar equivalents relative to 1 molar equivalent of the former hydroxyl group. A solution was prepared. To this mixed solution, a solvent (Planet thinner # 743 No. 2 manufactured by Origin Electric Co., Ltd.) was further added to prepare an acrylic urethane paint having a viscosity of about 10 seconds with an Iwata viscosity cup meter.
The adjusted acrylic urethane paint was applied to the surface of various substrates using a spray gun so that the film thickness of the coated film after drying was about 20 μm. Then, after leaving still at normal temperature (25 degreeC) for 5 minutes, it left still at 80 degreeC for 30 minutes, forcedly dried and produced the coating film with a film thickness of about 20 micrometers, and was set as evaluation object.

[Evaluation method of coating film]
The method used for the evaluation of the coating film after forced drying described above is shown below.
(Adhesion evaluation)
As a resin base material for producing a coating film on the surface, a resin base material in which a chromium plating layer is formed on the surface of ABS, a resin base material in which an aluminum vapor deposition layer is formed on the surface of ABS, and other layers on the surface A polycarbonate resin substrate in which no is formed was used. A cut area was formed by cutting the coating film formed on the surface of each resin substrate with a cutter in a 2 mm grid pattern. Cellophane tape was applied to the coating film to cover the cut area, and the cellophane tape was sufficiently adhered to the coating film using a finger. Thereafter, the cellophane tape was peeled off from the surface of the coating film at once, and it was evaluated whether or not peeling occurred in the coating film in the cut region. When there was no coating film peeling, it was set as acceptable, and when there was a coating film peeling, it was set as rejection.

(Hardness evaluation)
By applying a load of 1 kg to a Mitsubishi Uni Pencil (hardness H) sharpened by pencil sharpening, and rubbing the coating surface of the resin substrate with the load concentrated on the tip of the pencil core, It was evaluated whether or not scratches that could be recognized visually were attached. The evaluation was repeated 5 times, and when the number of wrinkles was 0 times and once, it was accepted, and when it was 2 times or more, it was rejected.
The hardness evaluation was performed on a coating film formed on the surface of a polycarbonate substrate whose surface is polycarbonate. This is the same for the following appearance evaluation and migration resistance evaluation.

(Appearance evaluation)
The smoothness (leveling) of the surface of the coating film prepared on the surface of the substrate was evaluated by visual observation, and it was determined to be acceptable if it was a practically no problem level, and rejected if it was a practically problematic level.

(Evaluation of migration resistance)
The coating film produced on the surface of the substrate was allowed to stand under normal temperature (25 ° C.) and humidity (50%) conditions. A polyethylene sheet was adhered to the surface of the coating film after 24 hours of curing, and a load of 500 g / cm ² was applied from above. Under the same conditions as the curing described above, after leaving for 24 hours with this load applied, the polyethylene sheet is peeled off from the surface of the coating film, and it is visually evaluated whether or not there is an abnormality in the state of the coating film surface. did.
When there was no abnormality in the appearance of the coating film surface and there was no migration trace, it was judged as acceptable, and when there was a migration trace on the coating film surface, it was judged as unacceptable.

Example 1
Acrylic polyol (mass average molecular weight 70000, solids hydroxyl value 77 mgKOH / g, manufactured by Mitsubishi Rayon Co., Ltd., Dianar LR-2713) as a main agent, polycarbonate diol (manufactured by Asahi Kasei Co., Ltd., Duranol T5650J) as a secondary resin, and xylyl as a polyisocyanate A coating film was formed using an acrylic urethane coating containing range isocyanate (Takenate D-110 manufactured by Mitsui Chemicals, Inc.).
For acrylic urethane paint, Planet Thinner # 743 No. In addition to 2, a leveling agent (BY-333 manufactured by BYK Japan) and a polyethylene wax (CE-502 manufactured by Koyo Chemical Co., Ltd.) were added. The amount of each component (parts by mass) is as shown in Table 1. As described above, the amount of the polyisocyanate compound was such that the polyisocyanate group was 1.2 molar equivalents relative to 1 molar equivalent of hydroxyl groups of the acrylic polyol.

(Example 2)
A coating film was formed in the same manner as in Example 1 except that an acrylic polyol having a weight average molecular weight of 80,000 and a solid hydroxyl value of 60 mgKOH / g (Dainal LR-1718 manufactured by Mitsubishi Rayon Co., Ltd.) was used as the main agent.
(Example 3)
A coating film was formed in the same manner as in Example 1, except that an acrylic polyol having a mass average molecular weight of 36000 and a solid hydroxyl value of 33 mgKOH / g (Acridic 57-773 manufactured by DIC Corporation) was used as the main agent.
Example 4
A coating film was formed in the same manner as in Example 1 except that an acrylic polyol having a mass average molecular weight of 50000 and a solid hydroxyl value of 48 mgKOH / g (ACRICID KU-220 manufactured by DIC Corporation) was used as the main agent.

(Comparative Example 1)
A coating film was formed in the same manner as in Example 1 except that an acrylic polyol (Dainal LR-2572 manufactured by Mitsubishi Rayon Co., Ltd.) having a mass average molecular weight of 9200 and a solid hydroxyl value of 80 mgKOH / g was used as the main agent. .
(Comparative Example 2)
A coating film was formed in the same manner as in Example 1 except that an acrylic polyol having a mass average molecular weight of 20,000 and a solid hydroxyl value of 34 mgKOH / g (Acridic ZHP-1234 manufactured by DIC Corporation) was used as the main agent.
(Comparative Example 3)
A coating film was formed in the same manner as in Example 1 except that an acrylic polyol having a weight average molecular weight of 20000 and a solid hydroxyl value of 34 mgKOH / g (Acridic AL142 manufactured by DIC Corporation) was used as the main agent.

The amount of each component and the evaluation results of Examples 1 to 4 and Comparative Examples 1 to 3 are shown in Table 1 below.

From the evaluation results in Table 1, it was found that the migration resistance of the coating film formed from the acrylic urethane coating is affected by the solid hydroxyl value of the acrylic polyol contained as the main agent. By setting the solid substance hydroxyl value to 30 mgKOH / g or more, a coating film having good migration resistance was obtained. However, from the results of Comparative Example 1, it can be said that when the mass average molecular weight is less than 10,000, the adhesiveness of the coating film becomes insufficient, so that the mass average molecular weight is preferably 10,000 or more.
From the results of Example 3 and Comparative Example 2, it can be said that when an acrylic polyol having a solid hydroxyl value of about 30 mg KOH / g is used, the mass average molecular weight is preferably 30000 or more. From the results of Example 3 and Comparative Example 3, it can be said that when an acrylic polyol having a mass average molecular weight of about 35,000 is used, the solid hydroxyl value is preferably 30 mgKOH / g or more.

  Since the acrylic urethane paint of the present invention forms a coating film with good migration resistance, the components of the packing material are difficult to migrate to the coating film surface when the coated product is shipped and transported. For this reason, it is possible to shorten the curing time until packing, shipping and transportation after painting. Therefore, the present invention is suitable for manufacturing a coated product having a short life cycle that is difficult to secure a sufficient curing time after manufacturing, for example, packed, shipped and transported after a curing period of about a full day. Can be used.

[1] The acrylic urethane paint of the present invention is a two-component acrylic urethane paint containing an acrylic polyol as a main resin and a polyisocyanate compound as a curing agent, and the solid hydroxyl value of the acrylic polyol. It is a but 30 mgKOH / g or more and the weight average molecular weight of the acrylic polyol I der 30000, as a by-resin, the value of weight average molecular weight than the acrylic polyol is small, characterized in that it contains a polycarbonate diol .

[2] The acrylic urethane paint according to [1], wherein the polyisocyanate compound is an aromatic polyisocyanate compound having an aromatic ring.
[3] The acrylic urethane paint according to [2], wherein the polyisocyanate group of the polyisocyanate compound is 0.7 mole equivalent or more and 3.0 mole equivalent or less with respect to 1 mole equivalent of the hydroxyl group of the acrylic polyol.
[4] The acrylic urethane coating according to [2], wherein the polyisocyanate group of the polyisocyanate compound is 1.1 to 1.3 molar equivalents relative to 1 molar equivalent of the hydroxyl group of the acrylic polyol.
[5] The acrylic urethane paint according to [1] , wherein the polycarbonate diol has a number average molecular weight of 500 or more and 2000 or less, and a solid hydroxyl value of 50 mgKOH / g or more and 250 mg / KOH or less.
[6] A two-component acrylic urethane paint containing an acrylic polyol as a main resin and a polyisocyanate compound as a curing agent, wherein the acrylic polyol has a solid hydroxyl value of 30 mgKOH / g or more, The acrylic polyol has a mass average molecular weight of 30,000 or more, and has a weight average molecular weight smaller than that of the acrylic polyol as a secondary resin, a hydroxyl group-containing resin (non-aqueous dispersion resin (resin NAD dispersed in an organic solvent). An acrylic urethane paint characterized by containing
[7] The acrylic urethane paint according to any one of [ 1] to [6] , further containing a solvent.
[8] The acrylic urethane paint according to any one of [1] to [7] , further containing a colorant.
[9] A two-component acrylic urethane paint containing an acrylic polyol as a main resin and a polyisocyanate compound as a curing agent, wherein the acrylic polyol has a solid hydroxyl value of 30 mgKOH / g or more, And the acrylic urethane coating material whose mass average molecular weights of the said acrylic polyol are 70000 or more.
[10] A method for producing a coated product, comprising a step of forming a coating film on the surface of a product or a member constituting the product using the paint according to any one of [1] to [9].
[11] The method for manufacturing a painted product according to [10], wherein the painted product is a gaming machine.

The amount of each component and the evaluation results of Examples 1 to 4 and Comparative Examples 1 to 3 are shown in Table 1 below.

[2] The acrylic urethane paint according to [1], wherein the polyisocyanate compound is an aromatic polyisocyanate compound having an aromatic ring.
[3] The acrylic urethane paint according to [2], wherein the polyisocyanate group of the polyisocyanate compound is 0.7 mole equivalent or more and 3.0 mole equivalent or less with respect to 1 mole equivalent of the hydroxyl group of the acrylic polyol.
[4] The acrylic urethane coating according to [2], wherein the polyisocyanate group of the polyisocyanate compound is 1.1 to 1.3 molar equivalents relative to 1 molar equivalent of the hydroxyl group of the acrylic polyol.
[5] The polycarbonate diol has a number average molecular weight of 500 to 2000 and a solid hydroxyl value of 50 mg KOH / g to 250 mg KOH / g [
Acrylic urethane paint according to 1].
[ 6 ] The acrylic urethane paint according to any one of [1] to [ 5 ], further containing a solvent.
[ 7 ] The acrylic urethane paint according to any one of [1] to [ 6 ], further containing a colorant.
[ 8 ] A two-component acrylic urethane paint containing an acrylic polyol as a main resin and a polyisocyanate compound as a curing agent, wherein the acrylic polyol has a solid hydroxyl value of 30 mgKOH / g or more, And the acrylic urethane coating material whose mass average molecular weights of the said acrylic polyol are 70000 or more.
[ 9 ] A method for producing a coated product, including a step of forming a coating film on the surface of the product or a member constituting the product using the paint according to any one of [1] to [ 8 ].
[ 10 ] The method for producing a coated product according to [ 9 ], wherein the painted product is a gaming machine.

If the solid hydroxyl value of the soft resin is too low, the curing may be insufficient and the migration resistance may be lowered, and if it is too high, the shrinkage of the curing may become strong and affect the adhesion. Therefore, from the viewpoint of forming a coating film with good migration resistance and adhesion, it is preferably 50 mg KOH / g or more and 250 mg KOH / g or less, more preferably 100 mg KOH / g or more and 200 mg KOH / g or less, and more preferably not more than 130 mgKOH / g or more 150 mg KOH / g.

Claims (11)

A two-component acrylic urethane paint containing an acrylic polyol as a main resin and a polyisocyanate compound as a curing agent,
An acrylic urethane paint, wherein the acrylic polyol has a solid hydroxyl value of 30 mgKOH / g or more and a mass average molecular weight of the acrylic polyol of 30000 or more.   The acrylic urethane paint according to claim 1, wherein the polyisocyanate compound is an aromatic polyisocyanate compound having an aromatic ring.   The acrylic urethane paint according to claim 2, wherein the polyisocyanate group of the polyisocyanate compound is 0.7 molar equivalent or more and 3.0 molar equivalent or less with respect to 1 molar equivalent of the hydroxyl group of the acrylic polyol.   The acrylic urethane paint according to claim 2, wherein the polyisocyanate group of the polyisocyanate compound is 1.1 mol equivalent or more and 1.3 mol equivalent or less with respect to 1 mol equivalent of the hydroxyl group of the acrylic polyol.   The acrylic urethane paint according to any one of claims 1 to 4, further comprising a hydroxyl group-containing resin having a mass average molecular weight smaller than that of the acrylic polyol as a secondary resin.   The acrylic urethane paint according to claim 5, wherein the secondary resin is polycarbonate diol. The polycarbonate diol is
The number average molecular weight is 500 or more and 2000 or less,
The acrylic urethane paint according to claim 6, wherein the solid hydroxyl value is 50 mgKOH / g or more and 250 mg / KOH or less.   Furthermore, the acrylic urethane coating material of any one of Claims 1-7 containing the solvent.   Furthermore, the acrylic urethane coating material of any one of Claims 1-8 containing the coloring agent.   The manufacturing method of the coated product which includes the process of forming a coating film in the surface of the product or the member which comprises a product using the coating material of any one of Claims 1-9. The method for manufacturing a painted product according to claim 10, wherein the painted product is a gaming machine.