JP2018188516A - Composition for transparent matte coating material and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for transparent matte coating material which forms a strong coated film that has no glossiness and holds a color tone and a texture of a base material and has waterproof, antifouling and antiseptic effects, and does not contain an additional matting agent.SOLUTION: A composition for aqueous coating material is a composition for aqueous coating material by mixing and stirring 16.7-57.1 pts.mass of an acrylic polyol resin having two or more hydroxyl groups, 1.0-10.0 pts.mass of an isocyanate curing agent having two or more isocyanate functional groups, 20.0-60.0 pts.mass of a composite solvent, and 20.0-60.0 pts.mass of water so that the total amount thereof is 100.0 pts.mass, and converting the stirred substance into emulsion, where the composite solvent is made from 92.0-98.0 pts.mass of saturated hydrocarbon having a boiling point of 150-280°C, and 2.0-8.0 pts.mass of aromatic hydrocarbon having a boiling point of 1-170°C.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a matte transparent coating composition and a method for producing the same, and more particularly, to a transparent coating that has been matted so as not to impair the color and texture of the substrate even when applied to a non-glossy substrate. The present invention relates to a matte transparent coating composition for forming a film and a method for producing the same.

  Usually used for waterproofing, antifouling and antiseptic purposes on base materials such as wood, plaster, unglazed products, etc., which have a unique color and texture and have a non-glossy surface and are used for interior and exterior of buildings and fixtures. When this paint is applied, the article is glossy and the characteristic color and texture are lost, and when the varnish is applied, the original color is changed. In order to prevent this, a clear and matte paint has been required.

  Conventionally, such transparent matte paints include those containing granular silica as a matting agent (see, for example, Patent Document 1), those containing gel method silica particles (see, for example, Patent Document 2), and hydrophobic silica erosions. The thing containing gel (for example, refer patent document 3) and the thing containing a transparent resin bead (for example, refer patent document 4) were disclosed.

  However, since these paints must contain a large amount of matting agent in order to obtain a sufficient matting effect, the viscosity of the paint rises, and therefore a large amount of solvent dilution is required at the time of application, and it is easy to spill. Accordingly, a matting agent has to be added at the time of use, so that the workability of coating is deteriorated, and the obtained coating material has a problem that it becomes brittle because the binder resin component is small.

JP, 2006-204465, A Japanese Patent Laying-Open No. 2005-225928 JP2012-251168A JP-A-6-262133

  The present invention has been made to solve such a problem, and even when applied to a base material having a specific color tone and texture without a glossy surface, the color tone of the base material does not have a glossiness. It is an object of the present invention to provide a transparent matting paint composition that forms a strong coating film having waterproof, antifouling, and antiseptic effects while retaining its texture and does not contain a separate matting agent.

Another object of the present invention is to provide a matting paint composition that prevents the coating film from becoming brittle or rough due to the matting filler.
Furthermore, since the present invention does not use a matting filler, it prevents the paint viscosity from increasing due to the filler, thereby preventing the amount of solvent used and the coating workability from decreasing due to increased dripping. It aims at providing the manufacturing method of the composition for coating materials.

The composition for matte transparent paint of the present invention to solve the problem is 16.7-57.1 parts by mass of acrylic polyol resin having two or more hydroxyl groups (rounded off to the second decimal place, the same shall apply hereinafter), 2 or more 1.0 to 10.0 parts by mass of an isocyanate curing agent having an isocyanate functional group, 20.0 to 60.0 parts by mass of a composite solvent, and 20.0 to 60.0 parts by mass of water, the total amount being 100.0 masses. A composition for water-based paint emulsified by mixing and stirring so as to be part, and arranging the acrylic polyol resin and the isocyanate curing agent so as to be contained in different droplets,
When the total mass of the composite solvent is 100.0 parts by mass, 92.0 to 98.0 parts by mass of saturated hydrocarbons having a boiling point of 150 to 280 ° C. and aromatic carbonization having a boiling point of 135 to 170 ° C. The coating film formed by applying 2.0 to 8.0 parts by mass of hydrogen, applying the coating composition to a substrate, and drying and solidifying the film does not have a specific color and has a mirror surface with an angle of 60 ° on the surface. The gloss is 50% or less, the visible light transmittance of a coating film having a film thickness of 0.1 mm is 65% or more.

  The saturated hydrocarbon is one or more of saturated hydrocarbons having 9 to 16 carbon atoms or mineral spirit, and the aromatic hydrocarbon is xylene, 1,2,4-trimethylbenzene, 1, 3, 5- One or more selected from trimethylbenzene, ethylbenzene, and propylbenzene are preferable.

The acrylic polyol may be one or more selected from monomers and oligomers of acrylic esters having two or more hydroxyl groups, or co-oligomers of acrylic esters and isocyanate curing agents.
The isocyanate curing agent is preferably an aliphatic isocyanate having two or more isocyanate groups.

  Furthermore, the manufacturing method of the composition for matte transparent paints of this invention is 20.0-60.0 mass parts of acrylic polyol resin which has a 2 or more hydroxyl group, 20.0-60.0 mass parts of composite solvents, and water 20 Add 0.06 to 60.0 parts by mass to 100.0 parts by mass, stir the resulting mixture to produce a polyol suspension, and an isocyanate having two or more isocyanate functional groups Add 20.0-60.0 parts by mass of the curing agent, 20.0-60.0 parts by mass of the composite solvent, and 20.0-60.0 parts by mass of water to make 100 parts by mass, and stir the resulting mixture. An isocyanate suspension production stage for producing an isocyanate suspension by suspending, and mixing 5.0 to 20.0 parts by mass of the isocyanate suspension with 100.0 parts by mass of the polyol suspension and stirring the paint Composition The composite solvent has a boiling point of 150 to 280 ° C. and a saturated hydrocarbon of 92.0 to 98.98, when the total mass of the composite solvent is 100.0 parts by mass. It consists of 2.0 to 8.0 parts by mass of 0 parts by mass and an aromatic hydrocarbon having a boiling point of 135 to 170 ° C.

The present invention provides a strong coating film that has a waterproof, antifouling and antiseptic effect while retaining the color tone and texture of the base material even when applied to a base material having a specific color tone and texture without having a glossy surface. It is possible to provide a matte transparent coating composition capable of forming a surface and a method for producing the same.
The matte transparent coating composition of the present invention does not add a separate matting filler, so that the coating film does not become brittle or the surface is not rough and can form a beautiful and strong coating film. .

Furthermore, the matte transparent paint composition of the present invention does not include a separate matting filler, thus preventing an increase in the viscosity of the paint due to the filler and increasing the amount of solvent used and dripping due to the increase in viscosity. A decrease in workability can be prevented.
In addition, the conventional paint containing a matting filler had to be adjusted at the time of use because the filler was precipitated, but the matte transparent paint composition of the present invention does not use a filler. Therefore, it is not necessary to prepare at the time of use, and the coating composition can be stored stably.

It is a block diagram which shows the manufacturing process of the matte transparent coating composition of this invention, and the manufacturing process of a matte transparent coating using this coating composition.

  The matte transparent coating composition of the present invention is an aqueous coating composition in which a coating material and a composite solvent that form a transparent coating film are suspended in water to be emulsified, and is a composite solvent used as a solvent for an aqueous coating By controlling the composition of the film, the solvent composition changes as the solvent evaporates, and at the end of the film formation process, a solvent with low solubility remains so that fine irregularities are intentionally formed on the surface of the coating film. It is made to make the surface of the paint film matt.

Below, with reference to drawings, the matte transparent coating composition of this invention and its manufacturing method are demonstrated in detail.
Although the coating raw material which forms the transparent coating film used by this invention will not be restrict | limited especially if the objective of this invention is suitable, a urethane resin is preferable and acrylic urethane resin which is 1 type in a urethane resin is more preferable.

  As a most preferable example, the resin raw material is 16.7 to 57.1 parts by mass of an acrylic polyol having two or more hydroxyl groups, 1.0 to 10.0 parts by mass of an isocyanate curing agent having two or more isocyanate functional groups, and a solvent 20 0.060.0 parts by mass and 20.0-60.0 parts by mass of water (rounded to the first decimal place) are mixed and stirred so that the total amount becomes 100.0 parts by mass, and the acrylic polyol Examples of the composition for water-based paints that are emulsified by being disposed so that the resin and the isocyanate curing agent are contained in different droplets.

[Acrylic polyol]
The acrylic polyol used here is at least one selected from a monomer of an acrylic ester having two or more hydroxyl groups, an oligomer, and a co-oligomer of an acrylic ester and an isocyanate curing agent having two or more isocyanate groups. it can.

  As one of the preferred embodiments of the present invention, there can be mentioned an example in which a polyol having a relatively large molecular weight composed of an acrylic ester oligomer having a hydroxyl group is used and polymerized and solidified in combination with a low molecular weight aliphatic polyisocyanate curing agent. However, the acrylic urethane resin of the present invention is not limited to this.

  A variety of acrylic polyols can be used, and any acrylic polyol can be used as long as it can be used in the present invention. For example, acrylic polyol # 6000 (Taisei Chemical Co., Ltd.) can be illustrated as a specific example, but this is merely an example, and the present invention is not limited thereto. Since the polyol for acrylic urethane resin is well-known to those skilled in the art, detailed description is abbreviate | omitted.

  Here, the amount of the acrylic polyol having two or more hydroxyl groups is 16.7-57.1 parts by mass (rounded off to the second decimal place when the weight of the composition for water-based paint is 100.0 parts by mass, The same shall apply hereinafter), more preferably 20.0 to 50.0 parts by mass, and most preferably 20.0 to 40.0 parts by mass.

  Acrylic polyol constitutes the main component of the coating film, and if the content is less than 16.7 parts by mass, the resin component is decreased and the solvent is relatively increased, so that a coating film with sufficient thickness may not be formed. It is not preferable. On the other hand, if the acrylic polyol exceeds 57.1 parts by mass, the degree of crosslinking by the polyisocyanate may be reduced and a strong coating film may not be formed, and a large amount of resin components may be deposited early to ensure matte and transparency. This is not preferable because it may be difficult to control the opposite physical properties.

[Polyisocyanate]
The isocyanate curing agent having two or more isocyanate groups is not particularly limited as long as it can form a polymer by crosslinking reaction with an acrylic polyol having two or more hydroxyl groups, but an aliphatic isocyanate compound having two or more isocyanate groups can be used. More preferred. As a particularly preferred example, hexamethylene diisocyanate and its derivatives and isophorone disociocyanate can be exemplified, but the isocyanate curing agent used in the present invention is not limited thereto.

Here, the amount of the isocyanate curing agent is preferably 1.0 to 10.0 parts by mass, and more preferably 1.0 to 7.5 parts by mass.
If the amount of the isocyanate curing agent is less than 1.0 part by mass, the degree of crosslinking with the polyol may be reduced and a tough resin may not be formed. If the amount exceeds 10.0 parts by mass, an unreacted isocyanate curing agent remains. In addition, there is a possibility that the polymerization proceeds too quickly, and the resin component is polymerized and precipitated at an early stage, so that the transparency of the formed coating film may be lowered.

  Moreover, the property of the coating film to be produced often depends on the ratio of the mass of the isocyanate curing agent to the mass of the acrylic polyol. In the present invention, the mass ratio may be in the range of 1:20 to 1: 5. If the mass ratio of the isocyanate curing agent, acrylic polyol, and isocyanate curing agent is less than 1:20, a coating film having sufficient hardness may not be formed. If the mass ratio exceeds 1: 5, the coating becomes too hard. May become brittle and unreacted isocyanate curing agent may remain.

  Further, since the acrylic polyol having two or more hydroxyl groups and the polyisocyanate react when mixed, the coating composition emulsion is preferably arranged so as to be contained in separate droplets. That is, it is preferable that the acrylic polyol and the polyisocyanate are separately dissolved in a solvent to be emulsified with water and then mixed.

[Solvent and reaction]
The solvent used in the present invention is preferably a composite solvent consisting of an aliphatic saturated hydrocarbon having a boiling point of 150 to 280 ° C. and an aromatic hydrocarbon having a boiling point of 135 to 170 ° C.
Specific examples of saturated hydrocarbons include, for example, aliphatic hydrocarbons from nonane (boiling point 151 ° C.) to hexadecane (boiling point 287 ° C.), or mineral spirits (boiling point 150- One or more mixed solvents selected from 208 ° C. can be exemplified (the mixed solvent having a predetermined boiling range may include a solvent having a boiling point outside the predetermined range).

  Examples of the aromatic hydrocarbon include xylene (boiling points: o-xylene, 144 ° C., m-xylene, 139 ° C., p-xylene, 138 ° C.), 1,2,4-trimethylbenzene (boiling point 169 ° C.), 1 One or more selected from 3,5-trimethylbenzene (boiling point 165 ° C.), ethylbenzene (boiling point 136 ° C.), or propylbenzene (boiling point 159 ° C.) can be exemplified, but it is not limited thereto. Aromatic hydrocarbons generally have a higher solvency than aliphatic saturated hydrocarbons.

The composition for transparent coatings of the present invention has an aliphatic saturated hydrocarbon of 92.0 to 98.0 when the ratio of saturated hydrocarbon to aromatic hydrocarbon is 100.0 parts by mass of the solvent. It is preferably 2.0 to 8.0 parts by mass of an aromatic hydrocarbon and 93.0 to 97.0 parts by mass of an aliphatic saturated hydrocarbon and 3.0 to 7.0 parts by mass of an aromatic hydrocarbon. It is more preferable that
If the aromatic hydrocarbon exceeds 8.0 parts by mass and the aliphatic saturated hydrocarbon is less than 92 parts by mass, the solubility of the solvent becomes too high and the matte may not be frosted. If it exceeds 0.0 part by mass and the aromatic hydrocarbon is less than 2.0 fats, the solubility of the solvent becomes too low and a good coating composition or / and coating film may not be formed.

[Manufacture of paint composition]
FIG. 1 is a block diagram showing a process for producing a matte transparent paint composition of the present invention and a process for producing a matte transparent paint using the paint composition.
As shown in FIG. 1, the manufacturing process of the composition for transparent coatings of this invention consists of a polyol suspension manufacturing stage (S-1), an isocyanate suspension manufacturing stage (S-2), and a matte transparent coating. And a composition production stage (S-3).

  In the polyol suspension production stage (S-1), 20.0 to 60.0 parts by mass of an acrylic polyol resin having two or more hydroxyl groups, 20.0 to 60.0 parts by mass of a composite solvent, and 20.0 water. To 60.0 parts by mass to 100.0 parts by mass, and the resulting mixture is stirred and emulsified to produce a polyol suspension.

  In the isocyanate suspension production stage (S-2), 20.0 to 60.0 parts by mass of an isocyanate curing agent having two or more isocyanate groups, 20.0 to 60.0 parts by mass of a composite solvent, and water 20.0-60.0 mass parts is added, it is made 100 mass parts, and the produced | generated mixed liquid is stirred and suspended, it can emulsify and an isocyanate suspension can be manufactured.

Further, in the matte transparent paint composition production step (S-3), 5.0 to 20.0 parts by mass of an isocyanate suspension is mixed with 100.0 parts by mass of a polyol suspension and stirred to make the matte transparent. A coating composition can be produced.
Here, when the total mass is 100.0 parts by mass, the composite solvent has 92.0 to 98.0 parts by mass of saturated hydrocarbon having a boiling point of 150 to 280 ° C. and aromatic carbonization having a boiling point of 135 to 170 ° C. It preferably consists of 2.0 to 8.0 parts by mass of hydrogen.

Further, the matte transparent paint composition of the present invention contains water-based paint additives known to those skilled in the art such as a polymerization initiator, a reaction accelerator, an emulsifier, a thickener, a light stabilizer, and an excess isocyanate neutralizer. be able to.
The matte transparent paint composition of the present invention produced as described above is an aqueous paint which is an emulsion contained in droplets in which an acrylic polyol resin and an isocyanate curing agent are different, and the emulsion is stable under the conditions. Can be stored stably under.

  The composition for matte transparent coatings produced as described above has 16.7-57.1 parts by weight of polyol resin having two or more hydroxyl groups (rounded to the first decimal place, the same shall apply hereinafter), and two or more isocyanate groups. The isocyanate curing agent having 1.0 to 10.0 parts by mass, the solvent 20.0 to 60.0 parts by mass, and the water 20.0 to 60.0 parts by mass are mixed so that the total amount becomes 100.0 parts by mass. The composition for water-based paints, which is emulsified by being stirred and arranged so that the acrylic polyol resin and the isocyanate curing agent are contained in different droplets.

  In the aqueous coating composition, the total mass of the acrylic polyol resin and the isocyanate curing agent is 20 to 60 parts by mass, and the mass ratio of the acrylic polyol resin and the isocyanate curing agent is 62.5: 37. The mass ratio of the composite solvent to water may be in the range of 20.0: 60.0 to 60.0: 20.0.

[Manufacture of coating film]
In the matte transparent coating composition of the present invention, the acrylic polyol and the isocyanate curing agent are separately dissolved in the composite solvent as described above, emulsified with water, mixed, and then applied to the substrate and dried. As a result, the emulsion is peptized and separated into a coating material solution and water, and a polymerization reaction between the acrylic polyol and the polyisocyanate is started. On the other hand, although water and a solvent are evaporated separately, water with a low boiling point evaporates first.

When the emulsion is peptized, the acrylic polyol and the polyisocyanate curing agent are mixed, and the polymerization reaction proceeds to start the formation of the acrylic urethane resin coating. At the same time, the saturated hydrocarbon and aromatic hydrocarbon are mixed. From the solvent, which is a composite solvent, aromatic hydrocarbons having a high solubility and a low boiling point evaporate first, so that the solubility of the composite solvent gradually decreases, and unreacted or unreacted resin components are precipitated. It deposits on the surface of the coating film, dullness occurs and the surface becomes matte.
An object of the present invention is to control the amount and composition of the composite solvent so as to select conditions under which the surface is matted but the transparency and strength of the coating body are not lost.

[Coating]
The matte transparent coating composition of the present invention was applied to a substrate, dried and solidified, whereby 69.2 to 98.4% by mass of acrylic polyol and 1.6 to 30.8% by mass of polyisocyanate were polymerized. Acrylic urethane resin can be provided.
The present invention controls the amount and composition of the solvent so that it is frosted but the transparency and strength are not lost, and the resulting coating does not have a specific color and its surface In the present invention, a matte transparent coating composition having a specular gloss at an angle of 60 ° of 50 or less and a visible light transmittance of 65% or more for a coating film having a film thickness of 0.1 mm is provided.

  If the coating surface has a specular gloss at an angle of 60 ° of 50 or less on the surface, the coating film gives a sufficient matte feeling, and the visible light transmittance is 65% or more at a normal coating film thickness of 0.1 mm (visible). If the light transmittance is 65%, which is a degree of transparency of ordinary glass), it can be judged to be frosted and transparent.

[Production Example 1] Production of composite solvent When the total mass of the composite solvent is 100.0 parts by mass, 87.6 parts by weight of mineral spirit, 7.4 parts by weight of nonane, 1.5 parts by weight of xylene, A composite solvent V was produced by mixing 2.1 parts by weight of 1,2,4-trimethylbenzene and 1.3 parts by weight of ethylbenzene.
The mass ratio of the saturated aliphatic hydrocarbon to the aromatic hydrocarbon in the composite solvent V is 95.0: 5.0.

As described above, composite solvents V to Z were produced by changing the ratio of the mass of the saturated aliphatic hydrocarbon and the mass of the aromatic hydrocarbon as shown in Table 1.

[Example 1]
(1) Polyol suspension production stage 40.0 parts by mass of the acrylic polyol resin, 30.0 parts by mass of the composite solvent V shown in Table 1, and 30.0 parts by mass of water are mixed and stirred to form an emulsion. The polyol suspension of Example 1 was prepared.
(2) Production stage of siasinate suspension 60.0 parts by mass of isocyanate curing agent, 20.0 parts by mass of the above composite solvent V, and 20.0 parts by mass of water were added to make 100 parts by mass, and the resulting mixed liquid was The isocyanate suspension of Example 1 was prepared by stirring and suspending and emulsifying.
(3) Composition production stage for matte transparent paint 100 mass parts of the polyol suspension and 10.0 mass parts of the isocyanate suspension are mixed and stirred to produce the matte transparent paint composition production of Example 1. did.

[Examples 2 to 7] Examination of limit composition range of matte transparent paint composition The limit composition range of the matte transparent paint composition obtained by the production method according to claim 5 was examined.
(1) Production of polyol suspension Three types of polyol suspensions A1 to A3 shown in Table 2 were produced by mixing the acrylic polyol resin, the above composite solvent V, and water.

(2) Production of Isocyanate Suspension Three kinds of isocyanate suspensions B1 to B3 shown in Table 3 were produced by mixing an aliphatic isocyanate curing agent, the above composite solvent V, and water.

(3) Manufacture of matte transparent coating composition As in Example 1, except that three types of polyol suspensions shown in Table 2 and each of the three types of isocyanate suspensions shown in Table 3 are 100: 20. Further, from 18 kinds of coating compositions obtained by mixing at a ratio of 100: 5, a matte transparent coating composition having 6 kinds of limit composition concentrations in Examples 2 to 7 shown in Table 4 was produced. .

Table 5 shows the masses (parts) of polyol, isocyanate, composite solvent V, and water contained in 100 parts by mass of the matte transparent coating composition of Examples 2 to 7.

  As shown in Table 5, the composition range of the coating composition obtained by the method according to claim 1 is such that, as shown in claim 1, the total amount of the composition is 100.0 parts by mass. Range of 16.7-57.1 parts by weight of polyol resin, 1.0-10.0 parts by weight of isocyanate curing agent, 20.0-60.0 parts by weight of composite solvent, and 20.0-60.0 parts by weight of water (The remaining twelve critical coating compositions are also within this range).

[Claims 8 to 15 and Comparative Examples 1 to 8] Manufacture of Samples for Testing Physical Properties of Coating Films Similar to the method of Claim 1, except that acrylic polyol resin and isocyanate curing agent were mixed as shown in Table 6. The mass ratio of the polyol suspension to the isocyanate suspension and the mass ratio of the aliphatic saturated hydrocarbon to the aromatic hydrocarbon of the composite solvent were changed with Example 1 as the center value, and Examples 8 to 15 The compositions for matte transparent paints of Comparative Examples 1-8 were produced.

Table 7 shows the compositions of the matte transparent paint compositions of Examples 1 and 8 to 15 and Comparative Examples 1 to 8.

[Evaluation of matte transparent coating film]
(1) Preparation of materials for evaluation Using a spray coater on a wooden plywood panel that has been polished and finished horizontally with the matte transparent paint compositions of Examples 1 to 15 and Comparative Examples 1 to 8 produced above. Te was applied so that the coating amount of 100 g / m ^2, at room temperature in the dark for 7 days under ventilation drying, solidifying to produce a matte clear coat of the present invention, for the specular gloss and pencil hardness measured A sample was used.
Further, a circular glass plate having a diameter of 10 cm was placed on a part of the wooden plywood panel to prepare a sample for measuring light transmittance.

(2) Evaluation method a) Specular gloss The reflectance of incident light having an angle of 60 ° with respect to the normal to the coating film surface using a gloss meter (JIS K 5600-4-6 specular gloss at 60 °) According to the above).
The reflectivity of 60 ° incident light of 40% or less was evaluated as ◯, 40% and 50% or less as Δ, Δ exceeding 50% as ×, and ○ and Δ as acceptable.
Measuring equipment: Gloss Checker IG-320 (Horiba)
(B) Light transmittance The light transmittance T ₀ (%) of a sample for evaluation in which a paint was applied to a glass plate was measured with a glass transmittance meter, and the film thickness A (mm) of the coating film was measured with a laser microscope. . The light transmittance T of a coating film having a thickness of 0.01 (mm) was converted according to the following formula.
T = 100− (100−T ₀ ) × 0.01 ÷ A
The light transmittance T of a coating film of 0.01 (mm) is 75% (about the windshield of an automobile) or more, ◯, 65% (normal glass) or more and less than 75% is △, and less than 65% is ×. , ○ and △ were regarded as acceptable.
Measuring instrument Light transmittance: Glass transmittance meter MJ-TM110 (Sato Corporation)
Film thickness: Laser microscope VK-X250 (Keyence)
(C) Pencil hardness Using an Pencil hardness tester, the pencil hardness according to JIS K 5600 of the sample coated with the above matte transparent paint was measured. The hardness of the coating film of the present invention is not the subject of the invention, but the pencil hardness is measured as a measure of the properties of the coating film. X, and ○ and Δ were acceptable.
Measuring equipment: Pencil hardness tester (All Good Co., Ltd.)

The amount (mass part) of the coating film obtained from 100 parts by mass of the matte transparent coating composition of Examples 1 to 15 and Comparative Examples 1 to 8, the amount of acrylic polyol component in the coating film (mass part), and the specular gloss Table 8 shows the evaluation results of degree, light transmittance, and pencil hardness.

(3) Comparison of amount of acrylic polyol Table 9 shows a comparison between the mass number of the acrylic polyol contained in 100 parts by mass of the matte transparent coating composition of the present invention and the generated matte transparent coating.

  As shown in Table 9, the coating materials produced from the coating compositions of Examples 1, 3, 6, 8, and 9 had a specular gloss (50 or less) within the acceptable range, light transmittance (thickness 0.1 mm). 65% or more) and pencil hardness (HB or more), but the coating film produced from Comparative Example 1 in which the acrylic polyol content exceeds the upper limit (57.1 parts by mass) has a specular gloss value of the reference value. The light transmittance was below the reference value. Moreover, the coating film manufactured from the comparative example 2 whose acrylic polyol content is less than the lower limit (16.7 parts by mass) has a specular glossiness of a reference value or more and a light transmittance of a reference value or less. The pencil hardness was also B and did not reach the standard value.

(4) Comparison of isocyanate amount Table 9 shows a comparison between the mass number of the aliphatic polyisocyanate contained in 100 parts by mass of the matte transparent paint composition of the present invention and the produced matte transparent paint.

  As shown in Table 10, the coating films produced from the coating compositions described in Examples 1, 2, 5, 10, and 11 have a specular gloss (50 or less) and light transmittance (thickness within an acceptable range). 0.1 mm and 65% or higher) and pencil hardness (HB or higher). However, the light transmittance of the coating material of Comparative Example 3 in which the mass of the isocyanate curing agent of Comparative Example 3 exceeded the upper limit (10.0 parts by mass) was below the reference value. Moreover, the coating film manufactured from the comparative example 4 whose mass number of aliphatic polyisocyanate is less than an upper limit (1.0 mass part) has low performance as a coating film, pencil hardness is B, and specular glossiness is also a reference | standard. The value (50 or less) was not reached.

(5) Ratio of acrylic polyol amount and isocyanate amount Table of comparison of mass ratio of acrylic polyol suspension and aliphatic polyisocyanate curing agent suspension contained in the matte transparent coating composition of the present invention 11 shows.

As shown in Table 11, the coating films produced from the coating compositions described in Examples 1, 2, 4, 7, 8, 12, and 13 have a specular gloss (50 or less) within the acceptable range and light transmission. Rate (65% or more at a thickness of 0.1 mm) and pencil hardness (HB or more). However, the coating film produced from the coating composition of Comparative Example 6 in which the ratio of the polyol suspension to the isocyanate suspension was not less than the upper limit value formed a strong coating film, but the content of the isocyanate curing agent was Since it was too much, the specular gloss was 50% or more and the matte was insufficient. Moreover, the coating film manufactured from the coating composition of Comparative Example 5 in which the ratio of the isocyanate curing agent is lower than the lower limit cannot form a coating film having sufficient hardness, the pencil hardness is B, and the light transmittance is also high. It was below the standard value.

(6) Examination of solvent composition Table 12 shows a comparison between aliphatic hydrocarbons and aromatic hydrocarbons in the composite solvent used in the present invention. The solvents of Comparative Example 8, Examples 15, 1, 14, and Comparative Example 7 correspond to composite solvents Z, X, V, W, and Y (see Table 1).

  As shown in Table 12, the coating films produced from the coating compositions described in Examples 1, 14, and 15 showed excellent specular gloss, light transmittance, and pencil hardness above the reference value. The coating film produced from the coating composition described in Comparative Example 7 in which the ratio of the aliphatic hydrocarbon is less than the limit value, although forming a tough coating film, is not sufficiently matte and exceeds the standard specular gloss. In the coating composition described in Comparative Example 8 in which the ratio of the aliphatic hydrocarbon exceeded the limit value, the dissolving power of the composite solvent was insufficient, and an acrylic polyol suspension could not be produced.

  As mentioned above, although preferred embodiment regarding this invention was described, this invention is not limited to the said embodiment, All the changes in the range which does not deviate from the technical scope to which this invention belongs are included.

Or mow matte clear coating composition of the present invention to solve the problems, an acrylic polyol resin having two or more hydroxyl groups, the composite solvent, and a polyol suspension comprising water, an isocyanate having two or more isocyanate groups For aqueous coatings containing an isocyanate suspension comprising a curing agent, the above-mentioned composite solvent, and water, and a polymerization initiator, reaction accelerator, emulsifier, thickener, light stabilizer, and neutralizing agent for excess isocyanate as optional components. Additives are mixed and agitated, and the acrylic polyol resin and the isocyanate curing agent are arranged so as to be contained in different droplets.
When the total of the polyol suspension and the isocyanate suspension is 100.0 parts by mass, the water-based coating composition is 16.7 to 57.1 parts by mass (the second decimal point). rounded off position, hereinafter the same), the isocyanate curing agent 1.8 to 6.7 parts by weight, consists of the composite solvent 20.0 to 60.0 parts by weight, and water 20.0 to 60.0 parts by weight,
When the total mass of the composite solvent is 100.0 parts by mass, 92.0 to 98.0 parts by mass of saturated hydrocarbon having a boiling point of 150 to 280 ° C. and aromatic having a boiling point of 135 to 170 ° C. And 2.0 to 8.0 parts by mass of hydrocarbon,
The coating film formed by applying the aqueous coating composition on a substrate, drying and solidifying has no specific color, the specular gloss at an angle of 60 ° on the surface is matte to 50% or less, and the film thickness is The visible light transmittance of the coating film of 0.1 mm is 65% or more.

As a most preferred example, the resin raw material is 16.7 to 57.1 parts by mass of an acrylic polyol having two or more hydroxyl groups, 1.8 to 6.7 parts by mass of an isocyanate curing agent having two or more isocyanate functional groups, and a solvent 20 0.060.0 parts by mass and 20.0-60.0 parts by mass of water (rounded to the first decimal place) are mixed and stirred so that the total amount becomes 100.0 parts by mass, and the acrylic polyol it can be exemplified by the deployment so that the resin and the isocyanate curing agent is contained in different Do that droplet aqueous coating composition emulsified.

Here, the amount of the isocyanate curing agent is preferably 1.0 to 10.0 parts by mass, and more preferably 1.8 to 6.7 parts by mass.
If the amount of the isocyanate curing agent is less than 1.0 part by mass, the degree of crosslinking with the polyol may be reduced and a tough resin may not be formed. If the amount exceeds 10.0 parts by mass, an unreacted isocyanate curing agent remains. In addition, there is a possibility that the polymerization proceeds too quickly, and the resin component is polymerized and precipitated at an early stage, so that the transparency of the formed coating film may be lowered.

The composition for matte transparent coatings produced as described above has 16.7-57.1 parts by weight of polyol resin having two or more hydroxyl groups (rounded to the first decimal place, the same shall apply hereinafter), and two or more isocyanate groups. The isocyanate curing agent having 1.8 to 6.7 parts by mass, the solvent 20.0 to 60.0 parts by mass, and the water 20.0 to 60.0 parts by mass are mixed so that the total amount becomes 100.0 parts by mass. , stirring, is and the aqueous coating composition deployed to and emulsified as acrylic polyol resin and said isocyanate curing agent is contained in different Do that droplets.

[Example 1]
(1) Polyol suspension production stage 40.0 parts by mass of the acrylic polyol resin, 30.0 parts by mass of the composite solvent V shown in Table 1, and 30.0 parts by mass of water are mixed and stirred to form an emulsion. The polyol suspension of Example 1 was prepared.
(2) Lee isocyanate suspension and manufacturing steps isocyanate curing agent 60.0 parts by weight and the composite solvent V20.0 parts by weight of water 20.0 parts by weight, added were 100 parts by mass, the resulting mixture Was suspended and emulsified to produce the isocyanate suspension of Example 1.
(3) Matte transparent coating composition production stage The polyol suspension 100 . 0 part by mass and 10.0 parts by mass of an isocyanate suspension were mixed and stirred to produce the matte transparent coating composition composition of Example 1.

As shown in Table 5, the composition range of the coating composition obtained by the method according to claim 1 is such that, as shown in claim 1, the total amount of the composition is 100.0 parts by mass. polyol resin 16.7 to 57.1 parts by weight, an isocyanate curing agent 1.8 to 6.7 parts by weight, the composite solvent from 20.0 to 60.0 parts by weight, and the range of water from 20.0 to 60.0 parts by weight (The remaining twelve critical coating compositions are also within this range).

Claims (8)

16.7 to 57.1 parts by mass of an acrylic polyol resin having two or more hydroxyl groups (rounded off to the first decimal place, the same shall apply hereinafter) 1.0 to 10.0 parts by mass of an isocyanate curing agent having two or more isocyanate groups, 20.0 to 60.0 parts by mass of a composite solvent and 20.0 to 60.0 parts by mass of water are mixed and stirred so that the total amount becomes 100.0 parts by mass, and the acrylic polyol resin and the isocyanate are cured. A composition for water-based paint emulsified by being placed so as to be contained in different droplets of the agent,
When the total mass of the composite solvent is 100.0 parts by mass, 92.0 to 98.0 parts by mass of saturated hydrocarbon having a boiling point of 150 to 280 ° C. and aromatic having a boiling point of 135 to 170 ° C. And 2.0 to 8.0 parts by mass of hydrocarbon,
The coating film formed by applying the coating composition on a substrate, drying and solidifying has no specific color, and the specular gloss at an angle of 60 ° on the surface is matte to 50% or less, and the film thickness is 0. A composition for matte transparent paint, wherein the visible light transmittance of a coating film of 1 mm is 65% or more.   The saturated hydrocarbon is one or more of saturated hydrocarbons having 9 to 16 carbon atoms or mineral spirits, and the aromatic hydrocarbon is xylene, 1,2,4-trimethylbenzene, 1, 3, 5 The matte transparent paint composition according to claim 1, wherein the composition is one or more selected from trimethylbenzene, ethylbenzene, and propylbenzene.   2. The matte transparent according to claim 1, wherein the acrylic polyol is at least one selected from a monomer or oligomer of an acrylic ester having two or more hydroxyl groups, or a co-oligomer of an acrylic ester and a polyisocyanate curing agent. Composition for paint.   The matte transparent coating composition according to claim 1, wherein the isocyanate curing agent is an aliphatic isocyanate having two or more isocyanate groups. A method for producing the matte transparent paint composition according to claim 1,
Add 20.0 to 60.0 parts by mass of an acrylic polyol resin having two or more hydroxyl groups, 20.0 to 60.0 parts by mass of a composite solvent, and 20.0 to 60.0 parts by mass of water to add 100. A polyol suspension production stage in which 0 part by mass and the produced mixed liquid is stirred to produce a polyol suspension;
20.0 to 60.0 parts by mass of an isocyanate curing agent having two or more isocyanate groups, 20.0 to 60.0 parts by mass of a composite solvent, and 20.0 to 60.0 parts by mass of water 100 parts by mass, an isocyanate suspension production step of stirring and suspending the produced mixture to produce an isocyanate suspension;
A paint element biological production stage in which 5.0 to 20.0 parts by mass of the isocyanate suspension is mixed with 100.0 parts by mass of the polyol suspension and stirred to produce a paint composition;
Have
When the total mass of the composite solvent is 100.0 parts by mass, 92.0 to 98.0 parts by mass of saturated hydrocarbon having a boiling point of 150 to 280 ° C. and aromatic having a boiling point of 135 to 170 ° C. A method for producing a matte transparent paint composition, characterized by comprising 2.0 to 8.0 parts by mass of a hydrocarbon.   The saturated hydrocarbon is one or more of saturated hydrocarbons having 9 to 16 carbon atoms or mineral spirits, and the aromatic hydrocarbon is xylene, 1,2,4-trimethylbenzene, 1, 3, 5 The method for producing a matte transparent coating composition film according to claim 5, wherein the composition film is one or more of trimethylbenzene, ethylbenzene, and propylbenzene.   The acrylic polyol is one or more of a monomer or oligomer of an acrylic ester having two or more hydroxyl groups, or a co-oligomer of an acrylic ester having two or more hydroxyl groups and a polyisocyanate having two or more isocyanate functional groups. The method for producing a matte transparent paint composition according to claim 5. 6. The method for producing a matte transparent coating composition according to claim 5, wherein the isocyanate curing agent is an aliphatic isocyanate having two or more isocyanate groups.

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