JP5861101B2 - Painted - Google Patents

Description

The present invention relates to a coated product in which a coating film is formed with a low-temperature curable water / oil-repellent resin composition used to form a water / oil repellency coating film.

  In recent years, water and oil repellency functions such as water stains, scales, dirt and sweat are less likely to adhere to and are easy to remove, mainly on interior components (kitchens, baths, toilets, etc.) and home appliances. The demand for such products is increasing. Usually, a film having a water contact angle of 90 ° or more and an oil (especially oleic acid) contact angle of 40 ° or more is called a water / oil repellent coating, and such a water / oil repellent coating is used. Development of a coating material for forming the film has been actively conducted.

As such a resin composition for a coating material having excellent water and oil repellency, those having a fluororesin or a silicone compound as a main component are generally used, and a commonly used fluororesin is -CF ₂ A skeleton such as —CFX— or —CF ₂ —CF ₂ — is introduced.

  For example, Patent Document 1 proposes a water / oil repellent coating composition using an acrylic resin and a fluororesin. Patent Document 2 proposes a water- and oil-repellent fluororesin material having excellent adhesion to a substrate. Further, Patent Document 3 proposes a coating composition comprising a water- and oil-repellent fluororesin curable composition.

  However, the resin composition mainly composed of the fluororesin as described above has a problem that the formed coating film is soft, and there is also a problem in the abrasion resistance required at the time of wiping, and it is sufficiently durable. There is a problem that it is very difficult to secure the coating film with sufficient hardness and dirt wiping property.

On the other hand, as a water- and oil-repellent resin widely studied along with the fluororesin, a silicone resin containing a Si—CH ₃ group can be given. For example, Patent Document 4 proposes a surface treatment composition using a water-repellent hydrolyzable silane compound. Patent Document 5 proposes a water- and oil-repellent surface treatment agent using a silicon-based compound.

  However, silicon-based compound resins are superior to fluorine-based resins in terms of wiping off dirt (abrasion resistance), but the coating film applied to a substrate such as plastic is softer than the substrate. There was a problem that the hardness was inferior under the influence of. In addition, the abrasion resistance is superior to that of fluorine, but it does not reach a sufficient durability.

JP 63-199211 A JP-A-10-329280 Japanese Patent Laid-Open No. 2002-309054 JP 2000-129247 A Japanese Patent Laid-Open No. 2002-12859

  As mentioned above, in a coated product that has a water / oil-repellent coating on its surface that is difficult to remove and easy to remove, the surface has to be cleaned (dry wipe, water wipe, solvent, etc.) In order to ensure wear resistance and adhesion, the coating film is required to have high hardness and wear resistance.

  However, when wiping off dirt for a long period of time, the coating film gradually wears out, and the coating film is peeled off by abrasion by immersion in the coating film of the solvent used at the time of wiping, and the reliability of water and oil repellency is improved. The current situation is that it cannot be maintained. In addition, if the surface shape of the coated substrate, for example, irregularities such as wrinkles, is present on the surface of the substrate, the film thickness of the coating film becomes non-uniform, and the thin part of the coating film is easily peeled off. The reliability of water and oil repellency could not be maintained.

  Therefore, in order to widely apply the water / oil repellency resin composition to members such as interior equipment of homes and home appliances, it has sufficient hardness and sufficient wear resistance, and has high water repellency / There is currently a need for a resin composition that can provide a coating film with excellent oil repellency, and a resin composition that cures at a low temperature so that it can be applied to a plastic substrate. There is also a need to be.

The present invention has been made in view of the above points, and has high water / oil repellency, high coating film hardness, high wear resistance, and a plastic such as polycarbonate. An object of the present invention is to provide a coated product in which a coating film is formed with a low-temperature curable water- and oil-repellent resin composition capable of forming a coating film having high adhesion even to a substrate. is there.

  The water / oil repellent resin composition according to the present invention includes an acrylic polyol having a side chain containing a polysiloxane skeleton represented by at least one of formula (1) and formula (2) and having a fluoroalkyl group, It is characterized by comprising an isocyanate resin as a cross-linking agent and polymer fine particles having a content ratio of 1.0 to 20% by mass with respect to the solid content in the composition.

（式（１）中、Ｒ_１，Ｒ_２，Ｒ_３，Ｒ_４及びＲ_５は水素原子又は炭素原子数１〜１０の炭化水素基であり、それぞれ同一であっても異なっていてもよい。ｎは２以上の整数である。

(In Formula (1), R < ₁ >, R < ₂ >, R < ₃ >, R < ₄ > and R < ₅ > are a hydrogen atom or a C1-C10 hydrocarbon group, and may be the same or different. n is an integer of 2 or more.

In the formula (2), R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different. p is an integer of 0 to 10, and q is an integer of 2 or more. )
According to this invention, an acrylic polyol can be crosslinked with an isocyanate resin that reacts with a hydroxyl group and cured at a low temperature, and a high amount of fine polymer particles is contained in the crosslinked acrylic resin to maintain high hardness. In addition, it is possible to form a coating film with excellent wear resistance and slipperiness, and it has durability by having a polysiloxane skeleton added as a side chain to an acrylic polyol and a fluoroalkyl group. It is possible to form a coating film having excellent water and oil repellency and excellent wear resistance. In particular, the polysiloxane skeleton is of formula (1) or formula (2) to form a coating film that has higher water and oil repellency with superior durability and further improved wear resistance. Is something that can be done.

  In the present invention, the polymer fine particles are acrylic fine particles.

  According to this invention, by introducing acrylic fine particles into the coating film, it is possible to form a coating film having improved hardness and improved wear resistance.

The coated product according to the present invention is formed by providing a coating film of the above water- and oil-repellent resin composition on the surface of a substrate, and has a film thickness t of the coating film and an average particle diameter D of the polymer fine particles. The relationship is 0.3 ≦ D / t ≦ 3
The film thickness t of the coating film is 5 μm or more.

  By defining the relationship between the film thickness and the particle size of the polymer particles in this way, the coating film is formed to maintain high hardness, low temperature curing water and oil repellency with excellent wear resistance and durability. A coated product having a surface can be obtained.

  In the present invention, the base material is formed of a plastic material.

  According to the present invention, a soft substrate made of a plastic material is used to maintain a high hardness and a highly water- and oil-repellent surface with excellent wear resistance, adhesion, slipperiness, and durability. The coating body which has can be obtained. Since the water / oil repellent resin composition of the present invention can be cured at a low temperature as described above, a coating film can be formed on the base material of the plastic material.

  According to the present invention, an acrylic polyol can be cross-linked with an isocyanate resin that reacts with a hydroxyl group and cured at low temperature, and a high amount of fine polymer particles is contained in the cross-linked acrylic resin to maintain high hardness. In addition, it is possible to form a coating film having excellent wear resistance and slipperiness. In addition, by having a polysiloxane skeleton of formula (1) and formula (2) added to the acrylic polyol as a side chain and a fluoroalkyl group, it has excellent water and oil repellency with excellent durability and abrasion resistance. It is possible to form a coating film with further improved wear characteristics.

  Embodiments of the present invention will be described below.

  The acrylic polyol used in the present invention has a side chain containing a polysiloxane skeleton and a molecular structure in which hydroxyl groups are bonded as side chains. In the present invention, the side chain polysiloxane structure containing a polysiloxane skeleton is represented by at least one of the above formulas (1) and (2).

In the above formulas (1) and (2), R _{1 to} R ₁₀ are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may be the same as or different from each other, for example, a methyl group , Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, phenyl group, cyclohexyl group, preferably methyl group or ethyl group . These hydrocarbon groups may be linear or branched. Moreover, n and q of Formula (1) and Formula (2) are integers of 2 or more, and the upper limit is not particularly set, but is preferably 30 or less.

  In this acrylic polyol, the dimethylsilicon group represented by the formula (1) or the formula (2) becomes a water / oil repellency group to exhibit water / oil repellency. Further, the hydroxyl group becomes a cross-linked site that reacts with the isocyanate group of the isocyanate resin to cross-link.

  Here, it is preferable that the polysiloxane skeleton represented by the formula (1) or the formula (2) is contained in the acrylic polyol (including the side chain) in the range of 10 to 70% by mass. When the content of the polysiloxane skeleton in the acrylic polyol is too large, the adhesion of the coating film to the substrate tends to be lowered, and when the content is too small, the water / oil repellency tends to be lowered. Since this polysiloxane skeleton is directly bonded to the molecular skeleton of the acrylic polyol, it does not easily fall off, and a coating film that exhibits stable water and oil repellency can be obtained over a long period of time. By improving the slip property, a coating film with improved wear resistance can be obtained.

  The hydroxyl value of the acrylic polyol is preferably in the range of 70 to 230 mgKOH / g, more preferably in the range of 100 to 200 mgKOH / g. If the hydroxyl value is too low, the number of hydroxyl groups that crosslink by reacting with isocyanate decreases, so the crosslinking density of the resulting coating film tends to decrease, and the coating film tends to have low hardness. On the other hand, if the hydroxyl value is too high, the number of hydroxyl groups that react with the isocyanate to crosslink increases and a hard coating film is obtained, but the compatibility between the acrylic polyol and the solvent decreases, and the resin stability is poor. Tend to be.

  The acrylic polyol contains a fluorine group in the resin skeleton in order to enhance the durability of water repellency. As the fluorine group, fluoroalkyl groups exemplified in the following formulas (3) to (6) are used, and can be bonded to the acrylic polyol skeleton at the time of synthesis of the acrylic polyol. As the amount of the fluoroalkyl group increases, the durability of the water-repellent performance of the resulting coating film is improved, but the compatibility of the acrylic polyol with the solvent and other resins tends to decrease. For this reason, it is preferable to adjust content of a fluoroalkyl group in the range of 1-70 mass% in acrylic polyol (a side chain is included).

― (CF ₂ ―CF ₂ ) ― (3)
― (CF ₂ ―CFH) ― (4)
— (CF ₂ —CH ₂ ) — (5)
― (CFH-CH ₂ ) ― (6)
The acrylic polyol obtained as described above preferably has a weight average molecular weight (Mw) of 20,000 to 150,000. More preferably, it is 25000-100,000, More preferably, it is 30000-50000. If the molecular weight of the acrylic polyol is too high, the compatibility with the solvent and other crosslinking agents tends to be poor, and if the molecular weight of the acrylic polyol is too low, the physical properties of the resulting coating film tend to be reduced.

  Next, the role of the crosslinking agent will be described. The isocyanate resin reacts with the hydroxyl group contained in the acrylic polyol to crosslink the acrylic resin to form a dense coating film. The obtained coating film forms a film having excellent flexibility and abrasion resistance as compared with a silicon-based film. In particular, interior equipment and household appliances for homes may wipe off dirt, so the required wear resistance and hardness are required to be very strict, and if the amount of isocyanate resin added is small, Their performance tends to decrease.

  Examples of the isocyanate resin include hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, isophorone diisocyanate and the above mixtures. If the amount of the isocyanate resin added is too large, a hard and dense coating film can be formed, but conversely, it tends to be a coating film that is brittle and has poor adhesion. Therefore, it is preferable to set the addition amount of the isocyanate resin in the range of 10 to 280% by mass with respect to the solid content of the acrylic polyol (including the side chain).

  The water / oil repellent resin composition of the present invention is prepared by further blending polymer fine particles with the acrylic polyol and the crosslinking agent. The polymer fine particles are not particularly limited, and examples thereof include acrylic resins, epoxy resins, polyester resins, polyurethane resins, ABS resins, and melamine resins. By incorporating polymer fine particles into the coating film, the wear resistance of the coating film is improved and a coating film with high hardness can be obtained. It is preferable to use acrylic fine particles such as acrylic resin fine particles from the viewpoint of improving the property, maintaining high hardness, and adhesion to the coating film.

  Here, if the addition amount of the polymer fine particles is small, the effect of improving the hardness and abrasion resistance of the coating film cannot be sufficiently obtained. Conversely, if the addition amount of the polymer fine particles is too large, There is a tendency that the unevenness of the surface of the coating film increases and the water and oil repellency decreases. Therefore, the content of the polymer fine particles is set in the range of 1.0 to 20% by mass with respect to the solid content of the total resin of the water / oil repellent resin composition.

  A coated product can be obtained by coating the surface of the substrate with the water / oil repellent resin composition of the present invention prepared by blending the acrylic polyol with the crosslinking agent and the polymer fine particles as described above.

  In addition, as the base material on which the water / oil repellent resin composition is coated, any substrate can be used without any particular limitation. However, a preferable base material particularly applicable in the present invention is formed by molding a plastic material. Among the plastic materials that are formed, polycarbonate, polypropylene, ABS resin, acrylic resin, and the like can be cited as preferable examples of plastic materials. Here, the water / oil repellent resin composition of the present invention can be cured at a low temperature without the need for heating to a high temperature by reacting the isocyanate resin with a hydroxyl group of an acrylic polyol and crosslinking with an isocyanate resin. It is. Therefore, it is possible to apply a water / oil repellent resin composition using such a plastic material as a substrate. In the present invention, the curing temperature of the water- and oil-repellent resin composition is not particularly limited, but is not higher than the heat resistance temperature of the plastic material forming the substrate and is from room temperature (25 ° C.) to about 120 ° C. A range is desirable.

  Then, when forming a coating film by coating the surface of the substrate with the water / oil repellent resin composition of the present invention, the average particle diameter D of the polymer fine particles contained in the water / oil repellent resin composition It is preferable to set the ratio D / t of the film thickness t of the coating film to be in the range of 0.3-3. When D / t is less than 0.3 and the particle size of the polymer fine particle is too small relative to the film thickness of the coating film, the effect of improving the hardness and abrasion resistance of the coating film by incorporating the polymer fine particle is effective. It becomes insufficient. Conversely, if D / t exceeds 3 and the particle size of the polymer fine particle is too large relative to the film thickness of the coating film, the surface roughness of the coating film increases and the water and oil repellency decreases. Tend. The film thickness t is preferably 5 μm or more. There exists a tendency for the abrasion resistance of a coating film to fall that a film thickness is less than 5 micrometers. The upper limit of the film thickness of the coating film is not particularly set, but generally about 100 μm is the upper limit of the film thickness. The average particle diameter D of the polymer fine particles is selected in relation to the film thickness t of the coating film and is not particularly limited, but is preferably set in the range of 2 to 30 μm. Here, the average particle diameter is a value measured by a laser diffraction / scattering method. In addition, when there are uneven portions such as wrinkles on the surface of the substrate on which the coating film is formed, it is preferable to set the average particle size of the polymer fine particles to 1/6 or more of the height dimension of the uneven portions. . In addition, the wear resistance is further improved by the synergistic effect of the polysiloxane skeleton of the acrylic polyol and the polymer fine particles.

  Next, the present invention will be specifically described with reference to examples.

Example 1
An acrylic polyol having a side chain having a dimethylsilicon skeleton represented by the formulas (1) and (2) and a fluoroalkyl group (“ZX-022H” manufactured by Fuji Chemical Industry Co., Ltd .: dimethylsilicon group / hydroxyl group-containing fluorine silicon Resin, solid content 46 mass%, hydroxyl value 120) was used.

  Further, as the isocyanate resin, hexamethylene diisocyanate resin (“Takenate D-170N” manufactured by Mitsui Chemicals, Inc .: solid content: 100% by mass) was used.

  Furthermore, cross-linked polymethyl methacrylate fine particles (“MBX-12” manufactured by Sekisui Plastics Co., Ltd., average particle size: 12 μm) were used as the polymer fine particles.

  Then, the polymer fine particles in the amount shown in Table 1 are dispersed in the acrylic polyol with a disper, and the isocyanate resin in the amount shown in Table 1 and methyl ethyl ketone in the amount shown in Table 1 as a solvent are added and mixed. An oil repellent resin composition was prepared. The content ratio of the polymer fine particles in the total solid content is 10% by mass.

  Next, a polycarbonate substrate is used, and the water- and oil-repellent resin composition prepared as described above is applied to the polycarbonate substrate by air spray so that the dry film thickness becomes 10 μm. A coated plate was prepared by drying at a temperature of 30 ° C. for 30 minutes.

(Example 2)
As the isocyanate resin, a tolylene diisocyanate resin (“Takenate D-103H” manufactured by Mitsui Chemicals, Inc .: solid content 50% by mass) was used in the same manner as in Example 1, but with the formulation shown in Table 1. A water / oil repellent resin composition was prepared. A coated plate was prepared in the same manner as in Example 1 using this water / oil repellent resin composition.

(Example 3)
As the isocyanate resin, xylylene diisocyanate resin (“Takenate D-120N” manufactured by Mitsui Chemicals Co., Ltd .: solid content: 75% by mass) was used in the same manner as in Example 1, but with the formulation shown in Table 1. A water / oil repellent resin composition was prepared. A coated plate was prepared in the same manner as in Example 1 using this water / oil repellent resin composition.

Example 4
As polymer fine particles, cross-linked polymethyl methacrylate fine particles (“MBX-12” manufactured by Sekisui Plastics Co., Ltd., average particle size: 12 μm) are used and blended at a content ratio of 3% by mass in the total solid content. In the same manner as in Example 1, a water / oil repellent resin composition was prepared with the formulation shown in Table 1.

  Then, this water- and oil-repellent resin composition was applied to the same polycarbonate substrate as in Example 1 so that the dry film thickness was 14 μm, and dried in the same manner as in Example 1 to produce a coated plate. .

(Example 5)
As polymer fine particles, cross-linked polymethyl methacrylate fine particles (“MBX-12” manufactured by Sekisui Plastics Co., Ltd., average particle size: 12 μm) are used and blended at a content ratio of 20% by mass in the total solid content. In the same manner as in Example 1, a water / oil repellent resin composition was prepared with the formulation shown in Table 1.

  Then, the same water-repellent / oil-repellent resin composition was applied to the same polycarbonate substrate as in Example 1 so that the dry film thickness was 17 μm, and dried in the same manner as in Example 1 to produce a coated plate. .

(Example 6)
As polymer fine particles, cross-linked polymethyl methacrylate fine particles (“MBX-12” manufactured by Sekisui Plastics Co., Ltd., average particle size: 12 μm) are used and blended at a content ratio of 1% by mass in the total solid content. In the same manner as in Example 1, a water / oil repellent resin composition was prepared with the formulation shown in Table 1.

  And this water-repellent / oil-repellent resin composition was applied to the same polycarbonate substrate as in Example 1 so that the dry film thickness was 8 μm, and dried in the same manner as in Example 1 to produce a coated plate. .

(Example 7)
In the same manner as in Example 1 except that cross-linked polymethyl methacrylate fine particles (“MBX-5” manufactured by Sekisui Plastics Co., Ltd., average particle size of 5 μm) are used as the polymer fine particles, the composition shown in Table 1 A water / oil repellent resin composition was prepared.

  And this water-repellent and oil-repellent resin composition was applied to the same polycarbonate substrate as in Example 1 so that the dry film thickness was 5 μm, and dried in the same manner as in Example 1 to produce a coated plate. .

(Example 8)
In the same manner as in Example 1 except that cross-linked polymethyl methacrylate fine particles (“MBX-30” manufactured by Sekisui Plastics Co., Ltd., average particle size of 30 μm) are used as the polymer fine particles, the composition shown in Table 1 A water / oil repellent resin composition was prepared.

  Then, this water- and oil-repellent resin composition was applied to the same polycarbonate substrate as in Example 1 so that the dry film thickness was 15 μm, and dried in the same manner as in Example 1 to produce a coated plate. .

Example 9
A coated plate was produced in the same manner as in Example 1 except that coating was performed so that the dry film thickness was 17 μm.

(Example 10)
A coated plate was produced in the same manner as in Example 1 except that coating was performed so that the dry film thickness was 5 μm.

(Example 11)
In the same manner as in Example 1 except that cross-linked polymethyl methacrylate fine particles (“MBX-2H” manufactured by Sekisui Plastics Co., Ltd., average particle size 2 μm) are used as the polymer fine particles, the composition shown in Table 1 A water / oil repellent resin composition was prepared.

  Then, the same polycarbonate substrate as in Example 1 was coated with this water / oil repellent resin composition so that the dry film thickness was 6 μm, and dried in the same manner as in Example 1 to prepare a coated plate.

(Example 12)
As polymer fine particles, cross-linked polymethyl methacrylate fine particles (“MBX-30” manufactured by Sekisui Plastics Co., Ltd., average particle size: 30 μm) are used and blended at a content ratio of 10% by mass in the total solid content. In the same manner as in Example 1, a water / oil repellent resin composition was prepared with the formulation shown in Table 1.

  And this water-repellent / oil-repellent resin composition was applied to the same polycarbonate substrate as in Example 1 so that the dry film thickness was 8 μm, and dried in the same manner as in Example 1 to produce a coated plate. .

(Example 13)
Other polymer fine particles (cross-linked polymethyl methacrylate fine particles (“MBX-2H” manufactured by Sekisui Plastics Co., Ltd., average particle diameter: 2 μm)) were used and blended at a content ratio of 10% by mass in the total solid content. In the same manner as in Example 1, a water / oil repellent resin composition was prepared with the formulation shown in Table 1.

  Then, this water- and oil-repellent resin composition was applied to the same polycarbonate substrate as in Example 1 so that the dry film thickness was 10 μm, and dried in the same manner as in Example 1 to produce a coated plate. .

(Example 15)
A coated plate was produced in the same manner as in Example 1 except that an acrylic resin substrate was used as the substrate.

(Example 16)
A coated plate was produced in the same manner as in Example 1 except that an ABS resin substrate was used as the substrate.

(Comparative Example 1)
A water / oil repellent resin composition was prepared in the same manner as in Example 1 except that the polymer fine particles were not used. A coated plate was prepared in the same manner as in Example 1 using this water / oil repellent resin composition.

(Comparative Example 3)
An acrylic polyol having a side chain having a dimethylsilicon skeleton represented by the formulas (1) and (2) and a fluoroalkyl group (“ZX-022H” manufactured by Fuji Chemical Industry Co., Ltd .: dimethylsilicon group / hydroxyl group-containing fluorine silicon Resin, solid content 46 mass%, hydroxyl value 120) was used.

  As a curing agent, a melamine resin (“Uban 225” manufactured by Mitsui Chemicals, Inc .: solid content 60% by mass) was used.

  Furthermore, cross-linked polymethyl methacrylate fine particles (“MBX-12” manufactured by Sekisui Plastics Co., Ltd., average particle size: 12 μm) were used as the polymer fine particles.

  Then, a water / oil repellent resin composition was prepared in the same manner as in Example 1 with the formulation shown in Table 1 using these materials.

  Next, polycarbonate is used as the base material, and the resin composition prepared as described above is applied to the polycarbonate base material by air spray so that the dry film thickness becomes 6 μm, and dried at a temperature of 80 ° C. for 30 minutes. By doing so, a coated plate was produced.

(Comparative Example 4)
A water- and oil-repellent resin composition in the same manner as in Example 1 with an acrylic polyol (“ACRYDIC 52-666B” manufactured by DIC Corporation: hydroxyl group-containing resin, solid content 50 mass%, hydroxyl value 148). Was prepared.

  Next, polycarbonate is used as the base material, and the resin composition prepared as described above is applied to the polycarbonate base material by air spray so that the dry film thickness becomes 9 μm and dried at a temperature of 80 ° C. for 30 minutes. By doing so, a coated plate was produced.

(Comparative Example 5)
Using an acrylic polyol having a side chain containing a polysiloxane skeleton and having no fluoroalkyl group (“GS-1015” manufactured by Toagosei Co., Ltd .: hydroxyl group-containing resin, solid content 45 mass%, hydroxyl value 72) A water / oil repellent resin composition was prepared in the same manner as in Example 1 by blending.

  Next, polycarbonate is used as the base material, and the resin composition prepared as described above is applied to the polycarbonate base material by air spray so that the dry film thickness becomes 7 μm and dried at a temperature of 80 ° C. for 30 minutes. By doing so, a coated plate was produced.

(Comparative Example 6)
A water- and oil-repellent resin in the same manner as in Example 1 with the composition shown in Table 1 using silica fine particles (“Pyrospher C-1510” manufactured by Fuji Silysia Chemical Ltd., average particle size 10 μm) instead of the polymer fine particles. A composition was prepared.

  Next, polycarbonate is used as the base material, and the resin composition prepared as described above is applied to the polycarbonate base material by air spray so that the dry film thickness becomes 13 μm, and dried at a temperature of 80 ° C. for 30 minutes. By doing so, a coated plate was produced.

(Comparative Example 7)
As polymer fine particles, cross-linked polymethyl methacrylate fine particles (“MBX-12” manufactured by Sekisui Plastics Co., Ltd., average particle size: 12 μm) are used and blended at a content ratio of 22% by mass in the total solid content. In the same manner as in Example 1, a water / oil repellent resin composition was prepared with the formulation shown in Table 1.

  Next, polycarbonate is used as the base material, and the resin composition prepared as described above is applied to the polycarbonate base material by air spray so that the dry film thickness becomes 18 μm, and dried at a temperature of 80 ° C. for 30 minutes. By doing so, a coated plate was produced.

(Comparative Example 8)
As polymer fine particles, cross-linked polymethyl methacrylate fine particles (“MBX-2H” manufactured by Sekisui Plastics Co., Ltd., average particle size: 2 μm) are used and blended at a content ratio of 0.5 mass% in the total solid content. The water / oil repellent resin composition was prepared in the same manner as in Example 1 with the formulation shown in Table 1.

  Next, polycarbonate is used as the base material, and the resin composition prepared as described above is applied to the polycarbonate base material by air spray so that the dry film thickness becomes 10 μm, and dried at a temperature of 80 ° C. for 30 minutes. By doing so, a coated plate was produced.

(Comparative Example 9)
For comparison, an unpainted polycarbonate substrate was subjected to the test.

(Comparative Example 10)
For comparison, an unpainted acrylic resin substrate was subjected to the test.

(Comparative Example 11)
For comparison, an unpainted ABS resin substrate was subjected to the test.

  About the coating board (Comparative Examples 9-11 is the surface of a base material) obtained by Examples 1-16 and Comparative Examples 1-8 as mentioned above, coating-film hardness, the abrasion property of a coating film, and stain resistance of a coating film And contact angle were tested and evaluated. The test method is as follows, and the results are shown in Table 1.

(1) Coating film hardness The hardness of the coating film was measured by the pencil method according to JISK5600-5-4.

(2) Abrasion Abrasion test is performed by rubbing the attached white cloth for dyeing fastness test attached to the "Abrasion Tester" made by Daido Science Co., Ltd. under the condition of 1000 reciprocations and 1000g load. Changes were evaluated according to the following criteria.
(Double-circle): There is no external appearance change, such as coating film peeling, in the test of 5000 times.
○: No change in appearance such as peeling of coating film.
(Triangle | delta): The abrasion trace has arisen partially.
X: It was completely worn and the substrate was visible.

(3) Pollution resistance (magic contamination)
The removability of traces written on the surface of the coating film with oil-based magic ink was evaluated according to the following criteria.
○: Well repelled, lightly removed, no stains.
Δ: The repellency is weak and can be removed, but the magic ink stain remains after the removal.
X: Not repelled and cannot be removed at all.

(4) Contact angle Contact angle measuring device (Contact angle measuring device) It was measured by Kyowa Interface Chemical Co., Ltd. model CA-A).

As can be seen from the results of Examples 1 to 16, the coating film formed by the water- and oil-repellent resin composition of the present invention has a coating film hardness that is higher than the hardness of the base material and is very hard, and also has good adhesion. Also, the contamination of the coating film (magic contamination test) is good despite containing polymer fine particles, and maintains good water repellency without any abrasion marks after the abrasion test. there were.
In addition, Examples 1-3 changed the isocyanate resin, and were excellent in abrasion resistance and antifouling property irrespective of the kind of isocyanate resin. In Example 1 and Examples 4 to 6, the content ratio of the polymer fine particles was varied. Among these, the coated products of Examples 4 and 5 having polymer fine particle content ratios of 3% by mass and 20% by mass were particularly excellent in wear resistance. In Examples 7 to 13, the ratio D / t between the average particle diameter D of the polymer fine particles and the film thickness t of the coating film was varied. Among these, the coated articles of Examples 7 to 10 having D / t of 0.7 to 2.6 were particularly excellent in wear resistance .
On the other hand, as seen in Comparative Example 1, the coating film not containing the polymer fine particles had reduced hardness and wear resistance . In Comparative Example 3 in which melamine was used as the curing agent, the coating film hardness was not improved, the wear resistance was inferior, and the contamination resistance was low. In Comparative Example 4 formed from an acrylic polyol having no polysiloxane skeleton and no fluoroalkyl group, although the coating film hardness was improved, the abrasion resistance and stain resistance were inferior. The comparative example 5 formed from the acrylic polyol which does not have a fluoroalkyl group was inferior also in abrasion resistance, and was also a thing with low stain resistance. In Comparative Example 6 in which silica was used for the fine particles, although the hardness was improved, the wear resistance was inferior. In Comparative Example 7 in which the polymer fine particle content ratio exceeds 20% by mass, the hardness and wear resistance are improved, but the stain resistance is lowered. Furthermore, Comparative Examples 9 to 11 having only the base material were greatly inferior in antifouling property and wear resistance.

Claims (3)

An acrylic polyol having a side chain containing a polysiloxane skeleton represented by at least one of formula (1) and formula (2) and having a fluoroalkyl group, an isocyanate resin as a crosslinking agent, and a content ratio of the composition A coating of a low-temperature curable water- and oil-repellent resin composition containing 1.0 to 20% by mass of acrylic resin fine particles with respect to the solid content therein is provided on the surface of the substrate, The relationship between the film thickness t and the average particle diameter D of the acrylic resin fine particles is 0.3 ≦ D / t ≦ 3
And a coated product having a coating film thickness t of 5 μm or more.

(In Formula (1), R < ₁ >, R < ₂ >, R < ₃ >, R < ₄ > and R < ₅ > are a hydrogen atom or a C1-C10 hydrocarbon group, and may be the same or different. n is an integer of 2 or more.
In the formula (2), R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different. p is an integer of 0 to 10, and q is an integer of 2 or more. ) The coated product according to claim 1, wherein the acrylic resin fine particles are crosslinked polymethyl methacrylate fine particles.   The coated article according to claim 1 or 2, wherein the substrate is formed of a plastic material.