JP2006022258A - Composition, molded product and method for producing cured coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition capable of forming a cured coating film having super water repellency of 150 ° C. or more and colorless transparency and having excellent surface hardness, a molded product having such characteristics, and a method for producing the same. .
SOLUTION: A compound having two or less radically polymerizable unsaturated double bonds and / or a resin containing no polymerizable unsaturated double bond in one molecule is composed of 100 parts by mass of a composition (coating film forming component). A composition which can form a cured product containing a total light transmittance of 90% or more, a haze value of 1% or less, and a contact angle with water of 150 degrees or more, contained in a proportion of 35 parts by mass or less.
[Selection figure] None

Description

  The present invention relates to a composition that can form a cured product that is colorless and transparent and has excellent surface hardness and super-water repellency, a molded product having a cured coating film comprising the cured product on a substrate surface, and a method for producing the same About.

  Resins such as acrylic resin, polycarbonate resin, polyester resin, or cyclic polyolefin resin are widely used as materials for moldings such as covers, lenses, resin glass, and films for protecting them because of their excellent transparency. . However, these resins have insufficient water repellency and surface hardness. For example, when water repellency is imparted to the surface of a molded product or a film protecting the molded product, the transparency and / or the surface hardness tends to decrease.

Therefore, as a method for making the solid surface water-repellent, a silicone compound such as polysiloxane or a compound partially containing fluorine in the molecule is directly applied to the solid surface, or the aforementioned silicone compound or fluorine is used. A technique for making a surface water-repellent by applying a resin containing a surfactant to a solid surface is widely known.
In recent years, in addition to a component that reduces the surface free energy of a cured coating film, inorganic fine particles are contained in the cured coating film to form fine irregularities on the surface of the cured coating film (for example, Patent Document 1). Reference), a method using a paint containing organic fine particles (see, for example, Patent Document 2), and further, after forming fine uneven protrusions on the surface of a solid by a treatment such as plasma as a method of imparting fine unevenness to the surface, There is known a method of water repellency by bonding a compound having a low surface free energy to a solid surface (see, for example, Patent Document 3 and Patent Document 4).

Japanese Patent Laid-Open No. 10-273617 JP-A-8-3479 JP-A-4-288349 JP 2001-131318 A

However, a cured coating film of a paint simply containing a silicone compound or a fluorine compound has a contact angle with water of 110 degrees or less, and an improvement in water repellency is desired.
In addition, the contact angle with water and the transparency are improved by the method using the paint containing inorganic fine particles and organic fine particles (Patent Documents 1 and 2) and the method using the water-repellent plasma treatment (Patent Documents 3 and 4). However, there exists a subject that the haze value of the obtained cured coating film tends to be high, and a colorless and transparent cured coating film cannot be obtained.
In particular, Patent Document 4 discloses a transparent molded article having a transparent and super-water-repellent surface of 150 ° or more. However, the transparency in Patent Document 4 means that the haze is about 6.7 to 22%, and there is a problem that a molded product having a colorless and transparent surface which is the object of the present invention cannot be obtained. there were.

Thus, a composition that is excellent in transparency and capable of forming a cured coating film having both water repellency and surface hardness, and a molded product having such characteristics and a method for producing the same have not yet been found. Desired.
An object of the present invention is to provide a composition capable of forming a cured coating film having super water repellency of 150 ° C. or more and colorless transparency, and having excellent surface hardness, and a molded product having such characteristics, and a method for producing the same Is to provide.

In the present invention, a compound having two or less radically polymerizable unsaturated double bonds in one molecule and / or a resin not containing a polymerizable unsaturated double bond is contained in 100 parts by mass of a composition (coating film forming component). A composition capable of forming a cured product having a total light transmittance of 90% or more, a haze value of 1% or less, and a contact angle with water of 150 ° or more; A fluoroalkylsilane compound is chemically bonded to the surface of the cured product layer formed by the step 1 of forming the cured product layer of the composition described above, the step 2 of processing the surface of the cured product layer by plasma etching, and the processed cured material layer of step 2. It exists in the manufacturing method of the cured coating film which has the process 3 to make.

The composition of the present invention is capable of forming a cured coating film that is colorless and transparent and excellent in super-water repellency, and thus has antifouling properties, water landing prevention properties, snow adhesion prevention properties, ice prevention properties, etc. Is suitable for practical use for members for building / building materials, home appliance parts, automobile parts, and the like.
In addition, the molded product of the present invention having such characteristics is desired in various fields as a product imparting functionality, and its industrial utilization is great.
Furthermore, since the manufacturing method of the present invention is a simple process, it is possible to reduce the environmental load with high productivity and energy saving, and industrial utilization is great.

Hereinafter, the present invention will be described in detail.
The contact angle with water as used in the present invention means that the obtained molded product is left in a constant temperature room at 20 ° C. for 1 hour, and then the contact angle with water on the surface of the cured coating is 20 ° C. It means a value obtained by measurement using Kyowa Interface Science Co., Ltd.
Moreover, the haze value as used in the field of this invention is measured according to JIS-K-7105 about the obtained molded article using a haze meter (Murakami Color Research Laboratory make, brand name: HM-150). Means the haze value obtained.

  The composition of the present invention comprises a compound having 2 or less radically polymerizable unsaturated double bonds in one molecule and / or a resin not containing a polymerizable unsaturated double bond (hereinafter referred to as component (A)). Curing of 100 parts by weight of the product (coating film forming component) in a proportion of 35 parts by weight or less, total light transmittance of 90% or more, haze value of 1% or less, and water contact angle of 150 degrees or more. It is a composition that can form a product.

Here, the term “two or less radicals in one molecule” is not particularly limited. In the present invention, “a cured product having a total light transmittance of 90% or more, a haze value of 1% or less, and a contact angle with water of 150 ° or more” means colorless and transparent, and excellent in surface hardness. It means a cured product with excellent water repellency.
When the total light transmittance is lower than 90%, the cured product is opaque or tends to be colored although it is transparent. On the other hand, when the haze value exceeds 1%, the transparency tends to decrease and the turbidity tends to increase. Furthermore, when the contact angle with respect to water is lower than 150 degrees, the properties such as antifouling property, anti-watering property, anti-snowing property and anti-icing property tend not to be sufficiently developed.
The composition of the present invention is particularly characterized in that it is a cured product having a contact angle with water of not less than 150 degrees, thereby providing extremely excellent antifouling properties, water-preventing properties, snow-preventing properties, and icing properties. It is practically possible to sufficiently exhibit characteristics such as prevention.

  The composition of the present invention contains component (A).

Specific examples of the compound having two radical polymerizable unsaturated double bonds in one molecule of the component (A) include, for example, ethylene glycol di (meth) acrylate and 1,3-propylene glycol di (meth). Acrylate, 1,4-heptanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate 2-butene-1,4-di (meth) acrylate, cyclohexane-1,4-dimethanol di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, 1,5-pentanedi (meth) acrylate, trimethylolethane Di (meth) acrylate, tri Chlodecane dimethanol di (meth) acrylate, trimethylolpropane di (meth) acrylate, dipropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 2,2-bis- (4- ( (Meth) acryloxypropoxyphenyl) propane, 2,2-bis- (4- (meth) acryloxy (2-hydroxypropoxy) phenyl) propane, bis- (2-methacryloyloxyethyl) phthalate,
Urethane di (meth) acrylate obtained by reacting isophorone diisocyanate and 2-hydroxypropyl (meth) acrylate, urethane di (meth) acrylate obtained by reacting dicyclomethane diisocyanate and 2-hydroxyethyl (meth) acrylate, dicyclomethane diisocyanate And urethane di (meth) acrylate such as urethane di (meth) acrylate obtained by reacting 2-hydroxyethyl (meth) acrylate with a urethanization reaction product of poly (repeating unit: 6 to 15) tetramethylene glycol,
Epoxy di (meth) acrylates such as epoxy di (meth) acrylate obtained by reacting bisphenol A type diepoxy with (meth) acrylic acid,
Examples thereof include bifunctional (meth) acrylates such as polyester (meth) acrylates such as polyester (meth) acrylate obtained by reacting polyethylene glycol with succinic acid and (meth) acrylic acid.

Moreover, as a specific example of the compound which has one radical polymerizable unsaturated double bond in 1 molecule among components (A), for example, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate And monofunctional (meth) acrylate having a polymerizable unsaturated double bond.
Specific examples thereof include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl. (Meth) acrylate, n-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentenoxyethyl (Meth) acrylate, isobornyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, Xyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid, ( And (meth) acryloylmorpholine.

In addition, among the components (A), specific examples of the resin not containing a polymerizable unsaturated double bond used in the present invention include, for example, a vinyl monomer or a mixture thereof in the presence of a radical polymerization initiator. Examples thereof include a copolymer obtained by a known method such as a combination method, a bulk polymerization method, and an emulsion polymerization method.
In the composition of the present invention, the content of the component (A) is 35 parts by mass or less in 100 parts by mass of the composition (coating film forming component). Within this range, a cured coating film having excellent surface hardness can be obtained, but a composition having a content exceeding 35 parts by mass tends to have high haze.
In addition, in the composition of the present invention, other copolymerizable compounds can be appropriately selected and used so that the desired characteristics can be expressed as long as the characteristics of the present invention are not impaired.

  Examples of such a compound include three or more (meth) acrylates in the molecule, such as (meth) acrylate having a polymerizable unsaturated bond such as urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate. ) A compound having an acryloyloxy group (hereinafter referred to as component (B)).

Specific examples of the component (B) include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tri Pentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, bis (2- (meth) acryloxye ) -Hydroxyethyl-isocyanurate, tris (2- (meth) acryloxyethyl) isocyanurate, urethane (meth) acrylate, 1,6-hexamethylene diisocyanate trimer with 2-hydroxyethyl (meth) Urethane tri (meth) acrylate reacted with acrylate, urethane hexa (meth) acrylate reacted with isophorone diisocyanate and pentaerythritol tri (meth) acrylate, trimethylolethane reacted with succinic acid and (meth) acrylic acid Polyester (meth) acrylate, trimethylolpropane and succinic acid, ethylene glycol, polyester (meth) acrylate obtained by reacting (meth) acrylic acid, and the like.
These can be used individually by 1 type or in combination of 2 or more types.

  Further, when plasma etching treatment is further performed on the surface of the cured coating film, unevenness is likely to be formed on the surface, and a cured coating film that maintains colorless transparency tends to be obtained.

If necessary, fine particles (hereinafter referred to as component (C)) may be added to the composition of the present invention.
If the component (C) is added to the composition of the present invention, the super water repellency can be further improved on the surface of the molded article, and the surface hardness and weather resistance can be imparted to the cured coating film.
In addition, the component (C) here is not limited to what is said to be granular in a strict sense, for example, in various arbitrary shapes such as scaly, fibrous, amorphous, and polyhedral, It is meant to include what can be called fine particles because of its fine shape.
The form of the component (C) used in the present invention is not particularly limited. For example, a form that exists as a powder, or fine particles that are dispersed as colloidal particles (dispersion liquid) in water, alcohol, organic solvent, or the like Is mentioned. In the present invention, from the viewpoint of durability of the cured coating film, it is preferable that fine particles exposed on the surface of the molded product are dispersed without agglomeration. Among these, since the component (C) is exposed from the surface of the cured coating film and minute protrusions are easily formed on the surface of the molded product, the component (C) is more preferably in a fine shape.

The kind of component (C) is not specifically limited, An organic compound or an inorganic compound may be sufficient. Specific examples include silicon oxide fine particles such as silicon dioxide (SiO ₂ ) and glass fiber, titanium dioxide (TiO ₂ ), aluminum oxide (Al ₂ O ₃ ), zinc oxide (ZnO), iron oxide (FeO, Examples thereof include fine metal oxide particles such as Fe ₂ O ₃ , Fe ₃ O ₄ ), antimony oxide (Sb ₂ O ₃ ), cerium oxide (CeO ₂ ), and tin oxide (SnO ₂ ).
These can be used individually by 1 type or in combination of 2 or more types.
Among these, silicon oxide fine particles and metal oxide fine particles are preferred because the obtained cured product is excellent in transparency and can impart surface hardness, abrasion resistance, weather resistance and scratch resistance.
Further, among them, silicon dioxide (SiO ₂ ) fine particles are particularly preferable because the resulting cured product is excellent in transparency.

Although the magnitude | size of the component (C) used for this invention is not specifically limited, Among these, it is preferable that a primary average particle diameter is the range of 10-100 nm, and it is more preferable that it is 20-60 nm.
When the primary average particle diameter exceeds 100 nm, the transparency of the resulting cured product tends to decrease, and when it is less than 10 nm, super-water repellency tends not to be sufficiently exhibited.

  In addition, the component (C) used by this invention improves this dispersion | distribution retainability in a composition, compatibility with a coating-film formation component, and a viewpoint which improves this transparency as needed from a viewpoint of improving transparency (meta). It is preferable to use one that has been surface-treated in advance with a silane compound such as acryloylalkoxysilane.

  Among these silane compounds, for example, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 2- Silane compounds such as (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane Etc. are mentioned as preferable examples.

  Further, in the composition of the present invention, the content of the component (C) is not particularly limited, but the composition (coating) can be formed on the surface of the cured coating film by a plasma treatment process after the coating film curing process. (Film-forming component) It is preferable to contain in 1-60 mass% in 100 mass parts.

  The composition of the present invention can be cured by active energy rays and / or heat, but is preferably cured by active energy rays such as electron beams and ultraviolet rays from the viewpoint of short time and energy saving. Among these, it is preferable to use ultraviolet rays because of its high versatility.

Moreover, when using an ultraviolet-ray as an active energy ray, it is preferable to contain a photoinitiator from a viewpoint of hardening acceleration.
Specific examples of the photopolymerization initiator include, for example, benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethyl ketal, 2,2-diethoxyacetophenone, 1 -Carbonyl compounds such as hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, ethylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-ethylanthraquinone; tetramethylthiuram monosulfide, Sulfur compounds such as tetramethylthiuram disulfide; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. And the like.
These can be used individually by 1 type or in combination of 2 or more types.

  Among these, benzophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, and acylphosphine oxide compounds are more preferable because of excellent curing acceleration.

You may make the composition of this invention contain a photoinitiator and / or thermal polymerization as needed. In that case, the range of 0.1-15 mass parts is preferable in the total amount of 100 mass parts of a composition (coating film formation component), and the range of 1-10 mass parts is more preferable.
If the lower limit of the content of the polymerization initiator is less than 0.1 parts by mass, the curability of the composition tends to be insufficient, and if the upper limit exceeds 15 parts by mass, the resulting molded product surface is obtained. There exists a tendency for the adhesiveness with a cured coating film to fall.

  In addition, the composition of the present invention includes an antifoaming agent, an anti-settling agent, a lubricant, an abrasive, an antirust agent, an antistatic agent, an ultraviolet absorber, light, and the like within a range that does not impair the target characteristics of the present invention. Various additives such as a stabilizer and an antioxidant may be appropriately added.

Furthermore, an organic solvent is added to the composition of the present invention as necessary for the purpose of adjusting the viscosity according to the coating method, improving the coating property during coating, or improving the appearance such as leveling properties. Also good.
Specific examples of the organic solvent include, for example, ketone compounds such as acetone, methyl ethyl ketone, and cyclohexanone; ester compounds such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and methoxyethyl acetate; diethyl ether, ethylene glycol dimethyl ether, dioxane, and the like. Ether compounds; aromatic compounds such as toluene and xylene; aliphatic compounds such as pentane and hexane; alcohol compounds such as isopropanol and butanol;

Next, the molded product of the present invention will be described in detail.
The molded product of the present invention has a cured coating film, which is made of a cured product of the above-described composition on a substrate, and is extremely excellent in super water repellency and colorless transparency. Therefore, when the substrate is colorless and transparent, a molded product having a surface excellent in water repellency and surface hardness can be obtained while maintaining the transparency of the molded product. Further, when the molded product is colored or colored, a molded product having a surface excellent in water repellency and surface hardness can be obtained without impairing the color of the substrate.

In the present invention, the material of the base material is, for example, polymethyl methacrylic resin, polycarbonate resin, polyester resin, poly (polyester) carbonate resin, polystyrene resin, ABS resin, AS resin, polyamide resin, polyarylate. Well-known synthetic resins such as various thermoplastic resins and thermosetting resins such as thermoplastic resins, polymethacrylimide resins, and polyallyl diglycol carbonate resins.
Moreover, the form of the molded article of the present invention may be a sheet-like article, a film-like article or the like, or a molded article having a three-dimensional structure, and is not particularly limited.

The manufacturing method of the present invention includes the following three steps, which will be described in detail below.
-Step 1 of forming a cured product layer of the composition of the present invention on a substrate
-Process 2 for processing the surface of the cured product layer by plasma etching
Step 3 for chemically bonding a fluoroalkylsilane compound to the surface of the cured product layer processed in Step 2

  First, in Step 1, the composition described above is applied to a substrate by a known method to form a coating film. The coating film is dried as necessary, and then the coating film is irradiated with active energy rays and / or Alternatively, the cured product layer may be formed by curing with heat.

Here, examples of the application method of the composition include brush coating, spray coating, dip coating, spin coating, and flow coating. What is necessary is just to select this application | coating method suitably according to the shape of a molded object, and the viscosity of a composition.
In addition, when an organic solvent is included in the coating composition to improve the appearance such as coating properties and leveling properties during coating, the coating film formed on the substrate surface is dried and It is desirable to cure the coating film after volatilizing the organic solvent.
From the viewpoint of productivity, the coating film is dried by heating the coating film with, for example, an IR heater and / or warm air, and volatilizing the organic solvent at 60 to 130 ° C. for 3 to 20 minutes. Is preferred.

The method for curing the coating film is not particularly limited, but it is preferable to use an active energy ray such as an ultraviolet ray or an electron beam because it is highly productive and energy saving can reduce the environmental load.
Among them, it is more preferable to use a general-purpose high-pressure mercury lamp and to cure it under the condition of an integrated light quantity of about 500 to 4000 mJ / cm ² when the irradiated ultraviolet energy is in the wavelength range of 340 to 380 nm.

In step 2, the obtained cured coating film surface is processed by plasma etching.
By performing this processing, the contact angle of water on the surface of the cured coating film on the substrate can be made extremely high. The plasma etching process condition may be a normal surface roughening process condition, and may be appropriately selected as desired.

  The atmosphere of the plasma etching treatment in step 2 is not particularly limited as long as it is appropriately selected from an inert gas such as argon and a reactive gas such as oxygen and tetrafluoromethane. The surface of the cured coating film that has been subjected to plasma etching in this way is processed into irregularities on the surface shape.

Specific examples of the fluoroalkylsilane compound include, for example, CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si (OCH _3). ) ₃ , CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) Cl ₂ etc. Is mentioned.
Among these, particularly when the number of fluorine atoms is large, the water repellency tends to be high. Therefore, CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) Cl _{2 and the} like are preferable.

The fluoroalkylsilane compound may be diluted with a solvent for the purpose of adjusting the viscosity appropriately depending on the coating thickness, coating conditions, coating method, and the like.
Examples of the solvent used for diluting the fluoroalkylsilane compound include lower alcohols such as ethanol and 2-propanol; fluorine solvents such as m-xylene hexafluoride; and the like. In order to lower the polycondensation temperature, an acid such as hydrochloric acid or acetic acid may be added. The method for applying the fluoroalkylsilane compound is not particularly limited, and various conventionally known methods can be used. Examples thereof include coating using an applicator and a bar coater, roll coating, spray coating, dip coating, and the like. Moreover, it is preferable to heat in order to accelerate the reaction between the hydroxyl group of the silicon oxide fine particles and / or the metal oxide fine particles and the fluoroalkylsilane compound.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, all “parts” in the examples mean “parts by mass”. Moreover, the measurement and evaluation method in an Example are as follows.

[Evaluation conditions]
(1) Appearance of coating film About the cured coating film formed on the obtained molded product, a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., trade name: HM-150) was used according to JIS-K-7105. And measure the total light transmittance (%) and haze value. The obtained values were evaluated according to the following criteria, and the results are shown in Table 1.
[transparency]
○: When the total light transmittance exceeds 90% and the haze value is 1% or less ×: When the total light transmittance is 90% or less and the haze value exceeds 1%
[appearance]

(2) Contact angle with water After the obtained molded product was left in a constant temperature room at 20 ° C. for 1 hour, the contact angle with water on the surface of the cured coating was measured at 20 ° C. with a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.). The obtained value is shown in Table 1. The contact angle with respect to the water obtained here is O when the angle is 150 degrees or more, and x when the angle is less than 150 degrees.

(3) Pencil hardness The pencil hardness of the cured coating film was measured according to JIS-K-5400, and the results are shown in Table 1.

<Example 1>
In a four-necked flask, 2000 g of silica sol (dispersion medium: iso-propanol, SiO ₂ concentration: 30% by mass, primary average particle size: 10 to 15 nm, trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) 382 g of 3-methacryloxypropyltrimethoxysilane (trade name: A-174, manufactured by Nihon Unicar Co., Ltd.) was added, the temperature was increased while stirring, and 139 g of 0.001N hydrochloric acid aqueous solution was started at the same time as the reflux of volatile components began. Was gradually added dropwise, and after completion of the addition, hydrolysis was performed under reflux.
After that, volatile components such as alcohol and water were distilled off, toluene was added and azeotropically distilled, and then the solvent was completely replaced with toluene to obtain colloidal silica whose surface was treated with a dispersion of toluene. (Solid content concentration after reaction: about 60% by mass).

Next, in a glass beaker, 25 parts of the obtained surface-coated colloidal silica in terms of solid content, 60 parts of tris (2-acryloxyethyl) isocyanurate, 12 parts of 1,9-nonanediol diacrylate Furthermore, 1.5 parts of 1-hydroxycyclohexyl phenyl ketone and 1.5 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide were weighed into a container as a photopolymerization initiator and well mixed and stirred. Thereafter, in order to adjust the mixture to a viscosity suitable for the spray coating method, the mixture was diluted with a mixed solvent in which n-butanol and butyl acetate were mixed at a ratio of 1: 1 to prepare a paint having a solid content of 30% by mass.
The resulting paint is spray coated to form a coating on a transparent polycarbonate plate (thickness 3 mm) and allowed to stand for 5 minutes in a hot air dryer with a cured film thickness of 10 μm and adjusted to approximately 60 ° C. The solvent in the coating film was removed by volatilization.

Next, the surface of the coating film from which the solvent was removed was irradiated with ultraviolet rays having an integrated light quantity of 340 to 380 nm of 1500 mJ / cm ² using a high-pressure mercury lamp with an lamp intensity of 80 W / cm in an air atmosphere to obtain a cured coating film. .
Thereafter, as a plasma treatment step, a molded product was obtained by etching the surface of the cured coating film for 10 minutes using CF ₄ gas at an output of 450 W. Next, the fluoroalkylsilane compound, CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (manufactured by Shin-Etsu Silicon Co., Ltd., trade name KBM-7803) was immersed in a hydrolyzed alcohol solution and then air-dried and then 80 Heat treatment was performed at 0 ° C. for 30 minutes.

<Example 2>
30 parts of the surface-coated colloidal silica obtained in Example 1 (in terms of solid content), 20 parts of dipentaerythritol hexaacrylate, 37 parts of tris (2-acryloxyethyl) isocyanurate, 1,6-hexanediol 10 parts of diacrylate, 1 part of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator, and 2 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide were weighed in a container and well mixed and stirred.
Thereafter, the same operation as in Example 1 was carried out except that the etching time was 5 minutes in the plasma treatment step to obtain a molded product having a cured coating film.

<Examples 3-4, Comparative Examples 1-3>
Except using the composition shown in Table 1, its blending ratio, and the substrate, the same operation as in Example 1 was performed to obtain a molded product having a cured coating film.

<Comparative example 4>
A molded product having a cured coating film was obtained in the same manner as in Example 1 except that the composition, the mixing ratio and the base material shown in Table 1 were used and the treatment with the fluoroalkylsilane compound was not performed.

<Comparative Example 5>
A molded product having a cured coating film was obtained in the same manner as in Example 1 except that the composition, the mixing ratio and the base material shown in Table 1 were used and no plasma treatment was performed.

In addition, the value of CS in a table | surface is a solid content conversion value.
Abbreviations in the table are as follows.
UA: urethane acrylate with a molecular weight of 2500 synthesized from 2 mol of dicyclohexylmethanediol, 1 mol of nonabutylene glycol and 2 mol of 2-hydroxyethyl acrylate HDDA: 1,6-hexanediol diacrylate NDDA: 1,9-nonanediol diacrylate TAIC: Tris ( 2-acryloyloxyethyl) isocyanurate DPHA: dipentaerythritol hexaacrylate CS: condensate GF of colloidal silica and 3-methacryloxypropyltrimethoxysilane having an average particle size of 20 nm: primary average particle size of 7.2 μm Glass particles HCPK: 1-hydroxycyclohexyl phenyl ketone APO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide PC: poly Boneto plate (thickness 3mm)
PMMA: Polymethylmethacrylate plate (thickness 3 mm)

[Discussion]
As is apparent from Table 1, the coating films obtained in Examples 1 to 4 exhibited water repellency exceeding 150 degrees, and had excellent transparency and low-haze molded products. On the other hand, in the comparative example, the cured coating film is not subjected to plasma treatment, does not contain inorganic fine particles, or the inorganic fine particles are too large. Inferior results were obtained.

Claims (3)

  35 parts by mass of a compound having 2 or less radically polymerizable unsaturated double bonds in one molecule and / or a resin containing no polymerizable unsaturated double bond in 100 parts by mass of the composition (coating film forming component) A composition capable of forming a cured product having a total light transmittance of 90% or more, a haze value of 1% or less, and a contact angle with respect to water of 150 degrees or more, which is contained in a proportion of at most parts.   The molded article which has a cured coating film which consists of hardened | cured material of the composition of Claim 1 on a base material. The process 1 which forms the hardened | cured material layer of the composition of Claim 1 on a base material, the process 2 which processes this hardened | cured material layer surface by a plasma etching process, and fluoroalkyl on the hardened | cured material layer surface processed in the process 2 A method for producing a cured coating film, comprising the step 3 of chemically bonding a silane compound.