JP2009024145A - Fluororesin composition for coating and product using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluororesin composition for coating, which can be applied at a construction site and from which a heat-ray shielding film excellent in transparency, chemical resistance and weather resistance can be formed. <P>SOLUTION: The fluororesin composition for coating contains a fluororesin (A) having 30-200 mg-KOH/g hydroxyl value and heat-ray shielding inorganic fine particles (B) having 1-200 nm average particle diameter. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a fluororesin composition for paints and an article having a heat ray shielding film formed using the same.

In recent years, there has been an increasing demand for providing heat-ray shielding and ultraviolet shielding on transparent plastics and glass surfaces in order to remove harmful ultraviolet rays and unnecessary near-infrared rays from solar rays as much as possible and allow only visible light to pass through. is doing.
For example, in the case of architectural glass and vehicle glass, the temperature rise and cooling load in the building and the vehicle can be reduced by shielding infrared rays flowing into the building and the vehicle through the glass.

  Conventionally, as a method of forming a transparent film having such a function on glass, a dry method such as a sputtering method or a vapor deposition method is often used. However, a large-scale apparatus and a complicated process are required, and the product is a product. The cost is also very expensive. In addition, such a dry method is difficult to apply when it is desired to apply heat ray shielding to an existing window glass on site.

Examples of methods that can be applied to existing window glass in the field include, for example, a method of preparing and attaching a film having heat ray shielding properties, and a method of preparing and applying a paint containing a component capable of imparting heat ray shielding properties. .
However, the method of attaching the film has a problem in durability, such as bubbles generated on the adhesion surface between the glass and the film, and the film itself is likely to be discolored or faded due to the influence of ultraviolet rays. In the case of a large area glass, a seam of the film is generated.

Regarding the coating method, for example, in Patent Document 1 below, a treatment liquid containing an organosilicon compound is formed on a transparent glass plate to form a film made of tin oxide fine particles doped with antimony, and fills the gaps between the fine particles. A method for forming a heat ray-shielding film by impregnating and then firing to form an inorganic polymer matrix is described.
Patent Document 2 listed below describes a method of forming a transparent film having an infrared cutoff function from a film forming material containing tin-doped indium oxide powder, an organic resin, and a non-alcohol organic solvent. . Examples of the organic resin include acrylic resin, polycarbonate, polyvinyl chloride, urethane resin, melamine resin, alkyd resin, polyester, and epoxy resin (paragraph 0027).
Japanese Patent No. 3408578 Japanese Patent No. 2715859

However, the heat ray-shielding film obtained by the method described in Patent Document 1 has low chemical resistance, particularly alkali resistance, and the film may be dissolved by cleaning with a general glass cleaning agent. Is insufficient.
The film obtained by the method described in Patent Document 2 has poor weather resistance. For example, when it is used in a site requiring weather resistance such as a building window glass, the performance deteriorates in several years. This is not practical because

  The present invention has been made in view of the above circumstances, and is a fluorine for paint that is excellent in dispersion stability, can be applied on site, and can form a heat ray shielding film excellent in transparency, chemical resistance and weather resistance. An object is to provide a resin composition and an article using the same.

In order to solve the above-mentioned problems, the fluororesin composition for paints of the present invention comprises a fluororesin (A) and heat ray shielding inorganic fine particles (B), and the hydroxyl value of the fluororesin (A) is 30 to 200 mgKOH / g. And the heat-shielding inorganic fine particles (B) have an average aggregate particle diameter of 1 to 200 nm.
The number average molecular weight of the fluororesin (A) is preferably 20000 or less and 1000 or more.
The heat ray shielding inorganic fine particles (B) are at least one selected from the group consisting of tin and indium composite oxide fine particles, tin and antimony composite oxide fine particles, lanthanum hexaboride fine particles, and zinc oxide fine particles. Is preferred.
It is preferable that the fluororesin composition for paint further contains an ultraviolet absorber (C).
The ultraviolet absorber (C) is preferably at least one selected from the group consisting of benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and triazine ultraviolet absorbers.
The fluororesin (A) preferably contains an alkoxysilane (D) having a curing reactive site and having a reactive group that reacts with the curing reactive site.

The article of the present invention has a heat ray shielding film formed on the substrate using the fluororesin composition for paints of the present invention.
It is preferable that a primer layer is provided on the substrate, and the heat ray shielding film is formed on the primer layer.
The primer layer is preferably a layer formed using a silane coupling agent.
In particular, when the substrate is glass, the primer layer is preferably provided.

According to the fluororesin composition for coatings of the present invention, it is possible to form a heat ray shielding film that is excellent in dispersion stability, can be applied on site, and has excellent transparency, chemical resistance, and weather resistance.
The article of the present invention has a heat ray shielding film having good transparency, chemical resistance and weather resistance, which is formed on a substrate by on-site construction.

The fluororesin composition for coatings of the present invention (hereinafter sometimes simply referred to as a coating composition) contains a fluororesin (A) and heat ray shielding inorganic fine particles (B). Furthermore, it is preferable that an ultraviolet absorber (C) is included.
<Fluororesin (A)>
The fluororesin (A) (hereinafter also referred to as component (A)) is a polymer having polymerized units based on fluoroolefin. The component (A) is preferably soluble in a solvent, and various fluororesins known for paints can be used.
The fluororesin (A) may be a fluoroolefin homopolymer, but in addition to a polymer unit based on a fluoroolefin, a copolymer containing a polymer unit based on a monomer copolymerizable with the fluoroolefin is preferred.
The fluorine content in the fluororesin (A) is preferably 10% by mass or more. There exists a possibility that the weather resistance of a coating film (heat ray shielding film) may become inadequate that this fluorine content is less than 10 mass%. Moreover, when the weather resistance and coating workability | operativity of a coating film are considered, it is more preferable that this fluorine content rate is 15-50 mass%. More preferably, it is 40 mass% or less, and 30 mass% or less is still more preferable.

  The fluororesin (A) preferably has a curing reactive site that reacts with the curing agent to form a cross-linked bond. Examples of the curing reactive site include groups having active hydrogen such as a hydroxyl group, a thiol group, a carboxyl group, an amino group, and an amide group, an epoxy group, an isocyanate group, and an allyl group. Among these, from the viewpoint of easy availability and curing reactivity, a group having active hydrogen, particularly a hydroxyl group is preferred.

As the fluororesin (A), one having a hydroxyl value of 30 to 200 mgKOH / g is used. The value of the hydroxyl value in the present invention is a value measured by a method according to JIS K 0070. When the hydroxyl value of the fluororesin (A) is 30 mgKOH / g or more, good dispersion stability can be obtained even when the average particle size of the heat ray shielding inorganic fine particles (B) is as small as 200 nm or less. It is preferable in terms of pot life. Further, when the ultraviolet absorber (C) is contained, it is preferable because good dispersion stability can be obtained. The hydroxyl value of the fluororesin (A) is more preferably 40 mgKOH / g or more, further preferably 50 mgKOH / g or more, and most preferably 80 mgKOH / g or more.
On the other hand, when the hydroxyl value is 200 mgKOH / g or less, good solubility of the fluororesin (A) in the solvent can be obtained, and the viscosity of the resulting coating composition does not become too large, which is preferable. More preferably, it is 150 mgKOH / g or less, and 130 mgKOH / g or less is still more preferable.

The number average molecular weight of the fluororesin (A) is preferably 20000 or less and 1000 or more. The number average molecular weight in the present invention is a value measured by GPC using polystyrene as a standard substance.
When the number average molecular weight is 20000 or less, good dispersion stability of the heat ray shielding inorganic fine particles (B) and the ultraviolet absorber (C) can be easily obtained, which is preferable from the viewpoint of the pot life of the coating composition. More preferably, it is 15,000 or less, and further preferably 12,000 or less. On the other hand, it is preferable that the number average molecular weight is 1000 or more because high weather resistance and durability which are originally required for a fluororesin are easily expressed. The number average molecular weight is more preferably 3000 or more and even more preferably 5,000 or more.

The acid value of the fluororesin (A) may be 0 (zero), but is preferably greater than 0 and 10 mgKOH / g or less. The value of the acid value in the present invention is a value measured by a method according to JIS K 5601-2-1.
The higher the acid value, the better the dispersion stability of the heat ray shielding inorganic fine particles (B) and the ultraviolet absorber (C). On the other hand, it is preferable that the acid value is 10 mgKOH / g or less because it is difficult to be colored and storage stability is easily developed.
When the acid value is 0, good dispersion stability of the heat ray shielding inorganic fine particles (B) and the ultraviolet absorber (C) is obtained by adjusting the hydroxyl value and / or the number average molecular weight of the fluororesin (A). be able to.

As fluororesin (A), fluoroolefins such as tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, perfluoropropyl vinyl ether, vinyl ethers, vinyl carboxylates, allyl ethers, allyl carboxylates, isopropenyl A copolymer of a hydrocarbon monomer such as ethers and a monomer having a curing reactive site such as hydroxybutyl vinyl ether or glycidyl vinyl ether is preferable.
Examples of such a fluororesin made of a copolymer include JP-A-57-34107, JP-A-57-34108, JP-A-58-189108, JP-A-61-57609, JP-A-61-. No. 113607 and the like, and can be obtained from commercial products.
In particular, copolymers of fluoroolefins and vinyl ethers (fluoroolefin / vinyl ether copolymers) such as Lumiflon series (trade name, manufactured by Asahi Glass Co., Ltd.) are preferable in that good transparency and weather resistance can be obtained.
1 type may be used for a fluororesin (A) and it may use 2 or more types together. When the fluororesin (A) is a mixture of two or more, it is preferable that the hydroxyl value, number average molecular weight, and acid value of each fluororesin constituting the mixture are within the above range.

<Heat ray shielding inorganic fine particles (B)>
The heat ray shielding inorganic fine particles (B) (hereinafter sometimes referred to as the component (B)) are inorganic fine particles having a heat ray shielding function, and those having little reflection and absorption of visible light are preferably used.
Specifically, the heat ray-shielding inorganic fine particles (B) include tin and indium composite oxide fine particles (ITO), tin and antimony composite oxide fine particles (ATO), lanthanum hexaboride fine particles (LaB ₆ ), and oxidation. It is preferably at least one selected from the group consisting of zinc fine particles. Zinc oxide is preferable because it also has an ability to absorb ultraviolet rays. Zinc oxide may also contain dopants such as aluminum, gallium, indium, yttrium, boron, scandium and thallium.
Among the above, ITO, ATO, or lanthanum hexaboride (LaB ₆ ) is preferable in that it can effectively shield near infrared rays having a wavelength of 800 to 1800 nm that contribute to heat ray shielding.
In particular, ITO is preferable in that it has a high visible light transmittance in a film including the ITO, and a highly transparent film can be easily obtained, so that the appearance of the transparent substrate is not impaired. Uneven coating is difficult to occur. In addition, since ITO does not have photocatalytic performance, it is also preferable in that there is no possibility that the weather resistance deterioration of the coating film is accelerated even when used outdoors.

The average particle diameter of the heat ray shielding inorganic fine particles (B) contained in the coating composition of the present invention is 1 to 200 nm. If the average particle size of the heat ray shielding inorganic fine particles (B) is more than 200 nm, the transparency of the resulting coating film may be lowered, which is not preferable. On the other hand, if the average particle diameter is less than 1 nm, the heat ray shielding performance may be hardly exhibited, such being undesirable. The heat ray shielding inorganic fine particles (B) may be in the form of primary particles or aggregated particles in the coating composition. The state of the heat ray shielding inorganic fine particles (B) in the coating film reflects the state in the coating composition. For this reason, it is preferable that the heat ray shielding inorganic fine particles (B) are highly dispersed in the coating composition from the viewpoint of transparency and radio wave transmission of the obtained coating film. Therefore, when preparing a coating composition, it is preferable to disperse | distribute and use a heat ray shielding inorganic fine particle (B) previously in a dispersion medium. The average particle size of the heat ray shielding inorganic fine particles (B) is more preferably 10 to 150 nm, and further preferably 30 to 100 nm. In addition, the average particle diameter in this specification means the average particle diameter on a volume basis. The average particle diameter is a value measured in a state where the heat ray shielding inorganic fine particles (B) are dispersed in the coating composition. The particle diameter of the particles dispersed in the coating composition or in the dispersion medium is preferably measured by a laser light scattering method. As an apparatus for the laser light scattering method, specifically, a dynamic light scattering particle size analyzer (trade name: Microtrac UPA, manufactured by Nikkiso Co., Ltd.) is preferable. Further, in the present specification, as a specific method for measuring the average particle diameter, the coating composition is diluted with an organic solvent such as toluene, xylene, propylene glycol monomethyl ether acetate, etc., which can be used in the present invention, and the solid content concentration Is preferably measured by a laser light scattering method such as a dynamic light scattering particle size analyzer.
As a dispersion medium for the heat ray shielding inorganic fine particles (B), various solvents such as polar solvents such as water and alcohol, and nonpolar solvents such as toluene and xylene can be appropriately used. Further, it may be dispersed in the same dispersion medium as the solvent contained in the coating composition. As a dispersion method, a known method can be used, and a media mill such as ultrasonic irradiation, a homogenizer, a ball mill, a bead mill, a sand mill, and a paint shaker, or a high-pressure impact mill such as a jet mill or a nanomizer can be used. Various dispersants may be used to stabilize the heat ray shielding inorganic fine particles (B) in the dispersion. The material in which the heat ray shielding inorganic fine particles (B) are dispersed in the dispersion medium can also be obtained from commercial products.

<Ultraviolet absorber (C)>
The ultraviolet absorber (C) (hereinafter sometimes referred to as the component (C)) is a material that absorbs ultraviolet rays having a wavelength of 380 nm or less, and is easily dissolved or dispersed in the coating composition, and can absorb visible light. Those having little reflection and absorption are preferably used.
In the present invention, the ultraviolet absorber (C) is not essential, but the inclusion thereof is preferable in practice because an ultraviolet shielding effect is obtained in addition to the heat ray shielding effect.

Organic ultraviolet absorbers include benzotriazole compounds, benzophenone compounds having an absorption region on the long wavelength side; triazine compounds, cyanoacrylate compounds, oxalic acid anilide compounds having an absorption region on the short wavelength side, and the like. Can be mentioned. These can be obtained from commercial products.
Moreover, you may use an ultraviolet-ray shielding inorganic fine particle as a ultraviolet absorber (C). Specific examples include cerium oxide (CeO ₂ ) and titanium oxide (TiO ₂ ). These can be obtained from commercial products. The average particle size of the ultraviolet shielding inorganic fine particles is preferably 1 to 200 nm. If the average particle diameter is more than 200 nm, the dispersion stability of the resulting coating composition may be lowered, and the transparency of the resulting coating film may be lowered, which is not preferable. On the other hand, if the average particle size is too small, it is not preferable because ultraviolet shielding performance is hardly exhibited.

In view of less deterioration of the ultraviolet absorbent (C) itself due to ultraviolet rays or oxygen in the air, ultraviolet shielding inorganic fine particles are preferred. Of the ultraviolet shielding inorganic fine particles, TiO ₂ has a relatively strong catalytic action on the surface of the fine particles, and CeO ₂ is more preferable in view of such inconvenience.
Organic UV absorbers are preferred because they have good stability in the coating composition and are less likely to adversely affect the transparency and adhesion of the coating film. When using organic UV absorbers, light stabilizers (HALS), peroxide decomposers, quenchers, etc. are added as appropriate to the coating composition in order to prevent deterioration due to UV rays and oxygen in the air. May be.

A ultraviolet absorber (C) may use 1 type and may use 2 or more types together.
As the ultraviolet absorber (C), it is particularly preferable to use one or more selected from the group consisting of a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, and a triazine-based ultraviolet absorber. May be.

Examples of benzophenone ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, and the like.
Examples of benzotriazole ultraviolet absorbers include benzenepropanoic acid 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy C7-9 side chain and linear alkyl Ester (tinuvin 384-2: trade name, manufactured by Ciba Specialty Chemicals), 3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] isooctyl propionate ( Tinuvin 384: trade name, manufactured by Ciba Specialty Chemicals), 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) -2H-benzotriazole (tinuvin 328: trade name, Ciba Specialty Chemicals), 2- [2-hydroxy-3,5-bis (1,1-dimethylbenzyl) fur Nil] -2H-benzotriazole (Tinuvin 900: trade name, manufactured by Ciba Specialty Chemicals), 2- [2-hydroxy-3- (1,1-dimethylbenzyl) -5- (1,1,3 3-tetramethylbutyl) phenyl] -2H-benzotriazole (Tinuvin 928: trade name, manufactured by Ciba Specialty Chemicals), 3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] methyl propionate / polyethylene glycol 300 condensate (Tinuvin 1130: trade name, manufactured by Ciba Specialty Chemicals) and the like.

  Examples of triazine-based ultraviolet absorbers include 2- (4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl) -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine (Tinuvin 400: trade name, manufactured by Ciba Specialty Chemicals), 2- (4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl)- Examples include 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

  The benzophenone-based, benzotriazole-based, or triazine-based UV absorber is not limited to the above specific examples, and is known or well known in consideration of compatibility with the resin component contained in the coating composition, melting point, and the like. These benzophenone-based, benzotriazole-based, or triazine-based ultraviolet absorbers can be appropriately selected and employed.

Mixing and using at least one of the benzophenone ultraviolet absorber or benzotriazole ultraviolet absorber (i) and the triazine ultraviolet absorber (ii) as the ultraviolet absorber (C) provides sufficient ultraviolet shielding properties. It is preferable in obtaining.
These mixing ratios are not particularly limited, but it is preferable to use more (i). For example, the use ratio of (i) / (ii) is preferably 100/90 to 100/20, more preferably 100/70 to 100/30 on a mass basis.

<Content of (A), (B), (C) component>
When the coating composition contains the component (A) and the component (B) and does not contain the ultraviolet absorber (C), the total solid content of the component (A) and the component (B) is 100% by mass. The component (solid content) is preferably 20 to 95% by mass, the component (B) (solid content) is preferably 5 to 80% by mass, the component (A) is 30 to 90% by mass, and the component (B) is 10 to 10% by mass. A range of 70% by mass is more preferable.
When the component (A) is 20% by mass or more, good on-site workability and durability can be easily obtained, and when it is 95% by mass or less, the content of the component (B) is sufficiently secured and good heat ray ultraviolet rays are obtained. Easy shielding.
When the component (B) is 5% by mass or more, sufficient heat ray shielding performance is easily obtained, and when it is 80% by mass or less, the content of the fluororesin (A) serving as a binder is sufficiently ensured and good durability is achieved. It is easy to get sex.

When the coating composition contains the fluororesin (A), the heat ray shielding inorganic fine particles (B), and the ultraviolet absorber (C), the total solid content of the components (A), (B), and (C) is set to 100. When it is made into mass%, (A) component (solid content) is 20-90 mass%, (B) component (solid content) is 5-70 mass%, (C) component (solid content) is 1-15 mass%. It is preferable that
When the component (A) is 20% by mass or more, good on-site workability and durability are easily obtained, and when it is 90% by mass or less, the contents of the component (B) and the component (C) are sufficiently secured. It is easy to obtain a good heat ray ultraviolet ray shielding property.
When the component (B) is 5% by mass or more, sufficient heat ray shielding performance can be easily obtained, and when it is 70% by mass or less, the content of the fluororesin (A) serving as a binder is sufficiently ensured and good durability is achieved. It is easy to get sex.
When the component (C) is 1% by mass or more, sufficient ultraviolet shielding properties are easily obtained, and when it is 15% by mass or less, good compatibility with the fluororesin (A) is easily obtained, and the substrate and the coating material are coated. Good adhesion to the film is also easily obtained. When the compatibility with the component (A) is insufficient, the component (C) tends to bleed out from the coating film.
In particular, in order to achieve high heat ray shielding property, ultraviolet ray shielding property, chemical resistance and weather resistance at the same time, the component (A) is 30 to 60% by mass, the component (B) is 10 to 50% by mass, (C More preferably, the component is 5 to 15% by mass.

The solid content concentration of the coating composition is preferably in the range of 0.1 to 40% by mass. The solid content concentration of the coating composition in the present invention is a ratio (unit) of the total solid content of the component (A), the component (B), and the component (C) in the total amount (100% by mass) of the coating composition. : Mass%).
When the solid content concentration is 0.1% by mass or more, it is easy to suppress the occurrence of unevenness when the coating composition is applied on the substrate. Moreover, it is easy to ensure a film thickness that provides a sufficient heat ray shielding effect. When the solid content concentration is 40% by mass or less, workability at the time of coating is good, and a good appearance and transparency of the coating film are easily obtained. In addition, good stability as a coating composition is easily obtained, and sufficient storage stability is easily obtained. The solid content concentration is more preferably 10 to 40% by mass, and further preferably 20 to 35% by mass.

<Alkoxysilane (D)>
When the coating composition contains the fluororesin (A) having a curing reactive site, the alkoxysilane (D) having a reactive group that reacts with the curing reactive site (hereinafter also referred to as component (D)). May be included). By using the component (D), the durability of the coating film can be improved. Also, the heat ray shielding inorganic fine particles (B) and the component (D) react to obtain the same effect as the surface modification of the fine particles by the silane coupling agent, and the familiarity between the components (B) and (A). You can also expect the effect to improve.

Examples of the reactive group that reacts with the curing reactive site of the fluororesin (A) include an isocyanate group, an allyl group, an epoxy group, an acryloyloxy group, an amino group, a ketimine group, an amide group, a thiol group, and a hydroxyl group. However, what is contained in the category of (E) component mentioned later shall not be contained in (D) component.
In particular, alkoxysilane (D) having no active hydrogen is preferable from the viewpoint of stability.
Suitable reactive groups include acryloyloxy groups, isocyanate groups, epoxy groups, amino groups, and ketimine groups.
Suitable alkoxysilanes (D) include triethoxysilyl-N- (1,3dimethylbutylidene) propylamine, isocyanatepropyltrimethoxysilane, isocyanatepropyldimethoxymethylsilane, isocyanatepropyltriethoxysilane, isocyanatepropyldiethoxymethyl. Examples include silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, acryloyloxypropyltrimethoxysilane, and the like.

  It is preferable to use a alkoxysilane (D) having a ketimine group because the durability of the coating film can be further improved. This mechanism is considered as follows. In the coating composition, ketimine groups exist stably, and when the coating composition is applied, the ketimine groups are hydrolyzed by moisture in the air and the like, whereby the ketone compound is released and the active primary amine is regenerated. This amine rapidly accelerates the curing reaction of the coating film, and as a result, a coating film having high durability, particularly weather resistance, chemical resistance, and adhesion can be obtained.

  When the coating composition contains the component (D), the addition amount of the component (D) is preferably 0.1 to 50 parts by mass, and 1 to 30 parts by mass with respect to 100 parts by mass of the fluororesin (A). More preferred. When the amount of component (D) added is 0.1 parts by mass or more, the effect of component (D) addition is easily obtained. On the other hand, when the amount is 50 parts by mass or less, an increase in viscosity of the coating composition is easily suppressed.

<Polyfunctional organosilicon compound (E)>
When the coating composition contains a fluororesin (A) having a curing reactive site, a polyfunctional organosilicon compound (E) having an isocyanate group directly bonded to silicon (hereinafter also referred to as component (E)) May be included). By using the component (E), the durability of the coating film can be improved. In addition, when the component (E) has a hydrolyzable group, the heat ray shielding inorganic fine particles (B) and the component (E) react to obtain the same effect as the surface modification of the fine particles by the silane coupling agent. , (B) component and (A) component can be expected to improve the familiarity.
Component (E), the general formula _{R 4-p Si (-N =} C = O) compounds represented by _p is preferably. p is an integer of 1 to 4, and when a plurality of Rs are present (when p is 1 or 2), the plurality of Rs may be different from each other. R is a hydrolyzable group or other organic group, and when p is 1, at least one of the three Rs is a hydrolyzable group. The hydrolyzable group is not particularly limited, and examples thereof include an alkoxy group and an acyloxy group. An alkoxy group is preferable, an alkoxy group having 4 or less carbon atoms is more preferable, and a methoxy group or an ethoxy group is particularly preferable.
When R has an organic group other than a hydrolyzable group, the organic group includes an organic group having a carbon atom bonded to a silicon atom, such as an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group, and the like. preferable. Preferably, an alkyl group or an alkenyl group having 18 or less carbon atoms, or an optionally substituted phenyl group or benzyl group is exemplified. Most preferred is an alkyl group having 4 or less carbon atoms.

As a specific example of the component (E),
Silyltetraisocyanate: Si (N = C = O) ₄ ,
Methylsilyl triisocyanate: CH ₃ Si (N═C═O) ₃ ,
Butylsilyl triisocyanate: C ₄ H ₉ Si (N═C═O) ₃ ,
Octylsilyl triisocyanate: C ₈ H ₁₇ Si (N═C═O) ₃ ,
Methoxysilyl triisocyanate: CH ₃ OSi (N═C═O) ₃ ,
Ethoxysilyl triisocyanate: C ₂ H ₅ OSi (N═C═O) ₃ ,
Vinylsilyl triisocyanate: CH ₂ ═CHSi (N═C═O) ₃ ,
Dimethylsilyl _{diisocyanate: (CH 3) 2 Si (} N = C = O) 2,
Methylphenylsilyl diisocyanate: (CH ₃ ) (C ₆ H ₅ ) Si (N═C═O) ₂ ,
Dimethoxysilyl diisocyanate: (CH ₃ O) ₂ Si (N═C═O) ₂ ,
Examples include dibutoxysilyl diisocyanate: (C ₄ H ₉ O) ₂ Si (N═C═O) ₂ .
Moreover, the compound in which the isocyanate group of these organosilicon compounds was blocked with a suitable organic group can also be used, and when this is used, durability of a coating film and adhesiveness with a base material can be improved. When using the (E) component which has this blocked isocyanate group, a baking operation is performed at the time of coating film formation.

When the coating composition contains the component (E), the addition amount of the component (E) is preferably 0.01 to 50 parts by weight, and 0.1 to 30 parts by weight with respect to 100 parts by weight of the fluororesin (A). Part is more preferred. When the amount of the component (E) is 0.01 parts by mass or more, the effect of adding the component (E) is easily obtained, and when the amount is 50 parts by mass or less, the viscosity of the coating composition is easily suppressed.
When the curing agent described later is used, the curing reaction of the component (A), even if the curing reactive site of the component (A) reacts with the reactive group of the component (D) or the isocyanate group of the component (E). It is necessary for the sex part to remain, and the addition amount of the component (D) and the component (E) is adjusted as such. Specifically, when the number of moles of the curing reactive site present in the fluororesin (A) is 1, the total of the reactive groups in the component (D) and the isocyanate groups in the component (E) to be added. The number of moles is preferably 0.5 or less.

<Curing agent>
When the coating composition contains the fluororesin (A) having a curing reactive site, it is preferable to use a curing agent.
The curing agent is appropriately selected from known curing agents for paints, such as isocyanate curing agents, blocked isocyanate curing agents, aminoplast curing agents, polyvalent carboxylic acid curing agents, and polyamine amine curing agents. Can be used. The selection of the curing agent is preferably performed in consideration of the type of curing reactive site, curing characteristics, etc. of the fluororesin (A).
In particular, it is preferable that the fluororesin (A) has a hydroxyl group as a curing reactive site and a polyfunctional compound having reactivity with a hydroxyl group is used as a curing agent.
In addition, what is contained in the category of the said (E) component shall not be contained in a hardening | curing agent.

When using a curing agent that causes a curing reaction at room temperature, a main component containing the component (A) and a curing agent are prepared separately, and a two-component curable coating composition that mixes these during coating film formation; It is preferable to do. (A) It is preferable to make the main ingredient contain the other component which does not react with a component. A two-component curable coating composition can form a heat-shielding film on a substrate by applying a coating composition in which a main agent and a curing agent are mixed onto the substrate and drying the coating composition at room temperature.
Moreover, when using the hardening | curing agent which produces hardening reaction by heating, a hardening | curing agent and (A) component can be made to coexist in a coating composition, and it can be set as a one-component-type baking coating composition. In this case, a heat ray shielding film can be formed on the substrate by applying the coating composition on the substrate and baking it.
Examples of the curing agent that causes a curing reaction at room temperature include non-yellowing diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, and polyvalent isocyanate curing agents such as adducts and multimers thereof.
Examples of the curing agent that causes a curing reaction by heating include a blocked isocyanate curing agent and an aminoplast curing agent.
In particular, polyisocyanate curing agents containing isocyanate groups are useful. In this case, it is preferable to accelerate the curing by adding a curing catalyst such as dibutyltin dilaurate.

When the amount of the curing agent used is too small, sufficient curability cannot be obtained, and when it is too large, many unreacted sites of the curing agent remain, which is not preferable in terms of durability of the coating film. Although the usage-amount of a hardening | curing agent can be suitably set so that these troubles may not arise, 0.1-200 mass parts is preferable with respect to 100 mass parts of fluororesin (A), for example, and 1-100 mass parts is More preferred.
In particular, when a fluororesin (A) having a hydroxyl group is used as a curing reactive site and a curing agent containing an isocyanate group is used, OH provided from the fluororesin (A) in the coating composition and the curing agent are present. The NCO molar ratio [NCO] / [OH] is preferably 0.5 or more and 3.0 or less. When the [NCO] / [OH] is 0.5 or more, sufficient curability is easily obtained, and when it is 3.0 or less, the durability of the coating film caused by unreacted NCO groups is prevented from being lowered. Cheap.

<Organic solvent>
The coating composition preferably contains an organic solvent.
The organic solvent is not particularly limited as long as it does not react with the component (A), the component (D), the component (E), and the curing agent. Specific examples include aromatic solvents such as toluene and xylene; ketones such as methyl ethyl ketone (MEK) and methyl isobutyl ketone; esters such as butyl acetate and ethyl acetate; glycols such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate Examples include ethers; aliphatic solvents; ether solvents; petroleum solvents and the like. In addition to these, various commercially available thinners can also be employed, and these can be mixed and used at various ratios. Such an organic solvent is preferably selected as appropriate in consideration of the state of the object to be coated, the evaporation rate, the working environment, and the like.
The content of the organic solvent is preferably set so that the solid content concentration in the coating composition falls within the above-described preferable range.

<Other ingredients>
The coating composition can appropriately contain various known additives for coatings. For example, you may add a heat stabilizer, a viscosity modifier, a leveling agent, an antifoamer, etc. Moreover, you may contain other synthetic resins other than a fluororesin (A). Specific examples of the other synthetic resin include acrylic resin, polyester, polyurethane, silicone resin, alkyd resin, polyamide, and epoxy resin. When it contains this other synthetic resin, the range of 0.1-50 mass parts is preferable with respect to 100 mass parts of a fluororesin (A), and its 1-30 mass parts is more preferable.

<Coating composition>
The coating composition is obtained by uniformly mixing the components (A) and (B), which are essential components, and further the components contained as necessary.
When a curing agent is not used, it can be used as a one-pack lacquer type coating composition.
Preferably, a two-component curable coating composition is formed using a curing agent that causes a curing reaction at room temperature. For example, (A) and (B), and if necessary, a main agent containing (C) and / or (D) and a curing agent may be separately prepared and mixed immediately before the coating step. preferable. Furthermore, when using the component (E) having two or more isocyanate groups, the curing reaction proceeds when the component (A) and the component (E) coexist, so the component (E) should be added at the same time as the curing agent. Is preferred.
When component (D) and / or component (E) is contained in the main agent, in the step of preparing the main agent or in a film coated with a paint (reacts with moisture in the air), (D) component and / or ( It is preferable that the component (E) reacts with the component (A) to form a chemical bond therebetween. In addition, it is preferable that the component (D) and / or the component (E) and the component (B) react with each other during the mixing to form a chemical bond.
You may perform a heating etc. as needed. In this mixing step, all components contained in the main agent may be added and mixed at the same time as long as aggregation and gelation in the liquid do not occur, or they may be added and mixed in two or three stages. Good. For example, the component (D) and / or the component (E) and the component (A) may be mixed in advance, or the component (D) and / or the component (E) and the component (B) may be mixed in advance. Good.
Mixing is preferably performed in an organic solvent because a uniform mixing reaction is easily achieved.

<Article>
According to the present invention, an article having a heat ray shielding film formed using the coating composition of the present invention on a substrate is obtained. That is, a heat ray shielding film can be formed by applying a coating composition on a substrate. When the coating composition contains a solvent, it is dried after application to remove the solvent. You may heat-dry as needed. Moreover, you may bake-harden as needed. The heat ray shielding film may be formed only on one side of the substrate or on both sides.
The substrate is not particularly limited. A transparent substrate is particularly preferable. Specific examples of the transparent substrate include organic substrates such as polyethylene terephthalate, acrylic resin, polycarbonate, and fluororesin, and inorganic substrates such as glass.
Especially, since the coating composition of this invention can be hardened | cured by natural drying at normal temperature and has high site construction property, it is excellent in the application to the glass substrate, especially the window glass etc. of an existing building.

  A surface treatment can be appropriately performed on the film-forming surface of the substrate as necessary. Thereby, the wettability of a film formation surface becomes good and the adhesiveness to the base material of a coating film (heat ray shielding film) can be improved. The surface treatment method is not particularly limited, but is known plasma treatment, corona discharge treatment, UV treatment, ozone treatment or other discharge treatment; chemical treatment using acid or alkali, etc .; physical treatment using an abrasive, etc. Is mentioned.

Moreover, you may interpose a primer layer between a base material and a heat ray shielding film. That is, a primer layer may be provided on the film forming surface of the substrate, and a heat ray shielding film may be formed on the primer layer. By providing the primer layer, the adhesion of the heat ray shielding film is improved, and good adhesion can be obtained even when a substrate having insufficient adhesion with the heat ray shielding film is used. In particular, when the substrate is made of glass, it is preferable to provide a primer layer.
The primer layer can be formed using a commercially available primer for paint. In particular, when the substrate is made of an inorganic material such as glass, it is preferable to form the primer layer using a silane coupling agent such as a silane compound having an amino group.
The thickness of the primer layer can be appropriately selected. A very thin monomolecular layer level or a layer having a film thickness on the order of microns may be used.

Application | coating of a coating composition can be performed by a well-known method. For example, brush coating, roller coating, hand coating with a wipe or squeegee, spin coating, dip coating, coating by various printing methods, bar coating, curtain flow, die coating, flow coating, spray coating, sponge coating and the like can be mentioned. In particular, in the case of on-site construction, a sponge coat is preferable in that unevenness of the coating film hardly occurs and the size of the base material can be easily accommodated.
Further, for the purpose of increasing the mechanical strength of the film, after applying the coating composition, heating, ultraviolet irradiation, and / or electron beam irradiation, etc. may be appropriately performed within the range allowed in the process. The heating temperature is set in consideration of the heat resistance of the substrate. For example, when a base material is a fluororesin film, 40-100 degreeC is preferable.

The film obtained by applying the coating composition of the present invention on a substrate and drying and curing as necessary contains heat ray shielding inorganic fine particles (B), and is a heat ray shielding film having a heat ray shielding effect. is there. Further, when the ultraviolet ray absorbent (C) is contained in the coating composition in addition to the heat ray shielding inorganic fine particles (B), a heat ray ultraviolet ray shielding film having both the heat ray shielding effect and the ultraviolet ray shielding effect can be obtained.
The heat ray shielding film or the heat ray ultraviolet ray shielding film thus obtained is excellent in transparency, and is particularly suitable when the substrate is transparent. The transparency of the film can be evaluated by a haze value (unit:%). Specifically, the difference between the haze value of the base material before providing the film and the haze value measured for the film formed on the base material is preferably 1.0% or less, and 0.5% or less. Is more preferable. When the difference in haze value is 1.0% or less, the transparency of the coating film is good.
Further, as shown in Examples described later, the heat ray shielding film or the heat ray ultraviolet ray shielding film according to the present invention has good solvent resistance, acid resistance, and alkali resistance and excellent chemical resistance. Further, the accelerated weather resistance is good, and the adhesion, film hardness and boiling water resistance are also good, and the durability is excellent.

  The film thickness of the heat ray shielding film or the heat ray ultraviolet ray shielding film is preferably 0.5 to 100 μm. When the film thickness is 0.5 μm or more, good heat ray shielding property or heat ray ultraviolet ray shielding property and its effect sustainability can be sufficiently obtained. When the film thickness is 100 μm or less, generation of cracks, generation of interference fringes, and reduction in transparency are easily suppressed. In addition, when a scratch is entered, the scratch is less noticeable. The film thickness is more preferably 1 to 50 μm, further preferably 1 to 30 μm, and most preferably 2 to 10 μm.

By using the coating composition of the present invention, it is possible to form a heat ray shielding film or a heat ray ultraviolet ray shielding film having excellent durability by a method in which it is applied on-site to a window glass or the like of an existing building and naturally dried at room temperature. . Since the heat ray shielding film or heat ray ultraviolet ray shielding film obtained by the present invention is particularly excellent in transparency and weather resistance, it can be applied to both the indoor side and the outdoor side of the window glass. You may apply to both.
Further, the heat ray shielding film or the heat ray ultraviolet ray shielding film according to the present invention is formed on one surface of the window glass, and on the other surface, an antifouling film, a hydrophilic film, an antistatic film, a heat insulating film, An ultraviolet-cutting film or the like can also be provided.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Examples 1 to 7, 9 to 12, and 14 to 18 are examples, and examples 8, 13, and 19 are comparative examples. In the following, “%” is “% by mass” unless otherwise specified.

Table 1 shows the formulation in an example in which a fluororesin composition for paints was prepared. The unit of the blending amount is “part by mass”.
Table 1 shows each of (A), (B), and (C) when the solid content concentration (unit: mass%) of the coating composition obtained in each example and the total solid content is 100 mass%. The ratio (mass%) of the solid content contained in the component and the molar ratio of “NCO” / [OH] are shown. The total solid content here means the total solid content contained in the component (A), the component (B), and the component (C).

Each component described in Table 1 is as follows.
The average particle size of the heat ray shielding inorganic fine particles (B) was measured by a dynamic light scattering particle size analyzer (trade name: Microtrac UPA, manufactured by Nikkiso Co., Ltd.).
[solvent]
PGMEA: propylene glycol monomethyl ether acetate.
MEK: methyl ethyl ketone.
[Curing catalyst]
DBTDL: 1.0% PGMEA solution of dibutyltin dilaurate

[Fluororesin (A)]
The following fluororesins (A) are all fluoroolefin / vinyl ether copolymers having a hydroxyl group.
LF916F: manufactured by Asahi Glass Co., Ltd., trade name Lumiflon LF916F, 100% flake body, number average molecular weight 7,000, hydroxyl value 98 mgKOH / g, acid value 0 mgKOH / g, fluorine content 25.6% by mass.
LF200: manufactured by Asahi Glass Co., Ltd., trade name Lumiflon LF200, 60% xylene solution, number average molecular weight 12,000, hydroxyl value 52 mgKOH / g, acid value 0 mgKOH / g, fluorine content 26.7% by mass.
LF400: Asahi Glass Co., Ltd., trade name Lumiflon LF400, 50% xylene solution, number average molecular weight 12,000, hydroxyl value 47 mgKOH / g, acid value 5 mgKOH / g, fluorine content 26.5% by mass.
-LF710F: Asahi Glass Co., Ltd., trade name Lumiflon LF710F, 100% flake body, number average molecular weight 10,000, hydroxyl value 50 mgKOH / g, acid value 0 mgKOH / g, fluorine content 23.7% by mass.
LF810: manufactured by Asahi Glass Co., Ltd., trade name Lumiflon LF810, 45% mineral terpene solution, number average molecular weight 30,000, hydroxyl value 9 mgKOH / g, acid value 1 mgKOH / g, fluorine content 24.0% by mass.
[Comparative ingredients]
Acrylic resin: manufactured by Nippon Shokubai Co., Ltd., trade name U double S series UWS-2816, 46.8% xylene solution, unknown number average molecular weight, hydroxyl value 42.2 mgKOH / g, acid value 2.0 mgKOH / g.

[Heat ray shielding inorganic fine particles (B)]
ITO (70): ITO fine particle dispersion sol, manufactured by Mitsubishi Materials Corporation, ITO solid content concentration 20%, PGMEA dispersion, average particle diameter 70 nm.
ATO (220): ATO fine particle dispersion sol, manufactured by Catalyst Kasei Kogyo Co., Ltd., ATO solid content concentration 21.3%, dispersion dispersed in a mixture of MEK and toluene, average particle size 220 nm.
ATO (105): ATO fine particle dispersion sol, manufactured by Ishihara Sangyo Co., Ltd., ATO solid content concentration 30%, MEK dispersion, average particle diameter 105 nm.
ATO (50): ATO fine particle dispersed sol, manufactured by Sumitomo Metal Mining Co., Ltd., ATO solid content concentration 25%, toluene dispersion, average particle size 50 nm.
LaB ₆ (50): LaB ₆ fine particle dispersion sol, KHF-7AH manufactured by Sumitomo Metal Mining Co., Ltd., LaB6 solid content concentration 3.3%, toluene dispersion, average particle diameter 50 nm.
Zinc oxide (100): Zinc oxide fine particles (manufactured by Sakai Chemical Industry Co., Ltd., heat ray shielding zinc oxide EZ-1 was dispersed in PGMEA with a ball mill (solid content concentration 20%, PGMEA dispersion, average particle size 100 nm. )

[Ultraviolet absorber (C)]
Benzotriazole-based: benzotriazole-based UV absorber, manufactured by Ciba Specialty Chemicals, Inc., trade name TINUVIN 384-2, solid content concentration 95%.
Triazine-based: Triazine-based UV absorber, manufactured by Ciba Specialty Chemicals, trade name TINUVIN400, solid content concentration 85%.
Benzophenone series: Benzophenone series ultraviolet absorber, manufactured by Chemipro Kasei Co., Ltd., trade name KEMISORB 111, solid content concentration 100%.
-Cerium oxide system: UV-absorbing cerium oxide dispersion sol, manufactured by Taki Chemical Co., Ltd., trade name W-100, toluene solution, solid content concentration 10%.

[Alkoxysilane (D)]
Acrylic type: acryloyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone, trade name KBM5103.
Isocyanate type: Isocyanatopropyltriethoxysilane, manufactured by Shin-Etsu Silicone, trade name KBE9007.
Ketimine type: triethoxysilyl-N- (1,3 dimethyl-butylidene) propylamine, manufactured by Shin-Etsu Silicone, trade name KBE9103.
[Polyfunctional organosilicon compound (E)]
-Methylsilyl triisocyanate: Matsumoto Pharmaceutical Co., Ltd., trade name ORGATICS SI-310.
[Curing agent]
Curing agent a: trade name Sumijour N3300, manufactured by Sumika Bayer Urethane Co., Ltd., polyisocyanate curing agent.
Curing agent b: trade name Coronate HX, manufactured by Nippon Polyurethane Co., Ltd., polyisocyanate curing agent.

[Example 1]
(1) The curing catalyst, the component (A) and the component (B) were added to the solvent, and the mixture was stirred with a paint shaker at room temperature for 5 hours. Subsequently, (C) component was added and it stirred for further 2 hours, and obtained the main ingredient of the coating composition.
(2) A curing agent was added to the obtained main agent and stirred for 0.5 hour to obtain a coating composition.

[Example 2]
The curing catalyst, component (A), component (B), and component (D) were added to the solvent, and the mixture was stirred with a paint shaker at room temperature for 5 hours. Subsequently, (C) component was added and it stirred for further 2 hours, and obtained the main ingredient of the coating composition. Thereafter, a coating composition was obtained in the same manner as in Example 1, (2).
[Examples 3 to 5]
A coating composition was obtained in the same procedure as in Example 1.

[Example 6]
The main component of the coating composition was obtained in the same procedure as (1) of Example 1. A curing agent and the component (E) were added to the obtained main agent and stirred for 0.5 hour to obtain a coating composition.
[Example 7]
A coating composition was obtained in the same procedure as in Example 2.
[Example 8]
In this example, it replaced with (A) component and prepared the coating composition using the acrylic resin which is a comparative component.
That is, the curing catalyst, the acrylic resin, and the component (B) were added to the solvent, and the mixture was stirred with a paint shaker at room temperature for 5 hours. Next, component (C) was added, and the mixture was further stirred for 2 hours to obtain a main component of the coating composition. Thereafter, a coating composition was obtained in the same manner as in Example 1, (2).

[Example 9]
A solvent, a curing catalyst, 30 parts by mass of the component (A), the component (B), and the component (D) were added, and the mixture was stirred in a water bath at 50 ° C. for 2 hours. Next, 120 parts by mass of the component (A) and the component (C) were added, and the mixture was further stirred at room temperature for 2 hours to obtain a main component of the coating composition. Thereafter, a coating composition was obtained in the same manner as in Example 1, (2).
[Example 10]
A coating composition was obtained in the same procedure as in Example 1.

[Example 11]
A coating composition was obtained in the same procedure as in Example 2.
[Example 12]
In this example, a coating composition containing no component (C) was prepared.
That is, the curing catalyst, the component (A) and the component (B) were added to the solvent, and the mixture was stirred with a paint shaker at room temperature for 5 hours to obtain a main agent. Thereafter, a coating composition was obtained in the same manner as in Example 1, (2).
[Examples 13 to 19]
A coating composition was obtained in the same procedure as in Example 1.

<Evaluation>
[Dispersibility]
In each case, the obtained main agent was stored at room temperature for 1 month, and sedimentation stability was observed. In the examples other than Examples 13 and 19, there was little sedimentation, and the sedimented solid was easily redispersed by shaking lightly.
In Examples other than Examples 13 and 19, the average particle size of the heat ray-shielding inorganic fine particles (B) in the obtained coating composition was determined using a dynamic light scattering particle size analyzer (trade name Microtrac UPA, manufactured by Nikkiso Co., Ltd.). ) To confirm that the particle diameter is the same as that in the heat ray shielding inorganic fine particle dispersed sol of the raw material. Specifically, the obtained coating composition was diluted with propylene glycol monomethyl ether acetate (PGMEA) to adjust the solid content concentration to about 0.01 to 1.0% by mass, and then subjected to dynamic light scattering particle size analysis. It was measured by a meter.
In Examples 13 and 19, agglomeration was observed in the paint liquid, and the liquid was turbid, and even when the container was shaken, it was not fluid.

[On-site workability]
The coating composition obtained in each example was applied on a building window glass by a sponge coating method using a sponge bar, and then naturally dried at room temperature for 7 days to form a coating film. At the time of application, a part on the glass was coated once, and the other part was coated twice. In the case of coating twice, the above drying process was performed after the first coating was overcoated without drying.
The appearance of the coating film after drying was observed, and the leveling property and overcoatability were evaluated according to the following criteria. The results are shown in Table 2.
○: The appearance of the coating film is not uneven both in the part coated twice and the part coated once.
(Triangle | delta): The external appearance of a coating film has a nonuniformity only in the part coated twice.
X: The appearance of the coating film is uneven both in the part coated twice and the part coated once.

[Production of coating film (heat ray ultraviolet ray shielding film or heat ray shielding film)]
As a transparent substrate, a soda lime glass plate (100 mm × 100 mm, thickness 3.5 mm) was prepared, the surface was polished with cerium oxide, washed with distilled water and dried to obtain washed glass.
2 mL of an amino group-containing silane coupling agent (Shin-Etsu Silicone KBP-90 aqueous solution, 32% active ingredient diluted to 0.1% active ingredient with ethanol) is dropped onto the surface of the washed glass plate and spinned. After applying by a coating method, the primer layer was formed by drying at 25 ° C. for 2 minutes. Thus, a pretreated glass plate was obtained.
The coating composition obtained in each example was applied on the primer layer of the pretreated glass plate obtained above, dried and cured at 25 ° C. for 7 days, and a 4 μm-thick coating film (heat ray ultraviolet ray shielding film or heat ray) A shielding film) was formed. The film thickness was measured with a stylus method (DEKTAK3030 manufactured by Sloan Technology) from the step between the coating film and the substrate after scraping the coating film sample with a cutter. The samples thus obtained were evaluated.
In Examples 1, 4 to 10, 12 to 13, and 17 to 19, as a method of applying the coating composition on the primer layer of the pretreated glass plate, 2 mL of the coating composition is dropped and applied by spin coating. The method was used.
In Examples 2 and 14 to 16, a method of applying 2 mL of the coating composition by the bar coat method was used.
In Example 3, a method of applying 2 mL of the coating composition by the flow coat method was used.
In Example 11, a first sample (hereinafter referred to as Example 11-1) was prepared in the same manner as in Example 1 using the coating composition obtained in Example 11, and the following sponge was used using the same coating composition. A second sample (hereinafter referred to as Example 11-2) was produced by a coating method.
That is, when forming the primer layer, the silane coupling agent was applied to the surface of the cleaned glass plate using a sponge bar. Otherwise, a pretreated glass plate was obtained in the same manner as in Example 1. Moreover, the method of apply | coating 100 mL of a coating composition with a sponge bar was used as a method of apply | coating a coating composition on the primer layer of a pre-processed glass plate. Otherwise, a second sample (Example 11-2) was obtained in the same manner as in Example 1.

[Appearance of coating film]
The appearance of the coating film of the sample was evaluated by visual observation. The results are shown in Table 2.

[Haze value]
The haze value of the sample was measured as an index of transparency. The measurement was performed according to JIS-K7105 (1981), using a haze computer (manufactured by Suga Test Instruments Co., Ltd., model: HGM-3DP). If the haze value of the film was 1.0% or less, there was no practical problem. The results are shown in Table 2.
In addition, the haze value of the washed soda lime glass plate used as the transparent substrate was 0.1%.

[Light transmittance]
The visible light transmittance and solar radiation transmittance of the sample were measured by a method according to JIS-R3106 (1998). The higher the visible light transmittance, the higher the transparency, and 50% or more was regarded as having no practical problem. The solar radiation transmittance is lower than the visible light transmittance, and the larger the difference is, the higher the heat ray shielding property is. The difference (Tv−Te) between the visible light transmittance (Tv, unit:%) and the solar radiation transmittance (Te, unit:%) was 5% or more, and there was no practical problem.
In addition, the ultraviolet transmittance was measured by a method according to ISO 9050. The measurement was performed using a spectrophotometer (trade name: U-4100, manufactured by Hitachi Keiki Co., Ltd.). These results are shown in Table 2.

[Adhesion]
The adhesion of the coating film was evaluated in accordance with the adhesion test by the cross-cut method specified in JIS-K5600-5-6 (1999) and the classification of the test results. The classification 0 with no peeling of the coating film was rated as ◯, the classification 1-2 with partial peeling but no problem in practical use was rated as Δ, and the classification 3-5 with many peeling parts was marked as x. The results are shown in Table 3.
The results are shown in Table 3.

[Pencil hardness]
The scratch hardness of the coating film was measured by the pencil method specified in JIS-K5600-5-4 (1999). If it was 2B or more, there was no problem in practical use. The results are shown in Table 3.

[Solvent resistance]
Ethanol was immersed in a non-woven wiping cloth (trade name BEMCOT, M-1, 150 mm, manufactured by Asahi Kasei Co., Ltd.), and the coating film was wiped off under the condition that the coating film was worn 10 times with a load of 100 g. After wiping, ◯ indicates that there is no scratch, △ indicates that there is a slight scratch but there is no practical problem, and × indicates that there is scratch or film dissolution on the entire surface. The results are shown in Table 3.

[Acid resistance]
The entire sample was immersed in a 0.1 N aqueous solution of H ₂ SO ₄ for 24 hours. ○ if there is no change in the paint film such as discoloration or peeling of the coating film, △ if there is partial discoloration or peeling, such as at the edge, but there is no practical problem, × if there is a change It was. The results are shown in Table 3.

[Alkali resistance]
The entire sample was immersed in a 0.1N NaOH aqueous solution for 24 hours. ○ if there is no change in the paint film such as discoloration or peeling of the coating film, △ if there is partial discoloration or peeling, such as at the edge, but there is no practical problem, × if there is a change It was. The results are shown in Table 3.

[Boiling water resistance]
After the whole sample was immersed in boiling water for 2 hours, an adhesion test by a cross-cut method defined in JIS-K5600-5-6 (1999) was performed. The classification 0 with no peeling of the coating film was rated as ◯, the classification 1-2 with partial peeling but no problem in practical use was rated as Δ, and the classification 3-5 with many peeling parts was marked as x. The results are shown in Table 3.

[Accelerated weather resistance]
The sample was subjected to an accelerated weathering exposure test using a metal weather tester (manufactured by Daipura Wintes, trade name: Metal Weather). The exposure cycle under the following conditions was set to 17 times corresponding to 100 hours, and after a total 500 hour exposure test, the coating film appearance, solar transmittance, and adhesion were evaluated by the above methods. ◯ if there is no change between the evaluation result when the exposure test is not performed and the evaluation result after the exposure test, △ if there is a change in any of the film appearance, solar transmittance, or adhesion X indicates that there are changes in two or more items of solar radiation transmittance and adhesion. The results are shown in Table 3.
(Exposure cycle)
Mode: L + D (L: irradiation, D: dark condensation).
L: Temperature 63 ° C., humidity 50%, time 5 hr.
D: Temperature 30 ° C., humidity 98%, time 1 hr.
REST mode: No condensation.
Light amount: 50.0 mW / cm ² (365 nm).
Before and after D (10 sec) with shower.

From the results in the table, the film obtained in Example 8 using an acrylic resin instead of the component (A) was inferior in solvent resistance, acid resistance, alkali resistance and weather resistance, and was not practical.
In Example 13 where the hydroxyl value of the fluororesin (A) was small, the dispersion stability of the heat ray shielding inorganic fine particles (B) and the ultraviolet absorber (C) was inferior. Moreover, the haze value was high and transparency was inferior.
In Example 19 in which the average particle size of the heat ray shielding inorganic fine particles (B) was large, the haze value was high and the transparency was poor.

  By using the coating composition of the present invention, it is highly durable for general buildings such as buildings, offices, and houses, as well as glass, plastic, and various other transparent substrates such as vehicle windows, show windows, and showcases. A transparent heat ray shielding film can be formed.

Claims (10)

  Including the fluororesin (A) and the heat ray shielding inorganic fine particles (B), the hydroxyl value of the fluororesin (A) is 30 to 200 mgKOH / g, and the heat ray shielding inorganic fine particles (B) have an average particle size of 1 to A fluororesin composition for paint, which is 200 nm.   The fluororesin composition for paints according to claim 1 whose number average molecular weights of said fluororesin (A) are 20000 or less 1000 or more.   The heat ray shielding inorganic fine particles (B) are at least one selected from the group consisting of tin and indium composite oxide fine particles, tin and antimony composite oxide fine particles, lanthanum hexaboride fine particles, and zinc oxide fine particles. The fluororesin composition for paints according to claim 1 or 2.   The fluororesin composition for coating materials according to any one of claims 1 to 3, comprising an ultraviolet absorber (C).   The fluororesin composition for paint according to claim 4, wherein the ultraviolet absorber (C) is at least one selected from the group consisting of a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, and a triazine ultraviolet absorber. object.   The coating material according to any one of claims 1 to 5, wherein the fluororesin (A) includes an alkoxysilane (D) having a curing reactive site and a reactive group that reacts with the curing reactive site. Fluorine resin composition.   The article | item which has a heat ray shielding film formed using the fluororesin composition for coating materials as described in any one of Claims 1-6 on a base material.   The article according to claim 7, wherein a primer layer is provided on the substrate, and the heat ray shielding film is formed on the primer layer.   The article according to claim 8, wherein the primer layer is a layer formed using a silane coupling agent.   The article of claim 8 or 9, wherein the substrate is glass.