JP2021050334A - Composition for base material scattering prevention coating, base material scattering prevention coating, scattering preventive base material, method for forming scattering preventive base material and kit for forming base material scattering prevention coating - Google Patents

Abstract

To provide a composition for base material scattering prevention coating, a base material scattering prevention coating, a scattering preventive base material, a method for forming a scattering preventive base material and a kit for forming a base material scattering prevention coating whereby it is possible to sufficiently prevent the scattering of a base material that is broken.SOLUTION: A composition for base material scattering prevention coating contains an aqueous emulsion of a polycarbonate urethane resin and has thixotropy.SELECTED DRAWING: Figure 1

Description

The present invention relates to a composition for a base material shatterproof coating film, a base material shatterproof coating film, a shatterproof base material, a method for forming a shatterproof base material, and a base material shatterproof coating film forming kit.

A film for preventing glass from scattering is attached to the windows of buildings and automobiles so that the glass does not scatter when the windows are damaged. However, the glass shatterproof film for window sticking is severely deteriorated over time, it is difficult to use it for glass having irregularities such as frosted glass and template glass, and it is difficult for general consumers who do not have special technology to stick it. It is known to have problems such as.

Conventionally, various types of films for preventing scattering of a base material that scatters when broken, such as glass such as window glass, have been studied. For example, Patent Document 1 includes a first polyester base material layer, a bonding layer containing an ultraviolet absorber, a second polyester base material layer, and an acrylic pressure-sensitive adhesive layer having a thickness of 100 μm or more in this order. A glass shatterproof film is disclosed. A film such as that described in Patent Document 1 can adhere well to the inner surface of a template glass having irregularities such as patterns with a high adhesive force, and when peeled off, it adheres to the inner surface of the template glass. It is disclosed that the amount of adhesive residue that adheres can be reduced.

Patent Document 2 discloses that an adhesive having specific physical properties is used and combined with a plastic film, particularly a polyester film having additional performance. In Patent Document 2, such a combination provides good workability when attached to window glass of automobiles, buildings, etc., does not leave adhesive residue when peeled off, is highly transparent, and transmits heat rays and ultraviolet light. It is disclosed that it is possible to provide a laminated film for window attachment, which is excellent in anti-scattering performance.

On the other hand, in order to improve workability, a coating film for preventing base material scattering is also formed by applying a solution-type paint. For example, Patent Document 3 states that (a) caprolactone-modified acrylic resin 50 to 60% by weight, (b) acrylic polyol 10 to 20% by weight, (c) polyurethane resin 10 to 20% by weight, and (d) reaction as the main agent. Catalyst 0.1-1.5% by weight, (e) wetting additive 0.1-1.5% by weight, (f) pigment 1.0-1.5% by weight, and (g) solvent 5-20. A glass shatterproof coating film containing% by weight and containing a hexamethylene diisocyanate trimmer resin as a curing agent is disclosed.

JP-A-2018-65320 Japanese Unexamined Patent Publication No. 2000-96009 JP-A-2017-109918

However, as a result of detailed examination of conventional films such as the above-mentioned Patent Documents 1 and 2, the present inventor has found that the adhesion is sufficient for attaching to a base material, particularly a base material having irregularities on the surface such as frosted glass. It turns out that there is room for further improvement. If the adhesion is not good, it is difficult to sufficiently prevent the base material having irregularities on the surface from scattering even if such a film is used. Further, the conventional method of applying the base material scattering prevention coating film composition to a base material such as glass to form a coating film is excellent in workability, but can sufficiently prevent the base material from scattering. It has been found that it is difficult to form a coating film having the thickness of.

The present invention has been made in view of the above circumstances, and a composition for a base material scattering prevention coating film, a base material scattering prevention coating film, which can sufficiently prevent the base material from scattering when the base material is damaged. An object of the present invention is to provide a shatterproof base material, a method for forming a shatterproof base material, and a kit for forming a base material shatterproof coating film.

As a result of diligent research to achieve the above object, the present inventor has made the composition for base material scattering prevention coating film and the base material scattering prevention coating film having a predetermined composition and characteristics like a base material, particularly frosted glass. We have found that it is possible to sufficiently prevent the base material having irregularities on the surface from scattering when the base material is damaged, and have completed the present invention.

That is, the present invention is as follows.
[1]
A composition for a base material shatterproof coating film, which contains an aqueous emulsion of a polycarbonate-based urethane resin and has thixotropy properties.
[2]
The composition for a substrate shatterproof coating film according to [1], wherein the glass transition temperature of the polycarbonate-based urethane resin is −50 ° C. or higher and −10 ° C. or lower.
[3]
The composition for a substrate shatterproof coating film according to [1] or [2], which has a thixotropy index of 2 or more.
[4]
The composition for a substrate shatterproof coating film according to any one of [1] to [3], wherein the polycarbonate-based urethane resin has a breaking strength of 30 MPa or more and a breaking elongation of 200% or more. ..
[5]
The composition for a substrate shatterproof coating film according to any one of [1] to [4], further comprising an infrared absorber.
[6]
The composition for a substrate shatterproof coating film according to any one of [1] to [5], further comprising an ultraviolet absorber.
[7]
A base material shatterproof coating film which is a solidified product of the composition for a base material shatterproof coating film according to any one of [1] to [6].
[8]
A base material shatterproof coating film containing a polycarbonate-based urethane resin, wherein the surface of the base material shatterproof coating film has irregularities.
[9]
The base material shatterproof coating film according to [8], further comprising an infrared absorber.
[10]
The base material shatterproof coating film according to [8] or [9], further comprising an ultraviolet absorber.
[11]
The base material shatterproof coating film according to any one of [8] to [10], wherein the glass transition temperature of the polycarbonate-based urethane resin is −50 ° C. or higher and −10 ° C. or lower.
[12]
The substrate shatterproof coating film has a maximum convex height of 100 μm or more and 2000 μm or less from the standard thickness of the surface, and a deepest depth of 50 μm or more and 1500 μm or less from the standard thickness of the surface [7]. ] To [10]. The base material shatterproof coating film according to any one of [10].
[13]
A shatterproof base material comprising a base material and a base material shatterproof coating film according to any one of [7] to [12] arranged on at least one surface of the base material.
[14]
[13] The shatterproof base material according to [13], further comprising a solidified product of a cationic aqueous sealer between the base material and the base material shatterproof coating film.
[15]
The shatterproof substrate according to [14], wherein the cationic aqueous sealer contains an aqueous emulsion of a polyurethane resin.
[16]
The base material is one selected from the group consisting of inorganic glass, acrylic resin, polycarbonate resin, and fiber-reinforced plastic, and inorganic glass, acrylic resin, polycarbonate resin, and fiber-reinforced plastic provided with a shatterproof film. The shatterproof base material according to any one of [13] to [15] described above.
[17]
The step of applying the base material scattering prevention coating film composition according to any one of [1] to [6] to the surface of the base material, and drying the applied base material scattering prevention coating film composition. A method of forming a shatterproof substrate, including steps.
[18]
A step of applying the cationic aqueous sealer to the surface of the base material, a step of drying the applied cationic aqueous sealer, and a step of applying [1] to [6] to the surface of the solidified product of the cationic aqueous sealer. A shatterproof group comprising, in this order, a step of applying the base material shatterproof coating film composition according to any one and a step of drying the applied base material shatterproof coating film composition. How to form the material.
[19]
The step of applying the composition for a base material scattering prevention coating film and the step of drying the composition for a base material scattering prevention coating film are repeated twice or more in this order, [17] or [18]. The method for forming a shatterproof substrate according to.
[20]
The scattering according to any one of [17] to [19], wherein the composition for a base material scattering prevention coating film is applied by roller coating in the step of applying the base material scattering prevention coating film composition. A method for forming a preventive base material.
[21]
The roller coating is a roller coating using a roller having a coating surface that comes into contact with the surface of the base material or the surface of the cationic aqueous sealer.
The method for forming an anti-scattering base material according to [20], wherein the roller has an uneven shape on the coated surface.
[22]
A base material shatterproof coating film forming kit comprising the composition for a base material shatterproof coating film according to any one of [1] to [6] and a cationic aqueous sealer.

According to the present invention, a composition for a base material scattering prevention coating film, a base material scattering prevention coating film, an anti-scattering base material, and an anti-scattering property that can sufficiently prevent the base material from scattering when the base material is damaged. It is possible to provide a method for forming a base material and a kit for forming a base material shatterproof coating film.

It is schematic cross-sectional view which shows an example of the base material which formed the base material scattering prevention coating film of this invention partially. It is a schematic perspective view which shows an example of the roller used in the method of forming the base material scattering prevention coating film of this invention. It is Example data which evaluates the infrared ray shielding ability of the base material scattering prevention coating film of this embodiment.

Hereinafter, a mode for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are designated by the same reference numerals, and duplicate description will be omitted. In addition, the positional relationship such as up, down, left, and right shall be based on the positional relationship shown in the drawings unless otherwise specified. Furthermore, the dimensional ratios in the drawings are not limited to the ratios shown.

FIG. 1 is a schematic cross-sectional view partially showing an example of a base material on which a base material shatterproof coating film (hereinafter, also simply referred to as “coating film”) of the present invention is formed. This cross-sectional view shows a cross section that appears when a base material on which a base material scattering prevention coating film is formed (hereinafter, also referred to as “scattering prevention base material”) is cut in parallel with the thickness direction of the base material. The shatterproof base material 100 is a cationic water-based sealer (hereinafter, simply referred to as "simply") arranged between the base material 110, the base material shatterproof coating film 120, and the base material 110 and the base material shatterproof coating film 120. Also called "sealer". Not shown.) The base material shatterproof coating film 120 has irregularities on the surface and is adhered onto the base material 110 via a cationic water-based sealer. The base material scattering prevention coating film 120 is a solidified product of a base material scattering prevention coating film composition (hereinafter, also simply referred to as “coating film composition”), which will be described later.

(Base material)
The base material 110 is not particularly limited as long as it can scatter, and may be any material that can form a coating film via a sealer. Examples of the material of the base material include glass such as inorganic glass (for example, flat glass and wire-reinforced glass) and resins such as acrylic resin and polycarbonate resin, and the resin is impregnated with fibers to reinforce the fibers. It may be a resin (fiber reinforced plastic). Further, examples of the use of the base material include windows for buildings, windows for vehicles used for automobiles or trains, show windows, stained glass, water tanks, solar glass panels, and mirror surfaces.

Further, the surface shape of the base material does not have to be smooth, and the surface may have irregularities, curved surfaces, or a three-dimensional structure, such as frosted glass and template glass. May be good. Further, the base material may be made of one kind of material or may be made of two or more kinds of materials. For example, even if the glass surface has dirt or deposits such as dust, the coating film composition of the present embodiment is applied onto the glass surface and dried to form a coating film, thereby scattering the base material. It is possible to form a coating film having excellent properties of preventing the above (referred to as "base material scattering prevention property" in the present specification). Therefore, according to the present embodiment, for example, the base material scatters even on a base material (for example, glass, acrylic resin, polycarbonate resin, or fiber reinforced plastic) to which the adhesive residue is attached by peeling off the shatterproof film. It is possible to form a coating film having excellent preventive properties. Further, the base material may be glass, acrylic resin, polycarbonate resin or fiber reinforced plastic to which a shatterproof film is attached. The shatterproof film may be brittle due to aged deterioration, may be whitened, or may be deteriorated. For example, a part of the shatterproof film may be cracked, peeled off, or dropped off. Although the substrate scattering prevention property of such a film may be significantly impaired, the coating film formed by applying the coating film composition of the present embodiment on it and drying it without peeling off the film , Shows good substrate scattering prevention.

(Composition for coating film to prevent substrate scattering)
The composition for a base material shatterproof coating film of the present embodiment contains an aqueous emulsion of a polycarbonate-based urethane resin, has thixotropy properties, and is a coating film that prevents the base material from scattering when the base material is damaged. (In this specification, it is also referred to as a "base material shatterproof coating film"). By using such a coating film composition, it is possible to easily impart good base material scattering prevention property to the base material. Further, since the coating film composition of the present embodiment is a water-based paint and does not contain an organic solvent, or even if it contains an organic solvent, the amount of the coating film composition is small. preferable. Further, the coating film composition of the present embodiment can be applied to a base material having irregularities on the surface such as frosted glass or template glass with good coatability, and therefore has irregularities on such a surface. It is possible to impart excellent base material scattering prevention property to the base material. In addition, since it can be applied to a shatterproof film, particularly a shatterproof film that has deteriorated over time, with good coatability, excellent base material shatterproofness is imparted to the base material to which the film is attached. can do. As a result, the coating film composition can also be used for maintenance of the base material to which the anti-scattering property is imparted. Further, since the coating film composition of the present embodiment contains a polycarbonate-based urethane resin, the base material shatterproof coating film formed by the coating film composition has excellent water resistance, abrasion resistance, fire resistance and fire resistance. Has weather resistance.

(Thixotropy)
In the present embodiment, thixotropic property is a state in which the viscosity is relatively high in a steady state (for example, a state in which shear stress is not applied), and when shear stress is applied, the viscosity decreases, and shear stress is applied. It shows the property of returning to the original viscosity when stopped. Since the composition for coating film of the present embodiment has thixotropy property, the viscosity decreases when it is applied to a base material, which makes it easier to apply, while the viscosity increases after application to prevent dripping. be able to. As a result, the coating film obtained by drying the applied coating film composition is formed evenly on the base material and has high adhesion to the base material, and thus has good base material scattering prevention property. Can have. Further, even a general consumer who does not have a special technique can easily form a base material shatterproof coating film.

The thixotropy property is represented by the thixotropy index TI measured by a dynamic viscoelasticity measuring device (for example, a BH type viscometer manufactured by Toki Sangyo Co., Ltd.). In this embodiment, the thixotropy index TI is defined by the following formula (1).
TI = (viscosity at a liquid temperature of 23 ° C. at a rotation speed of 2 rpm) / (viscosity at a liquid temperature of 23 ° C. at a rotation speed of 20 rpm) ... (1)

The closer the thixotropy index TI is to 1, the more the behavior as a Newtonian liquid is exhibited, and the larger the thixotropy index TI is, the higher the thixotropy property is.

In the present embodiment, the thixotropy index TI of the coating film composition is not particularly limited as long as it is larger than 1, but from the viewpoint of further improving the base material scattering prevention property and further improving the workability at the time of coating film formation, for example, It is preferably 2 or more. When the thixotropy index TI is in the above range, the coating film composition further increases the difference between the low viscosity when applied to the substrate and the high viscosity after application, and thus further on the substrate. Since it is formed evenly and has higher adhesion to the base material, it is possible to have even better base material scattering prevention property. In addition, the workability at the time of forming the coating film can be further improved. From the same viewpoint, the thixotropy index TI is more preferably 3 or more, further preferably 4 or more, and further preferably 5 or more. The upper limit of the thixotropy index TI is not particularly limited, but the thixotropy index TI may be, for example, 8 or less, or 7 or less.

In the present embodiment, the thixotropy index TI of the coating film composition can be controlled by adjusting the average particle size of the polycarbonate-based urethane resin. Specifically, the average particle size of the polycarbonate-based urethane resin is preferably 0.01 μm or more and 1.5 μm or less, more preferably 0.02 μm or more and 1.0 μm or less, and 0.03 μm or more and 0.5 μm or less. Is even more preferable. Further, the thixotropy index TI can be set in the above range by adding the thixotropy-imparting agent described later to the coating film composition. Specifically, the thixotropy index TI can be set in the above range depending on the type and content of the thixotropy-imparting agent added to the coating film composition.

(viscosity)
In the present embodiment, the viscosity of the coating film composition is not particularly limited, but from the viewpoint of adjusting the thickness of the coating film to a preferable range and improving the workability at the time of forming the coating film, for example, at 23 ° C. It is preferably 10 Pa · s or more and 60 Pa · s or less, more preferably 15 Pa · s or more and 40 Pa · s or less, and even more preferably 20 Pa · s or more and 35 Pa · s or less. When the viscosity of the coating film composition is in the above range, the coating property and the substrate scattering prevention property of the coating film composition are further improved. The viscosity of the coating film composition is measured by a dynamic viscoelasticity measuring device (for example, a BH type viscometer manufactured by Toki Sangyo Co., Ltd.).

In the present embodiment, the viscosity of the coating film composition is the content of a solvent described later such as water or an organic solvent with respect to the total amount of the coating film composition, and the thixotropy-imparting agent which also has a role as a thickener. The above range can be obtained by adjusting the type and content. In addition, there is a tendency that the viscosity of the coating film composition can be increased by reducing the content of the solvent. For example, the content of the solvent is preferably 15% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 80% by mass or less with respect to the total amount of the coating film composition.

(Polycarbonate urethane resin)
The aqueous emulsion of the polycarbonate-based urethane resin in the present embodiment is an emulsion containing a solvent containing water as a main component and particles of the polycarbonate-based urethane resin dispersed in the solvent. This aqueous emulsion is obtained by emulsion polymerization of a polycarbonate polyol and a polyisocyanate in a solvent containing water as a main component. As a result of diligent research, the present inventor has conducted a coating film to prevent scattering of the base material when the composition for coating film contains a polycarbonate-based urethane resin rather than a case where the composition for a coating film contains a polyether-based urethane resin or a polyester-based urethane resin. It was clarified that the anti-scattering property of the base material is further improved. This is because the coating film composition contains a polycarbonate-based urethane resin having high elasticity, so that the adhesion to the base material is further improved and the coating film follows the base material when the base material is damaged. Is considered to be the result of further increase, but the factors are not limited to this.

Further, since the polycarbonate-based urethane resin has high flame retardancy, the coating film composition of the present embodiment has excellent fire resistance. Further, since the polycarbonate-based urethane resin is less likely to cause discoloration and deterioration even when exposed to sunlight for a long time, the coating film composition of the present embodiment has excellent weather resistance.

In the coating film composition of the present embodiment, the average particle size of the polycarbonate-based urethane resin particles is not particularly limited as long as the particle size can maintain the emulsion state, and is, for example, 0.01 μm or more and 1.5 μm or less. It may be 0.02 μm or more and 1.0 μm or less, or may be 0.03 μm or more and 0.5 μm or less. The average particle size of the resin particles is measured by a laser diffraction type particle size distribution measuring device (for example, a concentrated particle size analyzer, manufactured by Otsuka Electronics Co., Ltd., product name "FPAR-1000").

Further, in the present embodiment, the glass transition temperature Tg of the polycarbonate urethane resin is preferably −50 ° C. or higher and −10 ° C. or lower, more preferably −40 ° C. or higher and −15 ° C. or lower, and more preferably −35 ° C. It is even more preferable that the temperature is −20 ° C. or lower. When the glass transition temperature Tg is -10 ° C or lower, the coating film formed by solidification of the coating film composition is excellent in preventing substrate scattering even at a low temperature as compared with the case where it exceeds -10 ° C. You can keep your sex. Further, when the glass transition temperature Tg is −50 ° C. or higher, the coating film formed by solidification of the coating film composition is more excellent in base material scattering at room temperature as compared with the case where the temperature is lower than −50 ° C. It tends to have preventive properties. The glass transition temperature Tg of the resin is determined by a dynamic viscoelasticity measuring device (for example, manufactured by TA Instruments, product name "RSA3") or a thermomechanical analyzer (for example, manufactured by Hitachi High-Tech Science Co., Ltd., product name "TMA-"). It can be measured using 7000 ").

In the present embodiment, the glass transition temperature Tg of the polycarbonate-based urethane resin can be controlled by adjusting the molecular weight of the polycarbonate-based urethane resin and introducing a modifying group.

In the present embodiment, the 100% modulus of the polycarbonate urethane resin is preferably 5 MPa or more and 50 MPa or less, more preferably 7 MPa or more and 45 MPa or less, and even more preferably 10 MPa or more and 40 MPa or less. When the 100% modulus of the polycarbonate-based urethane resin is in the above range, the coating film formed by solidification of the coating film composition tends to have more excellent substrate scattering prevention property. In the present embodiment, the 100% modulus of the resin means the stress required to stretch the resin 100%, and is a tensile tester (for example, manufactured by Shimadzu Corporation, product name "Autograph AG-". It is measured by pulling the resin using "I"). The units "MPa" and "N / mm ² " are the same value.

In the present embodiment, the breaking strength of the polycarbonate-based urethane resin is preferably 30 MPa or more, more preferably 35 MPa or more, and even more preferably 40 MPa or more. When the breaking strength of the polycarbonate-based urethane resin is within the above range, the coating film formed by solidification of the coating film composition has more excellent impact resistance and further excellent substrate scattering prevention property. Tend to have. The upper limit of the breaking strength of the polycarbonate-based urethane resin is not particularly limited, but may be 500 MPa, 400 MPa, or 300 MPa. In the present embodiment, the breaking strength of the resin is measured by pulling the resin using a tensile tester (for example, manufactured by Shimadzu Corporation, product name "Autograph AG-I").

In the present embodiment, the breaking elongation of the polycarbonate-based urethane resin is preferably 200% or more, more preferably 250% or more, and even more preferably 300% or more. When the breaking strength of the polycarbonate-based urethane resin is within the above range, the coating film formed by solidification of the coating film composition has more excellent flexibility and further excellent substrate scattering prevention property. There is a tendency. The upper limit of the elongation at break of the polycarbonate-based urethane resin is not particularly limited, but may be 1000%, 900%, or 800%. In the present embodiment, the elongation at break of the resin is measured by pulling the resin using a tensile tester (for example, manufactured by Shimadzu Corporation, product name "Autograph AG-I").

In the present embodiment, the 100% modulus, breaking strength, and breaking elongation of the polycarbonate-based urethane resin can be controlled by adjusting the molecular weight of the polycarbonate-based urethane resin and introducing a modifying group. Further, the 100% modulus, breaking strength, and breaking elongation of the polycarbonate-based urethane resin may be adjusted by combining two or more kinds of polycarbonate-based urethane resins.

Further, from the viewpoint of further enhancing the base material scattering prevention property, the content of the polycarbonate-based urethane resin is preferably 3% by mass or more and 85% by mass or less with respect to the total amount of the coating film composition, and is 10% by mass. It is more preferably 80% by mass or more, and even more preferably 20% by mass or more and 75% by mass or less. When the content of the polycarbonate-based urethane resin is 3% by mass or more with respect to the total amount of the coating film composition, the substrate scattering prevention property is further improved as compared with the case where it is less than 3% by mass. Further, when the content of the polycarbonate-based urethane resin is 85% by mass or less with respect to the total amount of the coating film composition, the viscosity of the coating film composition is in a preferable range as compared with the case where it exceeds 85% by mass. It is maintained and tends to have higher workability when forming a coating film.

The polycarbonate-based urethane resin used in the present embodiment may be produced by a conventionally known method, or a commercially available product may be used. Examples of commercially available products include Takelac W-635 (trade name manufactured by Mitsui Kagaku Co., Ltd.), Eternacol UW-3100 (trade name manufactured by Ube Kosan Co., Ltd.), Eternacol UW-5502 (trade name manufactured by Ube Kosan Co., Ltd.), and Ucoat UX. -485 (trade name of Sanyo Kasei), WBR-2101 (trade name of Taisei Fine Chemicals), Merci 5030 (trade name of Toyo Polymer), Merci 5045 (trade name of Toyo Polymer), and R-4000 (trade name of Toyo Polymer). Kusumoto Kasei Co., Ltd. (trade name) and the like. Polycarbonate urethane resins may be used alone or in combination of two or more.

(solvent)
The solvent of this embodiment contains water as a main component. Therefore, the odor when forming the coating film is reduced, which is preferable in terms of environmental hygiene. In the present embodiment, the solvent is a liquid in the coating film composition other than the resin component. The solvent in this embodiment is not particularly limited as long as it contains water as the main component, but may include an organic solvent and a film-forming auxiliary described later. The organic solvent is not particularly limited, and examples thereof include hydrocarbons, ketones, alcohols, acetic acid esters, and glycol ethers. The organic solvent may be used alone or in combination of two or more.

From the viewpoint of environmental hygiene, the content of the organic solvent other than the film-forming auxiliary is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total amount of the coating film composition. It is even more preferably 5% by mass or less, further preferably 3% by mass or less, and even more preferably 1% by mass or less. From the same viewpoint, the content of the organic solvent containing the film-forming auxiliary is preferably 20% by mass or less, more preferably 15% by mass or less, based on the total amount of the coating film composition. It is even more preferably 10% by mass or less.

(Additive)
The coating film composition of the present embodiment has a binder, a curing aid, and thixotropy within a range that does not hinder the solution of the problem of the present invention from the viewpoint of further enhancing the base material scattering prevention property and the workability. Additives such as impartants, film-forming aids, UV absorbers, and infrared absorbers may be included. In particular, the coating film composition preferably contains a binder. Further, since the coating film composition of the present embodiment has thixotropy as described above, a coating film having a sufficient thickness can be formed on the base material as described later. Therefore, in the embodiment in which the coating film composition contains an ultraviolet absorber and / or an infrared absorber, the ultraviolet absorber and / or infrared rays are compared with the coating film formed by the conventional coating film composition. The effect of the absorbent can be further exerted.

The binder is not particularly limited as long as it can be used as a binder for an aqueous emulsion, and for example, resins such as acrylic styrene resin, acrylic urethane resin, acrylic silicon resin, and modified polyester urethane resin can be used. Can be mentioned. The binder may be used alone or in combination of two or more. When the coating film composition of the present embodiment contains a binder, the coating film formed by solidification of the coating film composition is further improved in flexibility, flexibility, and adhesion to the substrate. , It tends to have more excellent substrate scattering prevention property. From the viewpoint of more effectively and surely exerting the above effects, the binder is preferably a modified polyester-based urethane resin, and more preferably an acrylic-modified polyester-based urethane resin. Regarding the content of the binder, from the viewpoint of more sufficiently and surely exerting the function as a binder and more effectively and surely preventing the deterioration of the effect due to the polycarbonate-based urethane resin, with respect to 100 parts by mass of the polycarbonate-based urethane resin. It is preferably 10 parts by mass or more and 500 parts by mass or less, more preferably 15 parts by mass or more and 450 parts by mass or less, and further preferably 20 parts by mass or more and 400 parts by mass or less. When a resin is used as the binder, it is preferably used in the form of a resin emulsion from the viewpoint of handleability.

The curing aid is not particularly limited, and examples thereof include an aqueous isocyanate curing agent, a polycarbodiimide curing agent, an oxazoline curing agent, a melamine curing agent, a polyethyleneimine curing agent, an aziridine curing agent, a zirconium curing agent, and an epoxy curing agent. .. The curing aid may be used alone or in combination of two or more. The content thereof is preferably 1 part by mass or more and 50 parts by mass or less, and 3 parts by mass or more and 30 parts by mass or less, based on 100 parts by mass of the total amount of the polycarbonate-based urethane resin and the binder. More preferably, it is 5 parts by mass or more and 20 parts by mass or less. By adding the curing aid in the above range, the coating film composition of the present embodiment is applied to the base material and then left at room temperature, and the urethane resin and the curing aid have a crosslinked structure. As a result, a coating film having further excellent adhesion between the coating film and the base material and at the same time having various properties such as film strength, chemical resistance, water resistance, or base material scattering prevention property is formed. To. The above-mentioned curing aid is preferably added to the coating film composition immediately before being applied to the substrate, for example.

The thixotropic property-imparting agent is not particularly limited, and is, for example, cellulose compounds such as carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose, and ammonium salts or alkali metal salts thereof, poly (meth) acrylic acid, and modified poly. Polycarboxylic acids such as (meth) acrylic acid, and polyvinyl alcohol-based polymers such as alkali metal salts, polyvinyl alcohols, modified polyvinyl alcohols, and ethylene-vinyl alcohol copolymers, and polyether polyol-based urethane resins. Examples thereof include urethane resins other than the polycarbonate-based urethane resin. The thixotropy-imparting agent may be used alone or in combination of two or more. As for the content thereof, the thixotropy index TI of the coating film composition is preferably adjusted to be 2 or more, more preferably 3 or more, and 4 or more. It is more preferable to adjust it, and it is further preferable to adjust it to 5 or more. By adding the thixotropy-imparting agent in the above range, the viscosity of the coating film composition decreases when it is applied to glass or the like, and increases after it is applied. The property can be further enhanced, and the base material scattering prevention property becomes even better.

The film-forming auxiliary is not particularly limited as long as it can assist the film-forming property of the aqueous emulsion, and for example, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, butyl carbitol, and di. Examples include propylene glycol methyl ether acetate, texanol, and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate. The film-forming auxiliary may be used alone or in combination of two or more. In terms of its content, the total of the polycarbonate-based urethane resin and the binder is from the viewpoint of more sufficiently and surely exerting the function as a film-forming auxiliary and more effectively and surely preventing the deterioration of the effect due to the polycarbonate-based urethane resin. It is preferably 0 parts by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 45 parts by mass or less, and 15 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the total amount of. Even more preferable.

The ultraviolet absorber is not particularly limited as long as it can absorb ultraviolet rays, and is, for example, a salicylic acid derivative such as methyl salicylate, p-tert-butylphenyl-salicylate, and p-octylphenyl-salicylate; Aromatic ketones such as −hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and 4-dodecyloxy-2-hydroxybenzophenone; 2- (2'-hydroxy-5'-methylphenyl) ) Bentriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, and 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) Triazole derivatives such as benzotriazole; acrylic acid derivatives such as 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate; and as well as zinc oxide, zirconium oxide, cerium oxide, iron oxide, and titanium oxide. Examples include inorganic compounds. The ultraviolet absorber may be used alone or in combination of two or more. The content is preferably 0.1 part by mass or more and 20 parts by mass or less, and 0.3 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the total amount of the polycarbonate-based urethane resin and the binder. It is more preferable that the amount is 0.5 parts by mass or more and 5 parts by mass or less. By adding the ultraviolet absorber in the above range, it is possible to impart the ultraviolet shielding ability to the coating film and reduce discoloration and deterioration of the interior decoration without impairing the transparency. As the ultraviolet absorber, a triazole derivative is preferably used.

The infrared absorber is not particularly limited as long as it can absorb infrared rays, and is, for example, a cyanine compound, a naphthalocyanine compound, a phthalocyanine compound, an anthraquinone compound, a naphthoquinone compound, a diimonium compound, or a polymethine. Examples thereof include system compounds, phthalide compounds, ITO (In ₂ O _3- TiO ₂ system), ATO (ZnO-TiO ₂ system), tin-containing compounds, antimon-containing compounds, tin-antimon oxides, and dithiol metal complexes. The infrared absorber may be used alone or in combination of two or more. The content is preferably 0.1 part by mass or more and 20 parts by mass or less, and 0.3 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the total amount of the polycarbonate-based urethane resin and the binder. It is more preferable that the amount is 0.5 parts by mass or more and 5 parts by mass or less. By adding the infrared absorber in the above range, it is possible to impart infrared ray shielding ability to the coating film and reduce the temperature change in the room without impairing the transparency. As the infrared absorber, a tin-antimony oxide is preferably used.

The coating film composition of the present embodiment is a colorant, a defoaming agent, an antioxidant, a deodorant, an antibacterial agent, an antifungal agent, and a fungicide, as long as it does not hinder the solution of the problem of the present invention. It may contain additives such as fragrances.

(Transmittance)
The coating film composition of the present embodiment preferably transmits visible light in order for the coating film to have good daylighting properties. Specifically, the transmittance of a sample having a smooth coating film having a thickness of 70 μm produced as described below is preferably 85% or more with respect to visible light having a wavelength of 750 nm, and is 90. % Or more is more preferable. Further, the transmittance of the sample having a smooth coating film having a thickness of 140 μm is preferably 80% or more, more preferably 85% or more with respect to visible light having a wavelength of 750 nm. Further, the transmittance of the sample having a smooth coating film having a thickness of 320 μm is preferably 60% or more, more preferably 70% or more with respect to visible light having a wavelength of 750 nm. The sample is formed on the quartz glass and the quartz glass by applying the coating composition to the quartz glass having a thickness of 5 mm and drying the sample to form a smooth coating having a predetermined thickness on the quartz glass. It is produced as a sample composed of the above-mentioned coating film. The transmittance can be obtained by measuring the transmission spectrum of the above sample using an ultraviolet-visible spectrophotometer. When the transmittance of the sample having the coating film having the predetermined thickness is in the above range, the coating film formed by applying the coating film composition has excellent daylighting property and is a window glass of a building. It is advantageous to use it for daylighting glass in factories and factories.

(Base material shatterproof coating film)
The base material scattering prevention coating film of the present embodiment can be obtained, for example, by solidifying the above-mentioned base material scattering prevention coating film composition. The base material shatterproof coating film of the present embodiment preferably contains a polycarbonate-based urethane resin and has irregularities on the surface. Here, the "surface" of the coating film means a surface opposite to the base material side. By providing the coating film of the present embodiment with the above structure, it is possible to sufficiently prevent the damaged base material from scattering. As a result of diligent research, the present inventor has a higher anti-scattering property when the coating film contains a polycarbonate-based urethane resin than when the coating film contains a polyether-based urethane resin or a polyester-based urethane resin. It was revealed that it would be. The factors may be explained in the section of the coating film composition, but the factors are not limited thereto.

As a result of diligent research, the present inventor has clarified that the coating film of the present embodiment has irregularities on the surface, so that the coating film is less likely to be cracked as compared with the case where the surface is smooth. I made it. Since the solidification of the coating film composition proceeds sequentially from the coating film surface to the base material side (hereinafter, referred to as "coating film deep portion"), when the coating film surface is smooth, the coating film surface is perfect. It is considered that solidification and shrinkage of the deep part of the coating film occur after solidification and loss of fluidity, which causes cracks in the coating film. However, when the coating film has irregularities on the surface, the surface area of the coating film increases and the drying rate of the deep coating film increases, so that the deep coating film starts to solidify before the coating film surface is completely solidified. , It is considered that cracks are less likely to occur. Further, it is considered that when the coating film has irregularities on the surface, the local elasticity of the coating film surface increases and cracks are less likely to occur. However, the factors of the above effects are not limited to these.

In general, cracks in the coating film are particularly noticeable when the amount of the coating film composition applied at one time is increased per area to be applied. Therefore, the amount of the coating film composition that can be applied at one time is Limited. When forming a coating film having a smooth surface, cracks are likely to occur as described above, so that the amount of the coating film composition that can be applied at one time is relatively small. Therefore, in this case, it is difficult to increase the thickness of the coating film to such an extent that sufficient substrate scattering prevention property can be exhibited. However, since the coating film of the present embodiment has irregularities on the surface of the coating film, cracks are unlikely to occur as described above, so that a relatively large amount of the coating film composition can be applied at one time. Therefore, in this case, the thickness of the coating film becomes sufficiently thick, and the coating film can exhibit sufficient substrate scattering prevention property.

When forming the coating film of the present embodiment, the amount of the coating film composition applied at one time is from the viewpoint of imparting better base material scattering prevention property to the base material without causing cracks. , is preferably 0.1 kg / m ² or more 2.0 kg / m ² or less, more preferably 0.2 kg / m ² or more 1.5 kg / m ² or less, 0.2 kg / m ² or more 1 even more preferably at .0kg / m ² or less, further preferably 0.2 kg / m ² or more 0.7 kg / m ² or less. When the amount of the coating film composition applied at one time is 2.0 kg / m ² or less, the coating film is less likely to crack as compared with the case where it exceeds 2.0 kg / m ^2. Further, when the amount of the coating film composition applied at one time is 0.1 kg / m ² or more, the substrate scattering prevention property is higher than that in the case of less than ^{0.1 kg / m 2.} Become.

In addition, as a result of intensive research by the present inventor, the coating film has irregularities on the surface, so that the coating film is thicker when it is applied multiple times (overcoating) than when the surface is smooth. It was clarified that a coating film can be formed. This is because when the coating film composition is further applied on the coating film, if the coating film has irregularities on the surface, a sufficient amount of the coating film is retained by holding the coating film composition to which the irregularities are applied. It is considered that the composition for use can be applied, but the factors are not limited to these. Therefore, if the coating film has irregularities on the surface, the coating film can be made thicker than before, and the base material scattering prevention property is further improved.

Further, when the coating film has irregularities on the surface, it is possible to impart designability to the base material. The uneven pattern is not particularly limited and can be arbitrarily selected. Examples of the uneven pattern of the coating film include a dot shape, a stripe shape, a random shape, a check shape, a herringbone shape, and a honeycomb shape.

The thickness of the coating film of the present embodiment is not particularly limited, but the reference thickness is preferably 10 μm or more, preferably 50 μm or more, from the viewpoint of imparting good base material scattering prevention property to the base material. Is more preferable, and 100 μm or more is even more preferable. Further, the reference thickness is preferably 2000 μm or less, more preferably 1000 μm or less, and even more preferably 500 μm or less from the viewpoint of further enhancing the transparency of the coating film. In the present embodiment, the reference thickness of the coating film can be controlled within the above range by adjusting the viscosity of the coating film composition. When the viscosity of the coating film composition is increased, the reference thickness of the coating film formed by applying the coating film composition once tends to be increased. Further, the reference thickness can be increased by repeatedly applying the coating film composition in a plurality of times. When recoating in a plurality of times, it is preferable that the coating film as the base has irregularities on the surface. This makes it easier to hold the coating film composition to be applied on the coating film, so that dripping can be further suppressed and the thickness of the coating film can be further increased.

From the viewpoint of more effectively and surely exerting the effect of the present invention on the unevenness of the coating film surface of the present embodiment, the maximum convex portion height from the reference thickness of the coating film of the present embodiment is 100 μm or more and 2000 μm or less. It is more preferable, it is more preferably 200 μm or more and 1500 μm or less, and even more preferably 250 μm or more and 1000 μm or less. When the maximum convex portion height from the reference thickness is 2000 μm or less, the substrate scattering prevention property is further improved as compared with the case where it exceeds 2000 μm. Further, when the maximum convex portion height from the reference thickness is 100 μm or more, cracks are less likely to occur as compared with the case where the maximum convex portion height is less than 100 μm, and a thicker coating film tends to be formed. The maximum convex height from the reference thickness of the coating film of the present embodiment can be controlled by, for example, applying the coating film composition by roller coating using a roller whose uneven shape is appropriately adjusted. ..

From the viewpoint of more effectively and surely exerting the effect of the present invention on the unevenness of the coating film surface of the present embodiment, the deepest depth from the reference thickness of the coating film of the present embodiment is 50 μm or more and 1500 μm or less. Is more preferable, and it is more preferably 100 μm or more and 1000 μm or less, and even more preferably 100 μm or more and 500 μm or less. When the depth of the deepest portion from the reference thickness is 1500 μm or less, the base material scattering prevention property is further improved as compared with the case where it exceeds 1500 μm. Further, when the depth of the deepest portion from the reference thickness is 50 μm or more, cracks are less likely to occur and a thicker coating film tends to be formed as compared with the case where the depth is less than 50 μm. The depth of the deepest portion from the reference thickness of the coating film of the present embodiment can be controlled, for example, by applying the coating film composition by roller coating using a roller whose uneven shape is appropriately adjusted.

The reference thickness of the coating film, the maximum convex height from the reference thickness, and the deepest depth from the reference thickness are calculated as follows. First, the cross section is exposed by cutting the coating film in parallel with the thickness direction of the coating film with a glass cutter, scissors, a laser cutter or the like. At this time, the coating film may be adhered to the base material, or may be cut after being peeled off from the base material. Then, by enlarging it with a microscope, a high-magnification camera, or the like, an image or an image of an exposed cross section is obtained. The cross-sectional image or video of the coating film thus obtained is analyzed by image processing software or the like to calculate the average value of the thickness of the coating film, and this is used as the reference thickness of the coating film. Further, the portion where the coating film is thickest in the cross-sectional image of the coating film is defined as the maximum convex portion, and the value obtained by subtracting the reference thickness of the coating film from the thickness of the maximum convex portion is the maximum convex portion height from the reference thickness. Sato. Further, the portion where the coating film is the thinnest in the cross-sectional image of the coating film or the like is defined as the deepest portion, and the value obtained by subtracting the thickness of the deepest portion from the reference thickness of the coating film is defined as the deepest portion depth from the reference thickness. Therefore, regarding the standard thickness of the coating film, the maximum convex height from the standard thickness, the deepest depth from the standard thickness, the maximum convex thickness and the deepest thickness, the following equation (2) , (3) holds.
Maximum convex part thickness = standard thickness + maximum convex part height from the standard thickness ... (2)
Thickness of the deepest part = standard thickness-depth of the deepest part from the standard thickness ... (3)

Here, for the reference thickness of the coating film, the maximum convex height from the reference thickness, and the deepest depth from the reference thickness, the above analysis was performed three times for a cross section having a length of 1 cm. Use the average value.

The hardness of the coating film surface of this embodiment is not particularly limited, but the scratch hardness (pencil method) measured according to Japanese Industrial Standard JIS K 5600-5-4: 1999 is between H and 5H (values at both ends). (Including) is preferable. When the hardness of the coating film surface is within the above range, the coating film tends to have a better balance between impact resistance and scratch strength. The scratch hardness (pencil method) of the coating film can be controlled by, for example, adjusting the content of the polycarbonate-based urethane resin.

The breaking strength of the coating film of the present embodiment is preferably 1.0 MPa or more, more preferably 1.5 MPa or more, and even more preferably 2.0 MPa or more at 60 ° C. When the breaking strength of the coating film is within the above range, the coating film tends to have more excellent impact resistance and more excellent anti-scattering property of the base material even at a high temperature. The upper limit of the breaking strength of the coating film of the present embodiment at 60 ° C. is not particularly limited, but may be 200 MPa, 100 MPa, or 50 MPa.

The breaking strength of the coating film of the present embodiment is preferably 1.0 MPa or more, more preferably 1.5 MPa or more, and even more preferably 2.0 MPa or more at 23 ° C. When the breaking strength of the coating film is within the above range, the coating film tends to have more excellent impact resistance and further excellent substrate scattering prevention property. The upper limit of the breaking strength of the coating film of the present embodiment at 23 ° C. is not particularly limited, but may be 200 MPa, 100 MPa, or 50 MPa.

The breaking strength of the coating film of the present embodiment is preferably 5.0 MPa or more, more preferably 6.5 MPa or more, and even more preferably 8.0 MPa or more at −5 ° C. When the breaking strength of the coating film is within the above range, the coating film tends to have more excellent impact resistance and further excellent substrate scattering prevention property even at a low temperature. The upper limit of the breaking strength of the coating film of the present embodiment at −5 ° C. is not particularly limited, but may be 200 MPa, 150 MPa, or 100 MPa. The breaking strength of the coating film can be measured by the method described in Examples. The breaking strength of the coating film can be controlled by, for example, adjusting the breaking strength of the polycarbonate-based urethane resin and / or the content of the polycarbonate-based urethane resin.

The elongation at break of the coating film of the present embodiment is preferably 150% or more, more preferably 170% or more, and even more preferably 200% or more at 60 ° C. When the breaking elongation of the coating film is within the above range, the coating film tends to have more excellent impact resistance and further excellent substrate scattering prevention property even at a high temperature. The upper limit of the elongation at break at 60 ° C. of the coating film of the present embodiment is not particularly limited, but may be 500%, 400%, or 300%.

The elongation at break of the coating film of the present embodiment is preferably 100% or more, more preferably 120% or more, and even more preferably 140% or more at 23 ° C. When the breaking elongation of the coating film is within the above range, the coating film tends to have more excellent impact resistance and further excellent substrate scattering prevention property. The upper limit of the elongation at break at 23 ° C. of the coating film of the present embodiment is not particularly limited, but may be 500%, 400%, or 300%.

The elongation at break of the coating film of the present embodiment is preferably 80% or more, more preferably 90% or more, and even more preferably 100% or more at −5 ° C. When the breaking elongation of the coating film is within the above range, the coating film tends to have more excellent impact resistance and further excellent substrate scattering prevention property even at a low temperature. The upper limit of the elongation at break at −5 ° C. of the coating film of the present embodiment is not particularly limited, but may be 400%, 300%, or 250%. The elongation at break of the coating film can be measured by the method described in Examples. The breaking elongation of the coating film can be controlled, for example, by adjusting the breaking elongation of the polycarbonate-based urethane resin and / or the content of the polycarbonate-based urethane resin.

Basis weight of the coating film of the present embodiment, more that it is 0.06 kg / m ² or more 1.8 kg / m ² or less is preferable, 0.09 kg / m ² or more 1.5 kg / m ² or less preferably, it is more preferably 0.12 kg / m ² or more 1.3 kg / m ² or less. When the basis weight is 1.8 kg / m ² or less, the transparency of the coating film is further improved as compared with the case where it exceeds 1.8 kg / m ^2. Further, when the basis weight is 0.06 kg / m ² or more, better base material scattering prevention property can be imparted to the base material as compared with the case where the basis weight is less than 0.06 kg / m ^2.

The polycarbonate-based urethane resin contained in the coating film of the present embodiment may be the same as the polycarbonate-based urethane resin contained in the above-mentioned coating film composition, or is further cured by a curing aid. You may. Examples of the curing aid include those described above. The preferable glass transition temperature Tg, 100% modulus, breaking strength, and breaking elongation of the polycarbonate-based urethane resin contained in the coating film of the present embodiment are the same as those described above.

In the coating film of the present embodiment, the content of the polycarbonate-based urethane resin is preferably 10% by mass or more and 100% by mass or less with respect to the total amount of the coating film from the viewpoint of further enhancing the base material scattering prevention property. It is more preferably mass% or more and 90 mass% or less, and even more preferably 20 mass% or more and 80 mass% or less.

From the viewpoint of further enhancing the anti-scattering property of the base material, the coating film of the present embodiment preferably contains a binder as long as it does not hinder the solution of the problem of the present invention. The binder may be the same as the binder contained in the coating film composition, or may be further cured with a curing aid. Examples of the curing aid include those described above. When the coating film of the present embodiment contains a binder, the coating film tends to have further improved flexibility, flexibility, and adhesion to the base material, and have more excellent base material scattering prevention property. .. The content of the binder is 0% by mass with respect to the total amount of the coating film from the viewpoint of more sufficiently and surely exerting the function as a binder and more effectively and surely preventing the deterioration of the effect due to the polycarbonate-based urethane resin. It is preferably 90% by mass or less, more preferably 10% by mass or more and 85% by mass or less, and even more preferably 20% by mass or more and 80% by mass or less.

The coating film of the present embodiment is an ultraviolet absorber, an infrared absorber, a colorant, a thixotropic property-imparting agent, as long as it does not hinder the solution of the problem of the present invention from the viewpoint of imparting an effect other than the base material scattering prevention property. It may contain additives such as a film-forming auxiliary, a defoaming agent, an antioxidant, a deodorant, an antibacterial agent, a fungicide, and a fragrance. Examples and preferable contents of the ultraviolet absorber, the infrared absorber, the thixotropy-imparting agent, and the film-forming auxiliary are as described above.

(Scatter-proof base material)
As shown in FIG. 1, the shatterproof base material 100 of the present embodiment is located between the base material 110, the coating film 120 located on one side of the base material 110, and between the base material 110 and the coating film 120. It is a base material containing a sealer, and is a base material having anti-scattering properties by adhering the base material 110 and the coating film 120 via the sealer. The base material and the coating film have the above-mentioned constitution. The shatterproof base material may be obtained by forming a coating film on an existing base material such as a window glass of a building or a window glass of an automobile. Alternatively, the shatterproof base material may be installed in the above-mentioned place after forming a coating film on the base material in advance before installing it in the place where it should be installed. Since the anti-scattering base material of the present embodiment has the above-mentioned structure, it is possible to prevent the fragments from scattering even when the substrate is damaged by an impact. In addition, the shatterproof base material also has excellent penetration resistance by providing a coating film. Further, since the anti-scattering base material of the present embodiment contains a coating film capable of having good transparency while having irregularities on the surface, the anti-scattering base material has good daylighting property. It is possible to suppress each other's visibility from the spaces on both sides of the space. Therefore, the shatterproof substrate is useful, for example, for building windowpanes that protect privacy. Further, since the shatterproof base material of the present embodiment contains a coating film that can be thickened, it is useful as a window glass having excellent soundproofing and dew condensation prevention properties.

(Cationic aqueous sealer)
The cationic aqueous sealer of the present embodiment is not particularly limited as long as it is an aqueous sealer containing a cationic aqueous resin emulsion and can improve the adhesiveness between the base material and the coating film. When a sealer is used in the present embodiment, peeling and deterioration of the coating film from the substrate can be suppressed more effectively. Further, when the sealer is used, when the base material contains an alkaline component, it is possible to more effectively prevent the coating film from being invaded by the alkaline component that can be eluted from the base material over time. Further, since the cationic aqueous sealer of the present embodiment is aqueous, it can be preferably applied to a base material in terms of environmental hygiene.

The cationic resin contained in the sealer is not particularly limited as long as it is a resin having a cationic group, and examples thereof include a polyurethane resin, an acrylic resin, and an epoxy resin having a cationic group. The cationic resin may be used alone or in combination of two. From the viewpoint of further improving the adhesiveness between the sealer and the coating film and imparting alkali resistance, the cationic aqueous sealer of the present embodiment preferably contains an aqueous emulsion of a polyurethane resin. Further, it is more preferable that the cationic aqueous sealer of the present embodiment further contains an acrylic resin. When the sealer contains an acrylic resin, the adhesiveness between the sealer and the coating film and the adhesiveness between the base material and the coating film are further improved. The cationic group in the cationic resin is not particularly limited, and examples thereof include a tertiary amino group. The average particle size of the resin particles in the sealer is not particularly limited, but may be, for example, 0.01 μm or more and 1.5 μm or less, 0.02 μm or more and 1.0 μm or less. It may be 0.03 μm or more and 0.5 μm or less.

The above-mentioned cationic aqueous sealer may be produced by a conventionally known method, or a commercially available product may be used. Examples of commercially available products include Perfect Sealer (trade name manufactured by Japan Permill Co., Ltd.) and the like.

The coating amount of the sealer of the present embodiment is not particularly limited as long enhance the adhesiveness between the substrate and the coating composition, is preferably 0.01 kg / m ² or more 1.0 kg / m ² or less , more preferably 0.02 kg / m ² or more 0.9 kg / m ² or less, and still more preferably 0.03 kg / m ² or more 0.7 kg / m ² or less. When the coating amount of the sealer is within the above range, the adhesion between the base material and the coating film composition is further improved, and the anti-scattering base material tends to have more excellent anti-scattering property. ..

(Method of forming shatterproof base material)
The method for forming the anti-scattering base material of the present embodiment (hereinafter, also referred to as “method for forming the anti-scattering base material”) includes a step of applying a cationic water-based sealer to the surface of the base material and a cationic water-based material. The steps of drying the sealer, applying the composition for the base material shatterproof coating film to the surface of the solidified product of the cationic aqueous sealer, and the step of drying the base material shatterproof coating film composition are in this order. By including the above, it is possible to form the anti-scattering base material 100 which is convenient and preferable in terms of environmental hygiene and has excellent anti-scattering property. Further, by including a step of applying a cationic water-based sealer to the surface of the base material, the adhesiveness between the base material and the coating film can be further enhanced, the anti-scattering property of the base material is further enhanced, and further, the coating is further enhanced. The film is hard to peel off from the base material. It is particularly effective when the base material is inorganic glass.

In the shatterproof substrate forming method of the present embodiment, the steps of applying the sealer and the coating composition are air spray coating, airless spray coating, dipping treatment coating, brush coating, screen printing, spray coating, ironing, and ironing. And various methods such as roller coating can be used. Among these, it is preferable to use roller coating. The roller coating may be performed by a roller used for ordinary roller coating, or may be roller coating using a roller having a coating surface that comes into contact with the surface of the above-mentioned base material or the surface of a cationic aqueous sealer. .. By using such roller coating, a uniform sealer or a base material shatterproof coating film can be easily and easily formed over a large area even on an already installed base material such as a window glass of a building. can do. In particular, since the coating film composition of the present embodiment has thixotropy, it can be easily and evenly applied to the base material by roller coating, and the obtained coating film has good adhesion to the base material. Become. Therefore, the anti-scattering property of the base material is further improved.

The roller has, for example, a configuration as shown in the schematic perspective view of FIG. According to FIG. 2, the roller 200 includes a roller main body 210 which is cylindrical and has a coating surface on the side surface of the cylinder, and a rotating shaft member 220 for rotating the roller main body 210 around the center of the cylinder. It includes a handle 240 for gripping and using the roller 200, and a connecting member 230 for connecting the handle 240 and the rotary shaft member 220. The coating film composition by the roller coating is a step of adhering the coating film composition to the coating surface of the roller in contact with the surface of the base material or the surface of the cationic aqueous sealer, and the base material. By including a step of rotating and moving the roller body around the center of the cylinder of the roller with the coating film composition in contact with the surface of the coating film or the surface of the cationic water-based sealer. The composition can be transferred from the coated surface to the surface of the substrate. Therefore, when the coated surface has irregularities as described below, the coating film composition is applied in a pattern corresponding to the irregularities.

In the shatterproof substrate forming method of the present embodiment, it is preferable to employ roller coating using a roller having irregularities on the coating surface. By adopting roller coating using such a roller, the present inventor further reduces cracks in the coating film when the coated coating film composition has irregularities and a shatterproof base material is produced. I made it clear that I could do it. This is considered to be due to the above-mentioned factors in the section of the base material shatterproof coating film, but is not limited to this. Further, by adopting such a roller coating, a thick coating film can be formed more easily, and the anti-scattering base material has a higher anti-scattering property. Further, by adopting such roller coating, unevenness is generated in the coated coating film composition, and a scatter-preventive base material having a design property can be formed. The uneven pattern is not particularly limited and can be arbitrarily selected. Examples of the uneven pattern of the coating film include a dot shape, a stripe shape, a random shape, a check shape, a herringbone shape, and a honeycomb shape.

In the method for forming a shatterproof substrate of the present embodiment, in order to form a desired uneven shape on the coating film surface, the surface shape of the coating surface of the roller is appropriately selected, and the coating having the desired uneven shape is formed by the roller. A film may be formed.

In the shatterproof substrate forming method of the present embodiment, the step of drying the coating film composition is not particularly limited, but it may be naturally dried or heated by heating the coating film composition. It may be dry. In the case of heat drying, the heating temperature for the coating film composition is preferably 150 ° C. or lower, and more preferably 100 ° C. or lower, because the coating film composition does not decompose. In the method for forming a shatterproof substrate of the present embodiment, natural drying is preferable from the viewpoint of reducing the environmental load.

In the shatterproof substrate forming method of the present embodiment, the step of applying the coating film composition and the step of drying the coating film composition may be repeated two or more times with both as a set. By repeating the process twice or more, the coating film to be formed can be made thicker, and an anti-scattering base material having more excellent anti-scattering property can be formed. When the surface of the coating film has irregularities, when the coating film composition is further applied on the coating film, a more sufficient amount of coating is applied by retaining the coating film composition to which the unevenness is applied. The film composition can be applied. Therefore, a thicker coating film can be formed, and an anti-scattering base material having a higher anti-scattering property can be formed.

The shatterproof base material forming method of the present embodiment may include a step of cleaning the surface of the base material prior to the step of applying the cationic aqueous sealer. The step of cleaning the base material is not particularly limited, but may be ultrasonic cleaning with pure water or high-pressure cleaning in which pure water is jetted at a high pressure. For the ultrasonic cleaning and high-pressure cleaning, a cleaning liquid containing a detergent such as a neutral detergent may be used, but the cleaning liquid is preferably washed away with pure water.

(Base material shatterproof coating film formation kit)
The base material shatterproof coating film forming kit of the present embodiment includes a composition for a base material shatterproof coating film and a cationic aqueous sealer. As a result, even a general consumer who does not have a special technique can form a base material shatterproof coating film which is convenient and preferable in terms of environmental hygiene. The base material scattering prevention coating film forming kit of the present embodiment may further include a roller having irregularities on the coated surface from the viewpoint of improving workability. The surface shape of the coating film surface of the roller included in the base material scattering prevention coating film forming kit may be appropriately changed according to the desired coating film surface shape. In the base material shatterproof coating film forming kit of the present embodiment, the configurations and preferred embodiments of the base material shatterproof coating film composition, the cationic aqueous sealer and the roller are the same as those described above.

Although the embodiment for carrying out the present invention has been described above, the present invention is not limited to the above-described embodiment. The present invention can be modified in various ways without departing from the gist thereof. For example, in another embodiment of the shatterproof base material according to the present invention, the base material shatterproof coating film may be formed on both sides of the base material. In this case, the same effect as that of the above-mentioned anti-scattering base material 100 is exhibited, and by providing coating films on both sides, the base material has a higher anti-scattering property.

Further, in another embodiment of the shatterproof base material according to the present invention, the sealer may not be included, and therefore the base material and the coating film may be in direct contact with each other. By not applying the sealer to the surface of the base material, it is possible to more easily provide the anti-scattering base material. This form is particularly useful when an acrylic resin, a polycarbonate resin, or a fiber reinforced plastic having good adhesiveness to a coating film is used as a base material.

Therefore, in another embodiment of the method for forming a shatterproof base material according to the present invention, the coating film composition may be applied to both surfaces of the base material, or a sealer may not be used.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[Measuring method of resin physical properties]
In the examples, the resin is pulled by using a tensile tester (manufactured by Shimadzu Corporation, product name "Autograph AG-I") for physical properties such as 100% modulus, breaking strength, and breaking elongation of the resin. It was measured by. For the above measurement, a dumbbell-shaped No. 3 sample was used in accordance with Japanese Industrial Standards (JIS K 6251: 2017).

[Method for measuring physical properties of coating film composition]
In the examples, the viscosity of the coating film composition and the physical properties such as thixotropy index TI are specified at 23 ° C. using a dynamic viscoelasticity measuring device (BH type viscometer manufactured by Toki Sangyo Co., Ltd.). Measured under rotating conditions. The thixotropy index TI was calculated according to the above formula (1) by measuring the viscosity at a rotation speed of 2 rpm and the viscosity at a rotation speed of 20 rpm. For the viscosity, the viscosity at a rotation speed of 2 rpm was measured.

[Preparation of coating film composition]
Aqueous emulsion of polycarbonate urethane resin (nonvolatile content: 37% by mass, anionic, average particle size of resin particles: 40 nm, resin Tg: -25 ° C, dry coating physical properties: 100% modulus; 15 MPa, breaking strength; 48 MPa , Breaking elongation; 350%) 80 parts by mass, aqueous emulsion of acrylic-modified polyester urethane resin as a binder (nonvolatile content: 37% by mass, anionic, average particle size of resin particles: 60 nm, resin Tg: -20 ° C. , Dry coating physical characteristics: 100% modulus; 12 MPa, breaking strength; 42 MPa, breaking elongation; 430%) 20 parts by mass, 10 parts by mass of texanol as a film-forming aid, modified silicon-based defoaming agent for high viscosity 0.80 parts by mass of agent, 0.75 parts by mass of polyether polyol urethane resin (manufactured by ADEKA, product name "Adecanol UH-420") as a thixotropy-imparting agent / thickener, and modified polyacrylic acid-based polymer A composition for coating film was obtained by mixing and stirring 0.30 parts by mass of a mold viscoelasticity adjusting agent (solid content: 12%, viscosity: 25 Pa · s, pH: 10.5) and 1 part by mass of water. .. The thixotropy index TI of the coating film composition was 5.5, and the viscosity was 30 Pa · s.

[Preparation of sealer]
As a cationic aqueous sealer, a mixture of acrylic resin and polyurethane resin (manufactured by Nippon Permil Co., Ltd., product name "Perfect Sealer") was prepared.

(Impact resistance test 1)
[Comparative Example 1]
As sample 1, a window glass with a sash of an existing plant to which a glass shatterproof film was attached was removed and prepared about 15 years ago. The glass shatterproof film was found to be embrittled and whitened, which is considered to be caused by its deterioration. Further, an attempt was made to peel off the glass shatterproof film, but the film could not be peeled off due to the embrittlement of the film and the strong adhesiveness of the adhesive. When an iron ball having a diameter of 4 cm and a mass of 260 g was dropped from a height of 1 m and collided with the sample 1, the film and the window glass were damaged and scattered. That is, it was found that the glass shatterproof property of the glass shatterproof film has already been lost.

[Example 1]
A cationic aqueous sealer was applied to the entire one side of Sample 1 by roller coating using a roller as shown in FIG. 2, and further dried at room temperature. The coating amount of the aqueous sealer was 0.05 kg / m ² . Next, the coating film composition prepared as described above was applied onto the above-mentioned aqueous sealer by roller coating using a roller as shown in FIG. 2, and further dried at room temperature. By repeating this coating and drying twice so that the coating amount of the coating film composition is 0.8 kg / m ² , the basis weight is 0.28 kg on the sample 1 as the base material via the aqueous sealer. A shatterproof base material on which a base material shatterproof coating film of / m ^{2 was formed was obtained.} The reference thickness of the base material shatterproof coating film was 280 μm, the maximum convex height from the reference thickness was 470 μm, and the deepest depth was 160 μm. When an iron ball having a diameter of 4 cm and a mass of 260 g was dropped from a height of 1 m on the side where the base material shatterproof coating film of the obtained anti-scattering base material was formed and collided with each other, cracks were observed in the window glass. However, no damage was observed in the base material scattering prevention coating film, and no scattering of glass was observed. That is, the glass shatterproof effect of the base material shatterproof coating film of the present invention was recognized.

(Impact resistance test 2)
[Comparative Example 2]
As sample 2, a window glass with a sash having a size of 630 mm × 555 mm × thickness 3 mm was prepared. When an iron ball having a diameter of 6.4 cm and a mass of 1 kg was dropped onto the sample 2 from a height of 1.25 m and collided with the sample 2, the window glass was broken and scattered.

[Example 2]
A cationic aqueous sealer was applied to the entire one side of Sample 2 by roller coating using a roller as shown in FIG. 2, and further dried at room temperature. The coating amount of the aqueous sealer was 0.05 kg / m ² . Next, by roller coating using a roller as shown in FIG. 2, 0.4 kg / m ^{2 of} the coating film composition prepared as described above is applied onto the above aqueous sealer, and further dried at room temperature. As a result, a shatterproof base material was obtained in which a base material shatterproof coating film having ^{a basis weight of 0.14 kg / m 2} was formed on the sample 2 as a base material via an aqueous sealer. The reference thickness of the base material shatterproof coating film was 140 μm, the maximum convex height from the reference thickness was 440 μm, and the deepest depth was 100 μm. When an iron ball with a diameter of 6.4 cm and a mass of 1 kg was dropped from a height of 1.50 m on the side where the base material shatterproof coating film of the obtained anti-scattering base material was formed and collided with the iron ball, the window glass cracked. Was not observed, and no damage to the base material scattering prevention coating film was observed. On the other hand, when an iron ball having a diameter of 8 cm and a mass of 2 kg was dropped from a height of 1.50 m and collided with the obtained side of the anti-scattering base material on which the base material anti-scattering coating film was not formed, the window glass was formed. Was damaged, the base material shatterproof coating film was partially damaged, and the glass was slightly scattered.

[Example 3]
A cationic aqueous sealer was applied to the entire one side of Sample 2 by roller coating using a roller as shown in FIG. 2, and further dried at room temperature. The coating amount of the aqueous sealer was 0.05 kg / m ² . Next, the coating film composition prepared as described above was applied onto the above-mentioned aqueous sealer by roller coating using a roller as shown in FIG. 2, and further dried at room temperature. By repeating this coating and drying twice so that the coating amount of the coating film composition is 0.4 kg / m ² , the basis weight is 0.14 kg on the sample 2 as the base material via the aqueous sealer. A shatterproof base material on which a base material shatterproof coating film of / m ^{2 was formed was obtained.} The reference thickness of the base material shatterproof coating film was 140 μm, the maximum convex height from the reference thickness was 440 μm, and the deepest depth was 100 μm. The result of the impact resistance test 2 was the same as that of Example 2.

[Example 4]
A cationic aqueous sealer was applied to the entire one side of Sample 2 by roller coating using a roller as shown in FIG. 2, and further dried at room temperature. The coating amount of the aqueous sealer was 0.05 kg / m ² . Next, the coating film composition prepared as described above was applied onto the above-mentioned aqueous sealer by roller coating using a roller as shown in FIG. 2, and further dried at room temperature. By repeating this coating and drying twice so that the coating amount of the coating film composition is 0.6 kg / m ² , the basis weight is 0.21 kg on the sample 2 as the base material via the aqueous sealer. A shatterproof base material on which a base material shatterproof coating film of / m ^{2 was formed was obtained.} The reference thickness of the base material shatterproof coating film was 210 μm, the maximum convex height from the reference thickness was 460 μm, and the deepest depth was 120 μm. When an iron ball with a diameter of 8 cm and a mass of 2 kg was dropped from a height of 1.50 m on the side where the base material shatterproof coating film of the obtained anti-scattering base material was formed and collided with each other, cracks were observed in the window glass. However, no damage was observed in the base material scattering prevention coating film, and no glass scattering was observed. On the other hand, when an iron ball having a diameter of 8 cm and a mass of 2 kg was dropped from a height of 1.50 m and collided with the obtained side of the anti-scattering base material on which the base material anti-scattering coating film was not formed, the window glass was formed. Was damaged, and the base material shatterproof coating film was partially damaged, but no glass shattering was observed.

[Example 5]
A cationic aqueous sealer was applied to the entire one side of Sample 2 by roller coating using a roller as shown in FIG. 2, and further dried at room temperature. The coating amount of the aqueous sealer was 0.05 kg / m ² . Next, the coating film composition prepared as described above was applied onto the above-mentioned aqueous sealer by roller coating using a roller as shown in FIG. 2, and further dried at room temperature. By repeating this coating and drying twice so that the coating amount of the coating film composition is 0.8 kg / m ² , the basis weight is 0.28 kg on the sample 2 as the base material via the aqueous sealer. A shatterproof base material on which a base material shatterproof coating film of / m ^{2 was formed was obtained.} The reference thickness of the base material shatterproof coating film was 280 μm, the maximum convex height from the reference thickness was 470 μm, and the deepest depth was 160 μm. When an iron ball with a diameter of 8 cm and a mass of 2 kg was dropped from a height of 1.50 m on the side where the base material shatterproof coating film of the obtained anti-scattering base material was formed and collided with each other, cracks were observed in the window glass. However, no damage was observed in the base material scattering prevention coating film, and no glass scattering was observed. On the other hand, when an iron ball having a diameter of 8 cm and a mass of 2 kg was dropped from a height of 1.50 m and collided with the obtained side of the anti-scattering base material on which the base material anti-scattering coating film was not formed, the window glass was formed. Was damaged, and the base material shatterproof coating film was partially damaged, but no glass shattering was observed. Compared with Example 4 in which the basis weight of the base material scattering prevention coating film was 0.21 kg / m ² , the degree of damage to the window glass and the base material scattering prevention coating film was reduced.

[Example 6]
A cationic aqueous sealer was applied to the entire one side of Sample 2 by roller coating using a roller as shown in FIG. 2, and further dried at room temperature. The coating amount of the aqueous sealer was 0.05 kg / m ² . Next, the coating film composition prepared as described above was applied onto the above-mentioned aqueous sealer by roller coating using a roller as shown in FIG. 2, and further dried at room temperature. By repeating this coating and drying twice so that the coating amount of the coating film composition is 1.0 kg / m ² , the basis weight is 0.35 kg on the sample 2 as the base material via the aqueous sealer. A shatterproof base material on which a base material shatterproof coating film of / m ^{2 was formed was obtained.} The reference thickness of the base material shatterproof coating film was 350 μm, the maximum convex height from the reference thickness was 470 μm, and the deepest depth was 160 μm. When an iron ball with a diameter of 8 cm and a mass of 2 kg was dropped from a height of 1.50 m on the side where the base material shatterproof coating film of the obtained anti-scattering base material was formed and collided with each other, cracks were observed in the window glass. No damage was observed in the base material scattering prevention coating film, and no scattering of glass was observed. Further, when an iron ball having a diameter of 8 cm and a mass of 2 kg was dropped from a height of 1.50 m and collided with the obtained side of the anti-scattering base material on which the base material anti-scattering coating film was not formed, the window glass was formed. Although cracks were observed, no damage to the base material scattering prevention coating film was observed, and no scattering of glass was observed.

(Impact resistance test 3)
[Comparative Example 3]
As sample 3, a wire-reinforced glass having a thickness of 6.8 mm was prepared. When the sample 3 was hit with a hammer a plurality of times until the glass was broken, the glass pieces were scattered.

[Example 7]
A cationic aqueous sealer was applied to the entire one side of Sample 3 by roller coating using a roller as shown in FIG. 2, and further dried at room temperature. The coating amount of the aqueous sealer was 0.05 kg / m ² . Next, the coating film composition prepared as described above was applied onto the above-mentioned aqueous sealer by roller coating using a roller as shown in FIG. 2, and further dried at room temperature. By repeating this coating and drying twice so that the coating amount of the coating film composition is 0.6 kg / m ² , the basis weight is 0.21 kg on the sample 3 as the base material via the aqueous sealer. A shatterproof base material on which a base material shatterproof coating film of / m ^{2 was formed was obtained.} The reference thickness of the base material shatterproof coating film was 210 μm, the maximum convex height from the reference thickness was 460 μm, and the deepest depth was 120 μm. The surface of the obtained shatterproof base material on which the base material shatterproof coating film was formed was hit with a hammer a plurality of times until the glass as the base material was broken. As a result, the glass as the base material was cracked, but the glass pieces were hardly scattered, and only fine glass pieces were observed.

[Example 8]
In the same manner as in Example 7, an anti-scattering base material was obtained by forming a base material scattering-preventing coating film having ^{a basis weight of 0.21 kg / m 2} on the sample 3 as a base material via an aqueous sealer. The surface of the obtained shatterproof base material on which the base material shatterproof coating film was not formed was hit with a hammer a plurality of times until the glass as the base material was broken. As a result, the glass as the base material was cracked, but the glass pieces were hardly scattered, and only fine glass pieces were observed. Further, as compared with Example 7 in which the surface on which the base material shatterproof coating film was formed was impacted, the deformation of the base material shatterproof base material was suppressed. From this, it was suggested that when the base material shatterproof coating film is formed on the surface of the base material opposite to the surface to which the impact is applied, it has an effect of suppressing the deformation of the base material.

[Example 9]
A cationic aqueous sealer was applied to the entire one side of Sample 3 by roller coating using a roller as shown in FIG. 2, and further dried at room temperature. The coating amount of the aqueous sealer was 0.05 kg / m ² . Next, the coating film composition prepared as described above was applied onto the above-mentioned aqueous sealer by roller coating using a roller as shown in FIG. 2, and further dried at room temperature. By repeating this coating and drying twice so that the coating amount of the coating film composition is 1.0 kg / m ² , the basis weight is 0.35 kg on the sample 3 as the base material via the aqueous sealer. A shatterproof base material on which a base material shatterproof coating film of / m ^{2 was formed was obtained.} The reference thickness of the base material shatterproof coating film was 350 μm, the maximum convex height from the reference thickness was 470 μm, and the deepest depth was 160 μm. The surface of the obtained shatterproof base material on which the base material shatterproof coating film was formed was hit with a hammer a plurality of times until the glass as the base material was broken. As a result, the glass as the base material was cracked, but the glass pieces were hardly scattered, and the fine glass pieces were not scattered.

(Evaluation of impact resistance of coating film)
A coating film composition similar to the coating film composition in the above impact resistance test was prepared. A cationic water-based sealer was applied to the entire surface of the 150 mm × 70 mm × 0.8 mm thick SPCC-SB steel sheet using a brush, and further dried at room temperature. The coating amount of the aqueous sealer was 0.05 kg / m ² . Next, using a brush, the coating film composition was placed on the above-mentioned aqueous sealer at a coating ^{interval of 5 hours so that the coating amount of the coating film composition was 0.6 kg / m 2} , and the coating film composition was divided into two times. It was applied. Then, it was cured under the following curing conditions (A).
Curing condition (A): After curing for 24 hours in a constant temperature and humidity chamber at 23 ± 2 ° C. and a relative humidity of 50 ± 5%, it was further cured in a constant temperature and humidity chamber at 50 ± 2 ° C. for 72 hours.

The impact resistance of the coating film was evaluated using the sample obtained as described above. Specifically, it is as follows. Using a device conforming to "6. DuPont type" of Japanese Industrial Standard JIS K 5600-5-3: 1999, the radius of the shooting type and cradle is 6.35 mm, the mass of the weight is 1000 g, and the drop height is 500 mm. As a result, an impact was applied to the coated surface of the sample. As a result, no abnormality such as cracking or peeling was observed on the coating film surface of the sample, and it was found that the coating film was excellent in impact resistance.

(Adhesion test)
A coating film composition similar to the coating film composition in the above impact resistance test was prepared. A cationic water-based sealer was applied to the entire surface of a glass plate having a size of 150 mm × 70 mm × thickness 2.0 mm using a brush, and further dried at room temperature. The coating amount of the aqueous sealer was 0.05 kg / m ² . Next, using a brush, the coating film composition was placed on the above-mentioned aqueous sealer at a coating ^{interval of 5 hours so that the coating amount of the coating film composition was 0.6 kg / m 2} , and the coating film composition was divided into two times. It was applied. Then, it was cured under the above-mentioned curing condition (A).

The adhesiveness of the coating film was evaluated using the sample obtained as described above. Specifically, it is as follows. According to Japanese Industrial Standards JIS K 5600-5-6: 1999, the number of cuts is 11 in each direction of the grid pattern (the number of grids is 100), the cut interval is 1 mm, and a single-edged cutting tool. Using (manual) as a cutting tool, a cut was made on the coated surface of the sample. As a result, it was found that the edges of the cut were completely smooth, there was no peeling in the eyes of any lattice (classification 0 in the above JIS standard), and the coating film had excellent adhesion.

(Measurement of scratch hardness)
A sample in which a coating film was formed on a glass plate was obtained in the same manner as in the above adhesion test. Using the obtained sample, the scratch hardness (pencil method) of the coating film surface of the sample was measured according to Japanese Industrial Standards JIS K 5600-5-4: 1999. As a result, the hardness of the hardest pencil on the coating film surface of the sample in which no cohesive failure was observed was 3H.

(Water resistance test)
A coating film composition similar to the coating film composition in the above impact resistance test was prepared. A cationic water-based sealer was applied to the entire surface of a glass plate having a size of 150 mm × 70 mm × thickness 2.0 mm using a brush, and further dried at room temperature. The coating amount of the aqueous sealer was 0.05 kg / m ² . Then, using a brush, the coating film composition was applied onto the above-mentioned aqueous sealer and cured under the above-mentioned curing conditions (A). The coating amount of the coating film composition was 0.1 kg / m ² .

Using the obtained sample, the water resistance of the coating film surface of the sample was measured according to "7. Method 1 (immersion method)" of Japanese Industrial Standard JIS K 5600-6-1: 2016. After immersing the sample in distilled water at 23 ° C. for 168 hours, when the coating film surface of the sample was observed, no abnormalities such as swelling, cracking, peeling, softening, deterioration of gloss, and discoloration were observed, and the coating film was found. It was found to be excellent in water resistance.

(Abrasion resistance test)
A sample in which a coating film was formed on a glass plate was obtained in the same manner as in the above adhesion test. Using the obtained sample, the wear resistance of the coating film surface of the sample was measured according to Japanese Industrial Standard JIS H 8682-3: 2013. 10 L of the abrasive (silicon carbide C # 36) is dropped on the surface of the sample on which the coating film is formed so that the falling speed of the abrasive is 400 g / min, and then the sample is applied. The membrane surface was observed. As a result, it was found that no exposed part of the glass plate was observed in the sample, and the coating film had excellent wear resistance.

(Tensile performance test)
A coating film composition similar to the coating film composition in the above impact resistance test was prepared. A coating film composition was applied onto a polyethylene plate using a spatula, and cured under the above curing conditions (A). The coating film thickness after drying was 1.0 mm. The obtained coating film was peeled off from a polyethylene plate, processed into a dumbbell-shaped No. 3 shape, and then used as a sample for a tensile test. The tensile test was carried out at a tensile speed of 500 mm / min and a test temperature of 60 ° C., 23 ° C. or −5 ° C. according to Japanese Industrial Standards JIS A 6021: 2011. The elongation rate was defined as the elongation rate between the grips at the time of fracture. As a result, the tensile strength (breaking strength) and elongation (breaking elongation) at 60 ° C. were 3.6 N / mm ² and 240%, respectively, and the tensile strength (breaking strength) and elongation (breaking strength) at 23 ° C. The elongation at break) was 2.6 N / mm ² and 150%, respectively, and the tensile strength and elongation at −5 ° C. were 9.3 N / mm ² and 110%, respectively.

(Measurement of formaldehyde emission)
A coating film composition similar to the coating film composition in the above impact resistance test was prepared. The coating film composition was applied onto the aluminum plate using a brush in ^two steps with a coating interval of 5 hours so that the coating amount of the coating film composition was 0.6 kg / m 2. Then, it was cured under the following curing conditions (B).
Curing condition (B): Cured for 7 days under the standard conditions (23 ± 2 ° C., relative humidity 50 ± 5%) of Japanese Industrial Standard JIS K 5600-1-6.

Using the sample obtained as described above, the amount of formaldehyde emitted from the coating film was measured according to "5. Desiccator method" of Japanese Industrial Standard JIS K 5601-4-1: 2012. The amount of water in the crystal dish was 100 mL. As a result, the amount of formaldehyde emitted from the coating film was below the detection limit (0.03 mg / L).

(Fire resistance test)
A coating film composition similar to the coating film composition in the above impact resistance test was prepared. A cationic water-based sealer was applied to the entire single surface of a 0.27 mm thick galvanized steel sheet (manufactured by Toa Rika) using a brush, and further dried at room temperature. The coating amount of the aqueous sealer was 0.1 kg / m ² . Next, using a brush, the coating film composition was placed on the above-mentioned aqueous sealer at a coating ^{interval of 5 hours so that the coating amount of the coating film composition was 0.6 kg / m 2} , and the coating film composition was divided into two times. It was applied. Then, it was cured under the above-mentioned curing condition (A).

Three galvanized steel sheets on which the coating film obtained as described above was formed were prepared and used for evaluation of the fire resistance of the coating film. The fire resistance of the coating film was evaluated in accordance with the international standard ISO 5660-1: 2015. As a testing machine, a cone calorie meter (radiant intensity: 50 kW / m ² ) was used for 20 minutes of measurement. As a result, the total calorific value of all the test specimens was ^{less than the specified value (8 MJ / m 2} ); the presence or absence of deformation, melting, cracks and other harmful deformations for fire prevention was not observed; and the maximum heat generation rate was high. The time that continuously ^{exceeded 200 kW / m 2} was less than the specified value (10 seconds). From the above, it was found that the coating film formed by using the same coating film composition as the coating film composition in the impact resistance test satisfies the specified value as a non-combustible material.

(Weather resistance test)
A sample in which a coating film was formed on a glass plate was obtained in the same manner as in the above adhesion test. The weather resistance of the coating film was evaluated using the obtained sample. Specifically, it is as follows. Sunshine according to "b) Sunshine carbon arc lamp type weather resistance tester" in "4. Types" of Japanese Industrial Standard JIS B 7753: 2007 "Sunshine carbon arc lamp type light resistance tester and weather resistance tester" The sample was irradiated with a meter for a total of 5000 hours. The appearance of the sample was observed every 500 hours from the start of the test (however, the observation was not performed when 1500 hours had passed from the start of the test). No swelling, cracking, peeling, etc. was observed.

In addition, according to the Japanese Industrial Standards JIS K 5600-4-7: 1999, every 500 hours have passed since the start of the test (however, data has not been obtained when 1500 hours have passed since the start of the test). Mirror glossiness was measured. As a result, the mirror glossiness was 93 before the test; 111 after 500 hours; 108 after 1000 hours; 97 after 2000 hours; 90 after 2500 hours; 82; 3500 hours after the test. After 75; 4000 hours, it was 75; after 4500 hours, it was 63; after 5000 hours, it was 59. From the above, it was found that the coating film formed by using the same coating film composition as the coating film composition in the impact resistance test has excellent weather resistance.

(Evaluation of infrared shielding ability)
A coating film composition similar to the coating film composition in the above impact resistance test was prepared. In this section, the coating film composition is referred to as "Sample A".

A tin-antimony oxide was added to Sample A as an infrared absorber to prepare a coating film composition. In this section, the coating film composition is referred to as "sample IR". In the sample IR, 1.25 parts by mass of the infrared absorber was added to 80 parts by mass of the aqueous emulsion of the polycarbonate-based urethane resin and 20 parts by mass of the aqueous emulsion of the acrylic-modified polyester-based urethane resin, for a total of 100 parts by mass.

A benzotriazole derivative was added to Sample A as an ultraviolet absorber, and a tin-antimony oxide was added as an infrared absorber to prepare a coating film composition. In this section, the coating film composition is referred to as "sample UV-IR". In the sample UV-IR, 1.00 parts by mass of the ultraviolet absorber and 1.00 parts by mass of infrared rays were added to 80 parts by mass of the aqueous emulsion of the polycarbonate-based urethane resin and 20 parts by mass of the aqueous emulsion of the acrylic-modified polyester-based urethane resin. 1.25 parts by mass of the absorbent was added, respectively.

The infrared shielding ability of each sample obtained as described above was evaluated as follows. First, on a transparent glass substrate having a thickness of 3 mm, each of the above samples was subjected to a spin coater (manufactured by Mikasa, product name "1HD7"), and the coating film had a predetermined thickness (sample A, sample). For each of IR and sample UV-IR, 3 sheets of 100 μm, 200 μm, and 300 μm) were applied and dried at room temperature. As a comparative example, a transparent glass substrate having a thickness of 3 mm was used. Further, as a reference example, a transparent glass substrate having a thickness of 3 mm to which a commercially available infrared shielding film having a thickness of 76 μm or 148 μm was attached was prepared.

Next, each of the glass substrate to which each sample obtained as described above is coated, the glass substrate as a comparative example to which the sample is not coated, and the glass substrate as a reference example to which the infrared shielding film is attached is attached. , Halogen heater (manufactured by Ushio, "infrared lamp QIR100-1050 / ZD / CL150"), installed 8 cm directly below. The glass substrate to which each sample was applied or to which a film was attached was installed so that the coated or attached surface faced the halogen heater. Further, a heat insulating material was installed at a position 8 cm away from the glass substrate in the direction opposite to the halogen heater so that the heat insulating material and the halogen heater were spaced 16 cm apart from each other with the glass substrate in between.

Subsequently, while irradiating the halogen heater is started, the front surface of the glass substrate (the surface facing the halogen heater), the back surface of the glass substrate (the surface opposite to the surface facing the halogen heater), and the halogen heater on the glass substrate are displayed. The measurement of the surface temperature of the surface of the heat insulating material (the surface facing the halogen heater and the glass substrate) installed in the opposite direction was started. A thermocouple was used to measure the surface temperature, and the measurement was continued at 10-second intervals. After each surface temperature became stable, the infrared shielding ability of each glass substrate was evaluated by calculating the arithmetic mean of the measured values from the start of the surface temperature measurement to the lapse of 40 minutes to 60 minutes. The results are shown in FIG.

From FIG. 3, it was found that in each of the samples, the surface temperature of the heat insulating material was lower and the infrared shielding ability was higher than that of the glass substrate of the comparative example. In particular, in the examples using the sample IR and the sample UV-IR, the surface temperature of the heat insulating material is about the same as that in the reference example to which the infrared shielding film is attached, and the glass substrate coated with the sample IR and the sample UV-IR. Was found to have even better infrared shielding ability. Further, in the examples using the sample IR and the sample UV-IR, the surface temperatures of the front surface and the back surface of the glass substrate are both higher than those in the comparative example, and the infrared absorber of the coating film efficiently absorbs infrared rays. I found out that there is.

(Measurement of UV shielding ability)
A coating film composition similar to the coating film composition in the above impact resistance test was prepared. In this section, the coating film composition is referred to as "Sample A".

A benzotriazole derivative was added to Sample A as an ultraviolet absorber to prepare a coating film composition. In this section, the coating film composition is referred to as "sample UV". In the sample UV, 1.00 parts by mass of the ultraviolet absorber was added to 80 parts by mass of the aqueous emulsion of the polycarbonate-based urethane resin and 20 parts by mass of the aqueous emulsion of the acrylic-modified polyester-based urethane resin, for a total of 100 parts by mass.

A benzotriazole derivative was added to Sample A as an ultraviolet absorber, and a tin-antimony oxide was added as an infrared absorber to prepare a coating film composition. In this section, the coating film composition is referred to as "sample UV-IR". In the sample UV-IR, 1.00 parts by mass of the ultraviolet absorber and 1.00 parts by mass of infrared rays were added to 80 parts by mass of the aqueous emulsion of the polycarbonate-based urethane resin and 20 parts by mass of the aqueous emulsion of the acrylic-modified polyester-based urethane resin. 1.25 parts by mass of the absorbent was added, respectively.

The infrared shielding ability of each sample obtained as described above was evaluated as follows. First, on a transparent quartz glass substrate having a thickness of 5 mm, each of the above samples was subjected to a spin coater (manufactured by Mikasa, product name "1HD7"), and the coating film had a predetermined thickness (Sample A, For each of the sample UV and the sample UV-IR, three sheets of 100 μm, 200 μm, and 300 μm) were applied and dried at room temperature.

Next, for each of the quartz glass substrates coated with each of the samples obtained as described above, a wavelength of 300 nm (UV) was used using an ultraviolet visible spectrophotometer (manufactured by Shimazu, product name “UV-1280”). -B) and a shielding rate of a wavelength of 350 nm (UV-A) were determined. Table 1 shows the measurement results of the shielding rate at a wavelength of 300 nm (UV-B), and Table 2 shows the measurement results of the shielding rate at a wavelength of 350 nm (UV-A). The shielding rate was calculated as 100-T (%) using the transmittance T (%) measured by an ultraviolet-visible spectrophotometer.

(Measurement of transmittance 1)
By applying a coating film composition similar to the coating film composition in the impact resistance test to a quartz glass substrate, three types of samples for transmittance measurement having different coating film thicknesses were obtained. A spin coater (manufactured by Mikasa, product name "1HD7") was used for coating the coating film composition. Using an ultraviolet-visible spectrophotometer (manufactured by Shimazu, product name "UV-1280"), the transmittance of each sample at a wavelength of 750 nm was measured as described above. As a result, the sample having a coating film having a thickness of 70 μm was 96.9%, the sample having a coating film having a thickness of 140 μm was 94.3%, and the sample having a coating film having a thickness of 320 μm was 88.6%. ..

(Measurement of transmittance 2)
The visible light transmittances of Sample A, Sample UV, Sample IR, and Sample UV-IR, which are the coating film compositions in the above-mentioned infrared and ultraviolet shielding ability measurement test, were measured. Specifically, it is as follows. First, on a quartz glass substrate, each of the above samples was subjected to a spin coater (manufactured by Mikasa, product name "1H-D7"), and the coating film had a predetermined thickness (sample A, sample UV, sample IR, And each of the sample UV-IR was applied so as to be 100 μm, 200 μm, and 300 μm), and dried at room temperature.

Next, each of the quartz glass substrates to which each of the samples obtained as described above was coated was transmitted with a wavelength of 750 nm using an ultraviolet visible spectrophotometer (manufactured by Shimazu, product name “UV-1280”). I asked for the rate. The measurement results are shown in Table 3.

From Table 3, the coating films obtained by all the samples have sufficiently high visible light transmittance, and all the coating films can sufficiently transmit visible light while blocking ultraviolet rays and / or infrared rays. all right.

The composition for a coating film for preventing base material scattering of the present invention can sufficiently prevent the base material from scattering when the base material is damaged. Therefore, when it is necessary to prevent the base material from scattering such as glass, it is an industry. There is a possibility of the above.

100 ... Anti-scattering base material, 110 ... Base material, 120 ... Base material anti-scattering coating film, 200 ... Roller, 210 ... Roller body, 220 ... Rotating shaft member, 230 ... Connecting member, 240 ... Handle.

Claims (22)

A composition for a base material shatterproof coating film, which contains an aqueous emulsion of a polycarbonate-based urethane resin and has thixotropy properties. The composition for a substrate shatterproof coating film according to claim 1, wherein the glass transition temperature of the polycarbonate-based urethane resin is −50 ° C. or higher and −10 ° C. or lower. The composition for a substrate shatterproof coating film according to claim 1 or 2, wherein the thixotropy index is 2 or more. The composition for a substrate shatterproof coating film according to any one of claims 1 to 3, wherein the polycarbonate-based urethane resin has a breaking strength of 30 MPa or more and a breaking elongation of 200% or more. The composition for a substrate shatterproof coating film according to any one of claims 1 to 4, further comprising an infrared absorber. The composition for a substrate shatterproof coating film according to any one of claims 1 to 5, further comprising an ultraviolet absorber. A substrate shatterproof coating film, which is a solidified product of the composition for a substrate shatterproof coating film according to any one of claims 1 to 6. A base material shatterproof coating film containing a polycarbonate-based urethane resin, wherein the surface of the base material shatterproof coating film has irregularities. The base material shatterproof coating film according to claim 8, further comprising an infrared absorber. The base material shatterproof coating film according to claim 8 or 9, further comprising an ultraviolet absorber. The base material shatterproof coating film according to any one of claims 8 to 10, wherein the glass transition temperature of the polycarbonate-based urethane resin is −50 ° C. or higher and −10 ° C. or lower. The claim that the base material shatterproof coating film has a maximum convex height of 100 μm or more and 2000 μm or less from a standard thickness of the surface, and a deepest depth of 50 μm or more and 1500 μm or less from the standard thickness of the surface. The base material shatterproof coating film according to any one of 7 to 10. A shatterproof base material comprising a base material and a base material shatterproof coating film according to any one of claims 7 to 12, which is arranged on at least one surface of the base material. The anti-scattering base material according to claim 13, further comprising a solidified product of a cationic aqueous sealer between the base material and the anti-scattering coating film of the base material. The anti-scattering substrate according to claim 14, wherein the cationic aqueous sealer contains an aqueous emulsion of a polyurethane resin. The base material is one selected from the group consisting of inorganic glass, acrylic resin, polycarbonate resin, and fiber-reinforced plastic, and inorganic glass, acrylic resin, polycarbonate resin, and fiber-reinforced plastic provided with a shatterproof film. The shatterproof base material according to any one of claims 13 to 15, which is the above. A step of applying the base material scattering prevention coating film composition according to any one of claims 1 to 6 to the surface of the base material, and a step of drying the applied base material scattering prevention coating film composition. A method for forming a shatterproof substrate, including. The step of applying the cationic aqueous sealer to the surface of the base material, the step of drying the applied cationic aqueous sealer, and any one of claims 1 to 6 on the surface of the solidified product of the cationic aqueous sealer. An anti-scattering base material comprising a step of applying the composition for a base material scattering prevention coating film according to item 1 and a step of drying the applied composition for a base material scattering prevention coating film in this order. Forming method. The step of applying the composition for a base material scattering prevention coating film and the step of drying the composition for a base material scattering prevention coating film are repeated twice or more in this order, according to claim 17 or 18. A method for forming a shatterproof substrate. The anti-scattering property according to any one of claims 17 to 19, wherein in the step of applying the composition for a base material scattering prevention coating film, the composition for a base material scattering prevention coating film is applied by roller coating. Method of forming a base material. The roller coating is a roller coating using a roller having a coating surface that comes into contact with the surface of the base material or the surface of the cationic aqueous sealer.
The method for forming an anti-scattering base material according to claim 20, wherein the roller has an uneven shape on the coated surface. A base material shatterproof coating film forming kit comprising the composition for a base material shatterproof coating film according to any one of claims 1 to 6 and a cationic aqueous sealer.

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