JP2003096396A - Coating material composition for forming insect-proofing layer and insect-proofing film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating material composition for forming an insect- proofing layer which can effectively prevent insects from coming flying by the attraction to light. SOLUTION: The coating material composition for forming the insect-proofing layer is obtained by dispersing inorganic oxide particles having an insect- proofing function and an average primary particle diameter of <=0.05 μm in a binder resin solution. The inorganic oxide particles are incorporated in an amount sufficient to form an insect proofing layer which comes to have a light transmittance of a wavelength of <=500 nm of <=15% and, simultaneously, a light transmittance of a wavelength of >=600 nm of >=50%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a coating composition for forming an insect repellent layer, which can effectively prevent insects from flying by being attracted by light, and a transparent film having an insect repellent layer formed from the coating composition. The present invention relates to an insect repellent film formed on the surface.

[0002]

2. Description of the Related Art Many insects flying at night are about 300 nm
Can recognize light in the wavelength range from 500 nm to 500 nm and is attracted to the light leaking from the room to the outside. Insects that have entered the room are mixed into foods as foreign matter, and insects that remain in windows are unsightly. There was a problem that the image of the store was down. Therefore, conventionally, as a method of preventing the attraction of insects, a method of attaching a film containing a UV absorber or a dye that absorbs UV light in combination with it to a window or the like (see, for example, Japanese Patent Publication No. 7-57153). ), A method of exterminating with an insecticide, a method of preventing invasion with an air curtain, etc. were adopted.

However, in the method of attaching the above-mentioned film, the ultraviolet absorber usually cuts well against ultraviolet light of 380 nm or less, but has a low cut rate for light of wavelengths longer than that, and prevents insects from being attracted. The effect is low, and the ultraviolet absorber and the dye are liable to deteriorate, resulting in poor durability. In addition, the method using the above insecticide,
Although insects and the like can be exterminated temporarily, there is no continuous attraction-preventing effect, and the above-mentioned method using an air curtain requires a large-scale device and maintenance.

[0004]

SUMMARY OF THE INVENTION The present invention has been made against the background of the problems of the prior art as described above, and has an excellent effect to prevent insects from being attracted to insects, and requires no maintenance. An object of the present invention is to provide a coating composition for forming and an insect repellent film provided with an insect repellent layer formed from the coating composition.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to achieve the above-mentioned objects, and as a result, have found that the above-mentioned objects can be achieved by the following constitutions, and have arrived at the present invention. That is, the present invention is a coating composition for forming an insect repellent layer, which comprises an inorganic oxide particle having an insect repellent function having an average primary particle diameter of 0.05 μm or less dispersed in a binder resin solution, which has a wavelength of 500 nm or less. An insect repellent characterized in that the inorganic oxide particles are blended in an amount sufficient to form an insect repellent layer having a transmittance of 15% or less and a light transmittance of 50% or more at a wavelength of 600 nm or more. The present invention relates to a coating composition for forming a layer. Further, the present invention is an insect repellent film in which a transparent film has an insect repellent layer having a light transmittance of 15% or less at a wavelength of 500 nm or less and a light transmittance of 50% or more at a wavelength of 600 nm or more. In addition, the present invention relates to an insect-repellent film, which is a coating film formed from the above-mentioned insect-repellent-layer-forming coating composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The insect-repellent layer-forming coating composition of the present invention is a binder resin,
It is composed of inorganic oxide particles having a pest control function, a solvent, and various additives such as a dispersant, a wetting agent, and a leveling agent, which are blended as necessary. As the binder resin,
As long as it is transparent, various binder resins that have been conventionally used for coating materials can be used, but the dispersion stability of the inorganic oxide particles described below is excellent, for example, an acid value of 0.5 to 15 mgKOH / g, preferably 1.0-10 mg KOH
Acrylic resins having a phosphoric acid group of / g, resins such as polyester resins and alkyd resins, and particularly acrylic resins having an acidic phosphoric acid group are preferable. As the binder resin, a copolymerizable ethylenically unsaturated monomer (a) having an acidic phosphoric acid group functional group and another ethylenically unsaturated monomer (b) copolymerizable with the monomer (a) are used. The weight average molecular weight obtained by radical polymerization by an ordinary means is, for example, 5,000 to 150,000, preferably
Acrylic resin of 8000 to 80,000 is preferable.

Examples of the monomer (a) include mono (2- (meth) acryloyloxyethyl) acid phosphate, mono (2- (meth) acryloylpolyoxyethyl) acid phosphate, and diphenyl2-.
(Meth) -acryloyloxyethyl phosphate and the like can be mentioned. Examples of the other monomer (b) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl. (Meth) acrylate-based monomers such as (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate; styrene-based monomers such as styrene and methylstyrene; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc. Hydroxyl group-containing monomer; Other than that, vinyl acetate, (meth) acrylonitrile, ethylene and the like are mentioned as typical monomers.

The ratio of the monomer (a) to the monomer (b) is such that the acrylic resin obtained has an acid value of 0.5 to, for example.
A ratio of 15 mgKOH / g, preferably 1.0 to 10 mgKOH / g is suitable, and in this range, a coating composition for forming an insect repellent layer which is uniformly dispersed without agglomerating inorganic oxide particles described below is produced. can do. As the inorganic oxide particles having the insect repellent function, various inorganic oxide particles can be used as long as they have the insect repellent function, but preferably α-iron oxide particles and dimanganese trioxide particles are suitable. Is. The average primary particle size of the particles is 0.05 μm.
m or less, preferably 0.03 μm or less. A suitable lower limit is, for example, 0.001 μm. When the average primary particle diameter exceeds 0.05 μm, the transparency of the obtained coating film is deteriorated, which is not preferable.

As the above-mentioned solvent, various solvents conventionally used for coating materials can be used as long as they dissolve or stably disperse the binder resin.
Specific examples include polar solvents such as methanol, ethanol, butanol, diacetone alcohol, diethylene glycol, isophorone, and cyclohexanone; non-polar solvents such as xylene and toluene, cyclohexane, hexane, and octane are typical examples. To be

In the coating composition for forming an insect repellent layer of the present invention, the mixture of the binder resin and the inorganic oxide particles having an insect repellent function is such that the resulting coating film has a light transmittance of 15 at a wavelength of 500 nm or less. % Or less, preferably 10% or less, and 50% or more, preferably 60% or more with light having a wavelength of 600 nm or more.
In addition, if the light transmittance of the wavelength of 500 nm or less exceeds 15%, insects are attracted to the light and fly in, so that the insect repellent effect is insufficient, and the light transmittance of the wavelength of 600 nm or more is 50%. When it is less than%, the transparency under visible light is deteriorated and, for example, when it is applied to a window glass, the room becomes dark, which is not preferable.

The compounding ratio of the binder resin and the inorganic oxide particles having an insect repellent function for forming a coating film having such a light transmittance varies depending on the types of both and is usually 100 parts by mass of the former. On the other hand, the latter is suitably 10 to 400 parts by mass, preferably 50 to 200 parts by mass.
Further, the amount of solvent is 20 to 60% by mass, preferably 30 to 50% by mass of the solid content of the insect-repellent-layer-forming coating composition from the viewpoint of storage stability of the insect-repellent-layer-forming coating composition and coating workability.
Mass% is suitable.

The insect-repellent-layer-forming coating composition of the present invention is prepared by adding a part of a solvent to a binder resin and an additive to be added as necessary to prepare a resin solution, and mixing inorganic oxide particles having an insect-repellent function with the resin solution. A ball mill, a sand grind mill, three rolls, a paint shaker, a homogenizer, an ultrasonic disperser, or a combination of these may be used to disperse, and then the remaining solvent may be added and mixed. However, the method is not limited to this. The insect-repellent film of the present invention is produced by applying the above-mentioned insect-repellent-layer-forming coating composition on a transparent substrate and drying it to form an insect-repellent layer on the insect-repellent film.

The transparent substrate is, for example, polyethylene.
, Polypropylene, polyethylene terephthalate,
Polycarbonate, polyvinyl chloride, polymethylmethacrylate
Plastic sheets such as rate and cellulose acetate
Rum is suitable. As a coating method, for example, a roll
Coating method, die coating method, gravure coating method, knife
Typical methods include coating method and bar coating method.
Be done. Further, the insect repellent layer is an inorganic oxide particle having an insect repellent function.
Child is 1.0 to 5.0 g / m ², Preferably 1.5 to
4.0 g / m²It is appropriate to have a film thickness such that
is there.

The insect-repellent film of the present invention can be used as it is, but a transparent adhesive layer is provided on at least one of the above-mentioned insect-repellent layer surface and the transparent film surface opposite to the insect-repellent layer to form a transparent substrate. It is also possible to use by pasting. Examples of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer include resin-based pressure-sensitive adhesives such as polymethyl methacrylate, polyvinyl ether, vinyl chloride-vinyl acetate copolymer, and polyvinyl butyrate. In addition, a release film that protects the surface of the pressure-sensitive adhesive layer until it is attached is required. As the release film, for example, a PET film or the like is used. Further, depending on the intended use of the insect-controlling film of the present invention, a hard coat layer may be provided on one surface for the purpose of imparting scratch resistance.

By providing an adhesive resin layer on both sides of the insect-repellent film of the present invention, and sandwiching and bonding the two glass sheets, it can be used as a laminated glass having an insect-repellent function. As the adhesive resin, for example, a modified product mainly composed of an ethylene-vinyl ester copolymer, a modified product mainly composed of an ethylene- (meth) acrylic acid ester copolymer, and a (meth) acrylic acid ester copolymer as a main component Modified product, modified product mainly composed of urethane polymer, modified product mainly composed of hydrogenated styrene-butadiene-styrene block copolymer, modified product mainly composed of vinyl chloride polymer,

Examples include modified products mainly composed of nylon copolymers and plasticized polyvinyl butyral. Further, the thickness of the adhesive resin layer is preferably 50 to 1000 μm. The method of bonding with the glass with the adhesive resin layer interposed on both sides of the insect-repellent film can be carried out by using a usual method. That is, there may be mentioned a method of laminating under heating and pressurization using an autoclave, or a method of evacuating the system and then heating for laminating.

[0017]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the scope of the present invention is not limited to these examples. In the examples, "part" and "%"
Is shown on a mass basis unless otherwise specified, and the unit of acid value is
It is “(mg KOH / g)”. Moreover, the average particle diameter of the inorganic oxide was calculated from the measured value of the specific surface area (BET value: m ² / g).

Example 1 (Preparation of Binder Resin Solution A) A flask equipped with a reflux tube, a thermometer, a dropping funnel and a stirrer was charged with 60 parts of xylene and heated to 90 ° C.
Furthermore, 20.0 parts of styrene and 19.2 of methyl acrylate
Part, a mixture of 0.8 parts of mono (2-methacryloyloxyethyl) acid phosphate and 1.0 part of azobisisobutyronitrile are added and reacted by heating,
Nonvolatile content 40%, weight average molecular weight of the resin is 50,000,
A resin solution A having an acid value of 5.6 was obtained.

(Preparation of coating composition for insect repellent layer
Preparation of Rum) 20 parts of α-iron oxide having an average primary particle diameter of 0.02 μm, 50 parts of resin solution A, 30 parts of xylene, and zirconia beads 2
50 parts were placed in a glass bottle and dispersed for 6 hours while confirming the dispersed state with a paint shaker, and then the zirconia beads were removed to obtain a coating composition for forming an insect repellent layer. This insect-repellent layer-forming coating composition was applied on a PET film having a thickness of 75 μm by wire bar coating so that α-iron oxide particles were 2 g / m ^{2 in} a dry film, and dried to obtain an insect-repellent layer. Was formed. A 10 μm thick polymethylmethacrylate adhesive was applied onto the insect repellent layer of the obtained insect repellent film, and this was adhered to a 3 mm thick glass plate to give a sample for evaluation.

Example 2 In the same manner as in Example 1, the α-iron oxide particles in the insect repellent layer were
After coating so as to be 4 g / m ² , an adhesive mainly composed of saponified ethylene-vinyl acetate copolymer on both sides of the insect-proof film (manufactured by Tosoh Corp., trade name Mersen G7011)
Was applied in a thickness of 250 μm, and was stuck between two 3 mm-thick glass plates to prepare a laminated glass, which was used as a sample for evaluation.

Example 3 Dimanganese trioxide 20 having an average primary particle diameter of 0.03 μm
Part, resin solution A 50 parts, xylene 30 parts and zirconia beads 250 parts were placed in a glass bottle and dispersed for 6 hours while confirming the dispersion state with a paint shaker, and then the zirconia beads were removed to prepare an insect repellent layer coating composition. I got a thing. This insect-repellent layer-forming coating composition was applied on a PET film having a thickness of 75 μm by wire bar coating so that the dimanganese trioxide particles were 4 g / m ^{2 in} a dry film, and dried to obtain an insect-repellent layer. Was formed. On the insect repellent layer of the insect repellent film obtained, 1
It was applied to a thickness of 0 μm and attached to a glass plate having a thickness of 3 mm to obtain a sample for evaluation.

Comparative Example 1 Benzotriazole type UV absorber (Cypro Kasei Co., Ltd.)
Made, product name Seesorb 703) 2 parts, resin solution A60
Parts and xylene 38 parts to dissolve in a solution to obtain an insect-repellent layer-forming coating composition. This insect-repellent layer-forming coating composition was applied by wire bar coating onto a PET film having a thickness of 75 μm so that the dry film thickness was 2 μm, and dried to form an ultraviolet absorbing layer. On the ultraviolet absorbing layer of the obtained film, a polymethylmethacrylate adhesive was applied in a thickness of 10 μm, and this was attached to a glass plate having a thickness of 3 mm to give a sample for evaluation.

Comparative Example 2 A coating composition for forming an insect repellent layer was prepared in the same manner as in Example 1, and the wire bar coat was used to deposit α-iron oxide particles at 8 g / m ² on a PET film having a thickness of 75 μm. It was applied so as to be dried and dried to form an insect repellent layer. A polymethylmethacrylate-based pressure-sensitive adhesive was applied on the insect-repellent layer of the obtained insect-repellent film in a thickness of 10 μm, and this was attached to a 3 mm-thick glass plate to give a sample for evaluation.

Comparative Example 3 An evaluation sample was prepared in the same manner as in Example 1 except that 20 parts of α-iron oxide having an average primary particle diameter of 0.10 μm was used.

Comparative Example 4 (Preparation of Binder Resin Solution B) A flask equipped with a reflux tube, a thermometer, a dropping funnel and a stirrer was charged with 60 parts of xylene and heated to 90 ° C., and then 20.0 parts of styrene. ,
20.0 parts of methyl acrylate and 1.0 part of azobisisobutyronitrile were added, and the mixture was heated and reacted to give a nonvolatile content of 40
%, A resin weight average molecular weight of 50,000 and an acid value of 0 were obtained.

(Preparation of coating composition for insect repellent layer
Preparation of rum) 20 parts of α-iron oxide having an average primary particle diameter of 0.02 μm, 50 parts of resin solution B, 30 parts of xylene, 1 part of pigment dispersant (manufactured by BYK, trade name Disperbyk-130) and 250 parts of zirconia beads in a glass bottle. After confirming the dispersion state with a paint shaker and performing dispersion for 6 hours, the zirconia beads were removed to obtain a coating composition for forming an insect repellent layer. This coating composition for forming an insect-repellent layer was coated with a wire bar coat on a PET film having a thickness of 75 μm to form α
-The iron oxide particles were applied so as to have a dry film thickness of 2 g / m ^2, and dried to form an insect repellent layer. On the insect repellent layer of the insect repellent film obtained, 1
It was applied to a thickness of 0 μm and attached to a glass plate having a thickness of 3 mm to give a sample for evaluation.

With respect to the evaluation samples obtained in the respective Examples and Comparative Examples, the light transmittance, the insect repellent performance, the haze, the room brightness,
Further, comprehensive judgment was made from these data, and the results are shown in FIG. 1, FIG. 2 and Table 1. The transmittance was measured with a spectrophotometer in the region from 300 nm to 1000 nm with the absorption of the glass plate, film, pressure-sensitive adhesive and adhesive of the evaluation sample corrected. In addition, the insect repellent performance was determined by attaching a sample for evaluation to a window, then turning on a fluorescent lamp in a room at night, and counting the number of flying beetles / m ² . The haze (cloudiness) was measured by a fully automatic haze meter (TC-H III DPK type) manufactured by Tokyo Denshoku Gijutsu Center Co., Ltd. The brightness of the room was visually judged by the brightness of the room during the day.

Further, in the durability test, the evaluation sample was subjected to an accelerated experiment with Super UV for 100 hours, and the spectrum before and after the durability test was measured. The results are shown in FIG. In addition, A to I in Table 1 indicate the following contents. A: Acid value of resin solid content (mgKOH / g) B: Average primary particle size (μm) of inorganic oxide particles C: Kind of inorganic oxide D: Content of inorganic oxide particles in insect repellent layer (g /
m ² ) E: Transmittance (%) F: Insect repellent performance (animals / m ² ) G: Haze (%) H: Daytime brightness (⊚: bright, △: dim, ×: dark) I: Overall evaluation (◎: Comprehensively good, ○: Comprehensively normal,
×: Overall bad)

[0029]

[Table 1] Table 1

From the above results, the insect repellent films of Examples 1 to 3 were excellent in insect repellent property, transparency and durability. On the other hand, in Comparative Example 1 in which an ultraviolet absorber was blended in place of the inorganic oxide particles having insect repellent performance, the insect repellent property and durability were poor. Further, in Comparative Examples 2, 3, and 4 having a light transmittance of less than 50% at a wavelength of 600 nm, although they had insect repellent properties, the transparency was poor, and the room was dark and haze was high.

[0031]

The coating composition for forming an insect repellent layer of the present invention can be applied to the surface of a transparent film to obtain an insect repellent film that effectively prevents insects from flying due to light, and prevents them from flying for a long time. Becomes

[Brief description of drawings]

FIG. 1 shows the wavelengths (n of the evaluation samples of Examples 1 to 3).
It is a figure which shows the transmittance | permeability (%) with respect to m).

FIG. 2 shows the wavelengths (n of the evaluation samples of Comparative Examples 1 to 4).
It is a figure which shows the transmittance | permeability (%) with respect to m).

FIG. 3 is a diagram showing spectrum changes before and after a durability test for evaluation samples of Example 1 and Comparative Example.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 7/12 C09D 7/12 C09J 7/02 C09J 7/02 Z (72) Inventor Hiroyuki Tanabe Tochigi Prefecture 8-15 Asahi-cho, Nishi-Nasuno-cho, Nasu-gun (72) Inventor Shinichi Sato 3-1-2, Fukuei, Ichikawa-shi, Chiba Gyuntoku Highrise Room 311 F-term (reference) 4F100 AA17B AA17H AA23B AA23H AG00D AK01B AR00C AS00B AT00A BA03 BA04 BA07 BA10B BA10C BA10D CA30B DE01B DE01H EH46 GB07 JL00 JL13C JN08B YY00B 4H011 AC06 BA01 BB18 BC01 BC18 BC19 DA15 DC05 DD07 DH02 4J004 AA06 AA08 AA10 AB01 CA02 CA02 CA10 DB12 CA02 CA03 DB02 CD03 CD02 CD03 CD05 CD02 CD03 CD05 CD05 CD03 CD05 CD02 CD03 CD05 CD05 CD02 CD03 CD05 CD05 CD02 CD03 CD05 CD02 CD03 CD05 CD02 CD03 CD05 CD02 CD03 CD05 CD02 CD03 KA20 NA02 NA17 PB05 PC08

Claims (6)

[Claims] 1. A coating composition for forming an insect repellent layer, which comprises an inorganic oxide particle having an insect repellent function having an average primary particle diameter of 0.05 μm or less dispersed in a binder resin solution, which has a thickness of 500 nm.
The inorganic oxide particles are blended in an amount sufficient to form an insect repellent layer having a light transmittance of 15% or less at the following wavelengths and a light transmittance of 50% or more at a wavelength of 600 nm or more. A coating composition for forming an insect repellent layer, comprising: 2. The inorganic oxide particles are α-iron oxide and / or
Alternatively, the coating composition for forming an insect repellent layer according to claim 1, which is dimanganese trioxide. 3. The binder resin has an acid value of 0.5 to 15.
A resin having a mgKOH / g phosphoric acid group.
The insect-repellent layer-forming coating composition as described in 1. 4. An insect repellent film comprising a transparent film and an insect repellent layer having a light transmittance of 15% or less at a wavelength of 500 nm or less and a light transmittance of 50% or more at a wavelength of 600 nm or more formed on the surface of the transparent film. The insect-repellent layer is a coating film formed from the insect-repellent-layer-forming coating composition according to any one of claims 1 to 3. 5. The insect repellent film according to claim 4,
An insect-repellent film comprising an adhesive layer provided on at least one of the surface of the insect-repellent layer and the surface of the transparent film opposite to the insect-repellent layer. 6. The insect repellent film according to claim 4,
An insect repellent film for laminated glass, comprising an adhesive resin layer provided on both surfaces of the insect repellent layer and the transparent film surface opposite to the insect repellent layer.