WO2016153050A1

WO2016153050A1 - Anti-fogging composition and anti-fogging film

Info

Publication number: WO2016153050A1
Application number: PCT/JP2016/059709
Authority: WO
Inventors: 崇後藤
Original assignee: 積水フィルム株式会社
Priority date: 2015-03-25
Filing date: 2016-03-25
Publication date: 2016-09-29
Also published as: JPWO2016153050A1

Abstract

The present invention addresses the problem of providing an anti-fogging composition having excellent transparency and long-lasting anti-fogging properties and anti-fogging performance, whereby an anti-fogging layer formed by applying the anti-fogging composition exhibits excellent scratch resistance and resistance to flexural whitening. The present invention provides an anti-fogging composition containing colloidal silica, a binder resin, a film-forming auxiliary, and a surfactant, the anti-fogging composition being characterized in that (1) the mass ratio (Ma/Mb) of the solid content mass (Ma) of the colloidal silica and the solid content mass (Mb) of the binder resin is 0.5-5.0, (2) the film-forming auxiliary includes carbon atoms and has a boiling point of 100°C or higher, and (3) the mass ratio (Ma + Mb)/(Mc) of the sum of the solid content mass (Ma) of the colloidal silica and the solid content mass (Mb) of the binder resin (Ma + Mb) and with respect to the mass (Mc) the film-forming auxiliary is 1.0-16.0.

Description

Antifogging composition and antifogging film

The present invention relates to an antifogging composition and an antifogging film.

Conventionally, there has been a demand for technology for imparting antifogging properties to products such as films in various fields. For example, in the agricultural field, when cultivating agricultural crops, in order to increase marketability and productivity, vinyl chloride film, special film mainly composed of polyethylene, ethylene-vinyl acetate copolymer and polyolefin resin, etc. House cultivation and tunnel cultivation, in which useful crops are cultivated by coating with agricultural films, are being actively performed.

The above-mentioned agricultural film has high transparency in order to transmit sunlight, and so-called anti-fog that water droplets attached to the inner surface of the film flow down along the inner surface of the film without falling on the cultivated crop. Property (droplet property) is required.

As a method of imparting antifogging properties to a film, a method of kneading an antifogging agent such as sorbitan fatty acid ester into a synthetic resin composition forming a film is used. This method is a method of causing the film to exhibit antifogging properties by bleeding out the kneaded antifogging agent to the resin surface. According to this method, the antifogging agent bleeds out from the film quickly. For this reason, there is a problem that the antifogging effect is reduced after one year has passed since the film was spread on the house.

An agricultural drip-proof film in which an aqueous acrylic-modified urethane resin coating layer containing colloidal silica particles is provided on one side of a synthetic resin film has been proposed as an agricultural film in which such problems have been solved ( (See claim 1 of Patent Document 1). As a coating layer of the agricultural drip-proof film, an aqueous emulsion composition containing an aqueous acrylic-modified urethane resin, colloidal silica particles, and a polyether-modified silicone surfactant is applied and dried. A film layer is described (see claim 2 of Patent Document 1).

JP-A-7-298791

However, in the above-mentioned drip-proof film for agriculture, an aqueous acrylic modified urethane resin and colloidal silica particles are used to improve the antifogging property. There is a problem that whitening occurs when it is bent, so-called whitening occurs.

In addition, the coating layer formed using the above-mentioned aqueous emulsion composition is inferior in scratch resistance, and when the surface is rubbed with moisture, the coating layer is damaged and the anti-fogging property is lowered. is there.

Therefore, the antifogging and antifogging performances are long-lasting and transparent, and the antifogging layer formed by applying the antifogging composition exhibits excellent anti-folding whitening and scratch resistance. Development of an anti-fogging composition capable of achieving this is desired.

The present invention has been made in view of the above problems, and is an anti-fogging layer formed by coating the anti-fogging composition with excellent anti-fogging property and anti-fogging performance for a long period of time and transparency. However, an object of the present invention is to provide an antifogging composition capable of exhibiting excellent resistance to whitening and scratch resistance.

As a result of intensive studies to achieve the above object, the inventors of the present invention contain colloidal silica, a binder resin, a film-forming aid and a surfactant, and (1) the solid content mass (Ma) of colloidal silica and The mass ratio (Ma / Mb) to the solid content mass (Mb) of the binder resin is 0.5 to 5.0, and (2) the film-forming aid contains carbon atoms and has a boiling point of 100 ° C. or higher. (3) The mass ratio (Ma + Mb) of the sum (Ma + Mb) of the solid content mass (Ma) of the colloidal silica and the solid content mass (Mb) of the binder resin to the mass (Mc) of the film-forming aid. ) / (Mc) is 1.0 to 16.0, it has been found that the above object can be achieved, and the present invention has been completed.

That is, the present invention relates to the following antifogging composition and antifogging film.
1. An antifogging composition containing colloidal silica, a binder resin, a film-forming aid and a surfactant,
(1) The mass ratio (Ma / Mb) between the solid content mass (Ma) of the colloidal silica and the solid content mass (Mb) of the binder resin is 0.5 to 5.0,
(2) The film-forming aid contains carbon atoms and has a boiling point of 100 ° C or higher.
(3) The mass ratio (Ma + Mb) / (total mass (Mb) of the colloidal silica and the total mass (Mb) of the binder resin and the mass (Mc) of the film-forming aid. Mc) is 1.0-16.0,
An antifogging composition characterized by the above.
2. Item 2. The antifogging composition according to Item 1, wherein the binder resin has a glass transition point of 0 to 100 ° C.
3. Item 3. The antifogging composition according to Item 1 or 2, wherein the content of the film-forming auxiliary is 0.1 to 10.0% by mass with respect to 100% by mass of the antifogging composition.
4). An antifogging film having an antifogging layer formed of the antifogging composition according to any one of Items 1 to 3 on at least one surface of the synthetic resin film.

The antifogging composition of the present invention is excellent in antifogging properties and long-lasting antifogging performance, and transparency, and the antifogging layer formed by coating the antifogging composition is excellent. Bending resistance and whitening resistance can be exhibited.

It is sectional drawing which shows an example of the laminated constitution of the anti-fogging film of this invention. It is sectional drawing which shows an example of the laminated constitution of the anti-fogging film of this invention.

The antifogging composition of the present invention contains colloidal silica, a binder resin, a film-forming aid, and a surfactant. (1) The solid content mass (Ma) of the colloidal silica and the solid content mass of the binder resin ( Mb) has a mass ratio (Ma / Mb) of 0.5 to 5.0, (2) the film-forming aid contains carbon atoms and has a boiling point of 100 ° C. or higher, (3) The mass ratio (Ma + Mb) / (Mc) of the sum (Ma + Mb) of the solid content mass (Ma) of the colloidal silica and the solid content mass (Mb) of the binder resin to the mass (Mc) of the film-forming aid is It is an antifogging composition that is 1.0 to 16.0.

Since the antifogging composition contains colloidal silica, it exhibits excellent antifogging properties and long-lasting antifogging performance.

The antifogging composition of the present invention contains a surfactant, and the mass ratio (Ma / Mb) of the solid content mass (Ma) of the colloidal silica and the solid content mass (Mb) of the binder resin. Is in a specific range, it is excellent in antifogging properties and long-lasting antifogging performance, and transparency, and the antifogging layer formed by coating the antifogging composition has excellent scratch resistance. Can be shown.

Further, the antifogging composition of the present invention contains a film-forming aid, and the total (Ma + Mb) of the solid content mass (Ma) of the colloidal silica and the solid content mass (Mb) of the binder resin, and the film-forming composition. Since the mass ratio (Ma + Mb) / (Mc) to the mass (Mc) of the auxiliary agent is 1.0 to 16.0, the antifogging composition maintains excellent antifogging properties and long-term durability of the antifogging performance. However, the anti-fogging layer formed by coating the anti-fogging composition can exhibit excellent anti-folding whitening properties.

In the present invention, when the glass transition point of the binder resin is 0 to 100 ° C., the anti-fogging layer formed by applying the anti-fogging composition has excellent scratch resistance and fold whitening resistance. In addition, it can exhibit anti-blocking properties.

Hereinafter, the antifogging composition and antifogging film of the present invention will be described in detail.

1. Antifogging composition The antifogging composition of the present invention is an antifogging composition containing colloidal silica, a binder resin, a film-forming aid and a surfactant, and (1) the solid content of the colloidal silica. The mass ratio (Ma / Mb) between the mass (Ma) and the solid content mass (Mb) of the binder resin is 0.5 to 5.0, (2) the film-forming aid contains carbon atoms, And the boiling point is 100 ° C. or higher, and (3) the sum (Ma + Mb) of the solid content mass (Ma) of the colloidal silica and the solid content mass (Mb) of the binder resin, and the mass (Mc) of the film-forming aid. ) And the mass ratio (Ma + Mb) / (Mc) is 1.0 to 16.0.

When the above (Ma / Mb) is smaller than 0.5, the antifogging layer formed using the antifogging composition cannot exhibit sufficient antifogging properties. When the (Ma / Mb) is larger than 5.0, the scratch resistance and transparency of the antifogging composition are lowered. The (Ma / Mb) is preferably 0.8 to 3.0, and more preferably 1.0 to 2.5.

When the above (Ma + Mb) / (Mc) is less than 1.0, the antifogging layer formed using the antifogging composition cannot exhibit sufficient antifogging properties, and the leveling properties are lowered. When (Ma + Mb) / (Mc) is larger than 16.0, the antifogging layer formed using the antifogging composition cannot exhibit sufficient whitening resistance and transparency. The (Ma + Mb) / (Mc) is preferably 1.0 to 14.0, and more preferably 5.0 to 10.0.

(Binder resin)
The binder resin contained in the antifogging composition of the present invention may be either a hydrophilic binder resin or a hydrophobic binder resin, but is a hydrophobic binder in that it can exhibit more excellent antifogging properties. Resins are preferred.

Examples of the hydrophilic binder resin include polyvinyl alcohol, ethylene-vinyl alcohol copolymer, vinyl acetate water-soluble resin, polyethylene oxide, cellulose acylate, polyethylene glycol, polyvinyl pyrrolidone, polyacrylamide, polyvinyl butyral, polyether ester amide, Modified cellulose such as poly (N-methylolacrylamide), hydroxyethylcellulose, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, water-soluble polyester resin, water-soluble polyvinyl acetal, poly-N-vinylacetamide, polyacrylamide, polyacryloylmorpholine, polyhydroxy Examples include acrylic acrylate, polyacrylic acid, and polyether-based materials.

Examples of the hydrophobic binder resin include acrylic resins, urethane resins, epoxy resins, and polyester resins, and acrylic resins are particularly preferably used.

Examples of the acrylic resin include a homopolymer or a copolymer of a (meth) acrylic monomer, and a copolymer of a (meth) acrylic monomer and another copolymerizable monomer. . In the present specification, “(meth) acrylic monomer” means an acrylic monomer or a methacrylic monomer, and the same applies to other portions described as (meth). .

Specific examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and n-butyl (meth) ) Acrylate, t-butyl (meth) acrylate, i-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl Alkyl (meth) acrylates such as (meth) acrylate, phenyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, containing functional groups such as glycidyl (meth) acrylate (meth) acrylate; (meth) acrylamide. These monomers can be used alone or in combination of two or more.

Specific examples of other monomers copolymerizable with the (meth) acrylic monomer include aromatic vinyl monomers such as styrene and α-methylstyrene; vinyl pyridine, vinyl alcohol, and vinyl imidazole. Vinyl monomers such as vinylpyrrolidone, vinyl acetate and 1-vinylimidazole; itaconic acid esters such as monomethyl itaconate and monoethyl itaconate; monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, monobutyl fumarate And maleic acid esters such as monomethylmalate, monoethylmalate, monopropylmalate, monobutylmalate, and the like. These monomers can be used alone or in combination of two or more.

As the urethane resin, for example, polyether, polyester, and polycarbonate anionic polyurethane resins can be used. These urethane resins may be used in the form of an aqueous composition or an emulsion.

As the urethane-based resin, an emulsion of a polycarbonate-based anionic polyurethane resin is preferable in terms of excellent adhesion to the synthetic resin film of the anti-fogging layer, water resistance and surface strength (scratch resistance), and the anti-fogging layer has water resistance. In view of further improving the anti-fogging property and scratch resistance, and shortening the time until the anti-fogging property is exhibited, the emulsion of the polycarbonate-based anionic polyurethane resin having a silanol group is more preferable. These urethane resins may be used alone or in combination of two or more.

The binder resin contained in the antifogging composition of the present invention preferably has a glass transition point (Tg) of 0 to 100 ° C. When the glass transition point of the binder resin is 0 ° C. or higher, the anti-fogging layer formed by coating the anti-fogging composition can exhibit excellent antiblocking properties, and the glass transition point is 100 ° C. or lower. By being, it is suppressed that the anti-fogging layer formed by applying the anti-fogging composition is dropped, and more excellent scratch resistance can be exhibited. In the present specification, the glass transition point of the binder resin is a value measured by a measuring method based on JIS K7121, and specifically, a differential scanning calorimeter (DSC; manufactured by Seiko Electronics Co., Ltd.). : SSC5200 (model number)) based on JIS K7121 (plastic glass transition temperature measurement method), measured in an inert gas at a temperature increase rate of 10 ° C./min. The measurement is performed after a predetermined amount of sample is weighed on a sample pan and dried at 130 ° C. for 3 hours.

In the antifogging composition of the present invention, the solid content of the binder resin is preferably 1 to 10% by mass, based on 100% by mass of the antifogging composition, and preferably 2 to 7% by mass. Is more preferable.

(Colloidal silica)
The antifogging composition of the present invention contains colloidal silica. Colloidal silica is a state in which silica particles represented by the chemical composition formula of SiO ₂ are dispersed in a liquid to form a colloid. When the silica particles are primary particles, the average particle size of the silica particles contained in the colloidal silica is preferably 100 nm or less, and more preferably 60 nm or less. The average particle diameter of the primary particles of the silica particles is preferably 1 nm or more, and more preferably 3 nm or more. In addition, in this specification, the average particle diameter of the primary particle of the silica particle which forms the said colloidal silica can be measured by the BET method based on JISZ8830.

As a commercial product of colloidal silica containing silica particles as the primary particles, colloidal silica manufactured by Nissan Chemical Industries, Ltd. Trade names: “ST-XS” (average particle diameter 4 to 6 nm), “ST-S” (average (Particle diameter 8-11 nm), “ST-30” (average particle diameter 10-15 nm), “ST-50” (average particle diameter 20-25 nm), “ST-20L” (average particle diameter 40-50 nm), “ ST-XL "(average particle size 40 to 60 nm) and the like.

The silica particles contained in the colloidal silica may be secondary particles in which the primary particles are bonded. When the silica particles are secondary particles, examples of colloidal silica include necklace-shaped colloidal silica and chain-shaped colloidal silica.

<Necklace-shaped colloidal silica>
Necklace-shaped colloidal silica is colloidal silica containing secondary particles in which primary particles of silica particles are bonded in a ring shape. That is, the necklace-like colloidal silica is colloidal silica containing secondary particles in which primary particles of several to dozens of silica particles are aggregated in a ring shape like a pearl necklace. The secondary particles contained in the necklace-shaped colloidal silica may have a branched chain branched from the necklace-shaped ring as long as the primary particles are aggregated in a ring shape. The ring formed by the primary particles is not limited to a perfect circle or ellipse, and may be a distorted ring. The shape of the secondary particles contained in the necklace-shaped colloidal silica can be observed with an electron microscope.

The primary particles of the silica particles forming the necklace-shaped colloidal silica are not particularly limited, and conventionally known particles can be used.

The average particle diameter of primary particles forming secondary particles contained in the necklace-shaped colloidal silica is preferably 5 to 30 nm, more preferably 8 to 25 nm. By using primary particles having an average particle diameter in the above range, an antifogging composition having more excellent antifogging properties can be obtained.

The secondary particles contained in the necklace-like colloidal silica are preferably connected to primary particles and are continuous with a length of 70 to 200 nm, and more preferably are continuous with a length of 80 to 150 nm. The length of the secondary particles is the length of one round of the ring of secondary particles formed by the bonding of the primary particles. By setting the length of the secondary particles contained in the necklace-shaped colloidal silica within the above range, the antifogging composition is more excellent in antifogging properties. The length of the secondary particles contained in the necklace-shaped colloidal silica can be measured by taking a photograph with an electron microscope and measuring the length of one round of the taken secondary particles.

Commercially available products of the necklace-shaped colloidal silica include necklace-shaped colloidal silica manufactured by Nissan Chemical Industries, Ltd. Trade names: “ST-PS-S”, “ST-PS-M”, “ST-PS-SO”, “ST -PS-MO "and" ST-PS-S-AK ".

<Chained colloidal silica>
The chain colloidal silica is colloidal silica including secondary particles in which several to ten or more primary particles of silica particles are bonded in a chain, and is a colloidal silica including secondary particles having no cyclic structure. The silica particles contained in the chain colloidal silica may be linear or branched as long as the primary particles are aggregated in a chain. The shape of the chain colloidal silica can be observed with an electron microscope.

The primary particles of the silica particles forming the chain colloidal silica are not particularly limited, and conventionally known particles can be used.

The average particle diameter of the primary particles forming the secondary particles contained in the chain colloidal silica is preferably 3 to 30 nm, and more preferably 10 to 15 nm. By using the primary particles of colloidal silica having a particle diameter in the above range, an antifogging composition having more excellent transparency can be obtained.

The secondary particles contained in the above-mentioned chain colloidal silica are preferably connected to primary particles and are continuous with a length of 30 to 150 nm, and more preferably are continuous with a length of 40 to 100 nm. The length of the chain colloidal silica is the total length of the main chain length of the chain-like secondary particles formed by bonding of the primary particles and the branch chain length. By setting the length of the chain colloidal silica in the above range, an antifogging composition having more excellent transparency can be obtained. The length of the chain colloidal silica can be measured by taking a photograph with an electron microscope, measuring the length of the main chain of the taken chain colloidal silica, and the length of the branched chain and summing them up.

Examples of commercial products of the above-mentioned chain colloidal silica include “Snowtex-UP” series, which is a chain colloidal silica manufactured by Nissan Chemical Industries, Ltd. More specifically, the trade name: “ST-UP” , “ST-OUP” and the like.

As the colloidal silica, colloidal silica containing silica particles that are primary particles, necklace-shaped colloidal silica, or chain-shaped colloidal silica may be used alone, or two or more of these may be used in combination.

In the antifogging composition of the present invention, the solid content of the colloidal silica is preferably 1 to 10% by mass, preferably 2 to 8% by mass, based on 100% by mass of the antifogging composition. Is more preferable.

(Film forming aid)
The antifogging composition of the present invention contains a film-forming aid. In the antifogging composition of the present invention, the film-forming aid is a substance that promotes fusion between the binder resin particles. The film formation of the binder forms the film by disintegrating the emulsion particles and fusing the emulsion particles together, and the film forming aid facilitates the disintegration of the emulsion particles, so that the emulsions are more easily fused. By facilitating fusion, the minimum film-forming temperature can be lowered, and a flexible and strong film can be formed.

If the minimum film-forming temperature is high, a hard film is formed, which is easily broken and whitening occurs. By containing a film-forming aid, the film becomes flexible and the cracking of the film can be reduced, so that whitening can be suppressed.

(Film forming aid)
The antifogging composition of the present invention contains a film-forming aid. By containing a film-forming aid, whitening of the coating film formed by the antifogging composition of the present invention can be suppressed. Although this mechanism is not clear, it is assumed that it is as follows. That is, the film-forming aid promotes fusion between the binder resin particles. The film formation of the binder is performed by disintegrating the emulsion particles and fusing the emulsion particles together, and the film forming aid facilitates the disintegration of the emulsion particles, so that the emulsions are more easily fused. By facilitating fusion, the minimum film-forming temperature can be lowered, and a flexible and strong film can be formed.

The film forming aid contains a carbon atom. When a film-forming auxiliary containing no carbon atom is used, the anti-fogging layer formed by applying the anti-fogging composition does not have sufficient whitening resistance. The film-forming aid has a boiling point of 100 ° C. or higher. When the film-forming auxiliary has a boiling point of less than 100 ° C., the anti-fogging layer formed by applying the anti-fogging composition has insufficient whitening resistance. The boiling point of the film-forming aid is preferably 120 ° C. or higher, more preferably 190 ° C. or higher, and further preferably 250 ° C. or higher. The upper limit of the boiling point of the film-forming aid is not particularly limited, but is preferably 350 ° C. or lower, more preferably 300 ° C. or lower, and further preferably 280 ° C. or lower. By setting the boiling point of the film-forming aid in the above range, the anti-fogging layer formed by applying the anti-fogging composition is further improved in whitening resistance.

In this specification, the boiling point of the film-forming aid is a value measured under conditions of 1 atm using FP81HT / FP81C (model number, manufactured by METTLER TOLEDO Co., Ltd.). Confirmation of containing carbon atoms is performed by measuring the organic matter in the antifogging composition as the total amount of organic carbon (carbon content) by using TOC (total organic carbon meter). Can do.

Examples of the film forming aid include compounds having an ether bond or an ester bond. For example, phthalic acid ester, adipic acid ester, trimellitic acid ester, phosphoric acid ester, citric acid ester, polyester, epoxidized vegetable oil, sebacin Acid ester, azelaic acid ester, maleic acid ester, benzoic acid ester, texanol, cellosulp, cellosorp acetate, butyl cellosorp, carbitol, carbitol acetate, butyl carbitol, butyl carbitol acetate and the like can be used. Among these, ethylene glycol diacetate, texanol, dibutyl phthalate or propylene glycol monomethyl ether is preferable, and texanol is more preferable because it shows more excellent whitening resistance. These can be used alone or in combination of two or more, but when two or more are used in combination, it is preferable to combine texanol and another film-forming aid.

In the antifogging composition of the present invention, the content of the film-forming auxiliary (the total amount when two or more types are used in combination) is 0.1 to 10.0 based on 100% by mass of the antifogging composition. The mass is preferably 0.5% by mass, and more preferably 0.5 to 5.0% by mass. By setting the content of the film-forming auxiliary in the above range, the antifogging layer can exhibit more excellent anti-folding whitening property while maintaining the antifogging property and the long-term sustainability of the antifogging performance.

(Surfactant)
The antifogging composition of the present invention contains a surfactant. Examples of the surfactant include polyhydric alcohol partial esters composed of polyhydric alcohols and higher fatty acids, including various known nonionic surfactants, anionic surfactants, and cationic surfactants. Of these, silicone-based surfactants and fluorine-based surfactants are suitable. Among these, a non-ionic surfactant or a silicone-based interface can be imparted with high leveling properties to the antifogging composition and can impart high antifogging properties to the antifogging layer formed using the antifogging composition. An activator is preferred. These may be used singly or in combination of two or more, but when used in combination, it is preferable to include at least a nonionic surfactant or a silicone-based surfactant. .

Specific examples of the nonionic surfactant include, for example, sorbitan such as sorbitan monostearate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan / alkylene glycol condensate and fatty acid ester. Surfactants: glycerol monopalmitate, glycerol monostearate, glycerol monolaurate, diglycerol monopalmitate, glycerol dipalmitate, glycerol distearate, diglycerol monopalmitate monostearate, triglycerol monostearate Glycerin-based surfactants such as rate, triglycerin distearate or their alkylene oxide adducts; polyethylene glycol monostearate, polyethylene glycol monopalmitate Polyethylene glycol surfactants such as polyethylene glycol alkylphenyl ether; trimethylolpropane surfactants such as trimethylolpropane monostearate; pentaerythritol surfactants such as pentaerythritol monopalmitate and pentaerythritol monostearate An alkylene oxide adduct of alkylphenol; an ester of a sorbitan / glycerin condensate and a fatty acid; an ester of a sorbitan / alkylene glycol condensate and a fatty acid; diglycerin dioleate sodium lauryl sulfate; sodium dodecylbenzenesulfonate; cetyltrimethylammonium Chloride; dodecylamine hydrochloride; lauric acid laurylamide ethyl phosphate; triethylcetylammonium salt Iodide; oleyl amino diethylamine hydrochloride; dodecyl pyridinium salts and isomers thereof; those containing acetylenic dialcohols and alkylene oxide adducts thereof and the like. Among these, acetylene dialcohol and its alkylene oxide adduct are preferable in that the surface tension can be particularly reduced.

Specific examples of the silicone surfactant include, for example, dimethyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, amino modified silicone oil, alkyl modified silicone oil, phenyl modified silicone oil, carboxyl modified silicone oil, high grade Fatty acid-modified silicone oil, epoxy-modified silicone oil, vinyl group-containing silicone oil, alcohol-modified silicone oil, polyether-modified silicone oil, alkyl / polyether-modified silicone oil, fluorine-modified silicone oil, alkoxysilane, reactive siloxane oligomer, and these Examples include silicone elastomers having the following structure. These may be used alone or in combination of two or more. Among these, polyether-modified silicone oil is preferable in that high leveling property can be imparted to the antifogging composition and high antifogging property can be imparted to the antifogging layer formed using the antifogging composition.

In the antifogging composition of the present invention, the content of the surfactant (when used in combination of two or more) is a total of 100 parts by mass of the solid content of the colloidal silica and the solid content of the binder resin. The content is preferably 2 to 30 parts by mass, and more preferably 5 to 15 parts by mass. By making content of surfactant into the above-mentioned range, transparency of an antifogging composition can improve more and can show the outstanding leveling property.

The colloidal silica, binder resin, film-forming aid, and surfactant are usually a commercially available product itself, or a product dispersed in a dispersion medium such as water, or a commercially available powder or the like is dispersed in water or the like. Any of those dispersed in a medium may be used.

The antifogging composition of the present invention may contain a dispersion medium. The antifogging composition of the present invention is a form in which the colloidal silica, binder resin, film-forming aid, surfactant, and other components described later as necessary are dispersed in a dispersion medium. Also good. Examples of the dispersion medium include water-miscible solvents including water. Specifically, water such as tap water, deionized water, and pure water; monohydric alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; Polyhydric alcohols such as ethylene glycol, diethylene glycol and glycerin; cyclic alcohols such as benzyl alcohol; cellosolve acetates; ketones and the like. These dispersion media are desirably used by mixing with water.

(Other ingredients)
If the antifogging composition of the present invention contains the colloidal silica, binder resin, film-forming aid and surfactant, further, an inorganic filler, an ultraviolet absorber, a light stabilizer, an oxidation agent, if necessary. Other components such as an inhibitor, a lubricant, a heat stabilizer, and an antistatic agent can be blended in usual amounts.

Examples of the inorganic filler include various commonly used compounds, and oxides such as calcium, magnesium, and aluminum, hydroxides, carbonates, silicates, and composites thereof are particularly preferable. Specifically, clay (kaolin clay, soft clay, hard clay, calcined clay, waxy clay), talc (talc, French chalk), asbestos (chrysotile, crocidolide, ammonite, anthroferrite, tremolite, actinolite), mica, Silicates such as bentonite, sericite, zeolite, attapulgite, pumice powder, slate powder, feldspar powder, wollastonite, froth earth, tripolystone, meteorite, hydrous or anhydrous precipitated calcium silicate, magnesium silicate; Hydrotalcites (hydrous or anhydrous aluminum / magnesium basic carbonate, sulfate, nitrate, phosphate, aluminum / zinc basic carbonate, sulfate, nitrate, phosphate); antimony trioxide, magnesium oxide, Titanium dioxide, zinc oxide, aluminum oxide Oxides such as (hydrous or anhydrous); calcium carbonate (heavy coal, light coal, colloidal coal or sedimentary coal cal, pepper, chalk, witching, arareite), magnesium carbonate (sedimentation, moisture and Carbonates such as anhydrous); barium sulfate (barite powder), precipitated barium sulfate, calcium sulfate (stone, soft stone, or precipitated), sulfates such as branfix; lime (aluminum hydroxide), magnesium hydroxide, etc. Consisting of carbon atoms (furnace, channel, lamp, thermal, acetylene), graphite, carbon fiber, carbon sphere, anthracite powder, etc .; copper, aluminum, bronze, lead, zinc, steel, etc. Metal powder, fiber, whisker or wire; glass such as fiber, sphere, foam, fly ash sphere, shirasu balloon Quality; barium ferrite; magnetite; molybdenum disulfide; potassium titanate, and the like. These may be used alone or in combination of two or more.

Examples of the UV absorber include UV absorbers such as benzotriazole, benzoate, benzophenone, cyanoacrylate, and phenyl salicylate. Among these, benzophenone ultraviolet absorbers and / or benzotriazole ultraviolet absorbers are preferably used.

As the light stabilizer, various compounds usually blended in the antifogging composition can be used. Specifically, for example, 4-acetoxy-2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidine) adipate, tris (2,2,6, And hindered amine compounds such as 6-tetramethyl-4-piperidyl) benzene-1,3,5-tricarboxylate.

Examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol, 2,2′-methylenebis (6-tert-butyl-4-ethylphenol), dilaurylthiodipropionate, and the like. .

Examples of lubricants or heat stabilizers include polyethylene wax, liquid paraffin, bisamide, stearic acid, zinc stearate, aliphatic alcohol, calcium stearate, barium stearate, barium ricinoleate, dibutyltin dilaurate, dibutyltin dimaleate, and organic phosphoric acid. Examples thereof include metal salts, organic phosphite compounds, phenols, β-diketone compounds and the like.

The above-mentioned other components can be used alone or in combination of two or more. The blending amount of each of the other components is preferably in a range that does not deteriorate the performance of the antifogging composition. Usually, the solid content of colloidal silica, the solid content of the binder resin, the film-forming aid, and the surface activity. The total of the agent and the dispersion medium can be selected in a range of 10 parts by mass or less with 100 parts by mass as the total.

The method for producing the antifogging composition of the present invention is not particularly limited, and a conventionally known method can be used. For example, a method of adding colloidal silica, a binder resin, a film-forming aid, a surfactant, and other components as required, and stirring and mixing with a stirring device such as a homogenizer can be mentioned.

2. Antifogging layer An antifogging layer can be formed by applying the antifogging composition of the present invention to the surface of a synthetic resin film or the like and drying it. The thickness of the antifogging layer is preferably about 0.1 to 3.0 μm, more preferably about 0.5 to 1.0 μm, as the solid content of the antifogging composition after coating.

The method for applying the antifogging composition to the surface of a synthetic resin film is not particularly limited. Known coating methods such as knife coating and brush coating may be mentioned. The antifogging composition of the present invention exhibits good leveling properties at the time of coating, and by drying the applied antifogging composition, the antifogging composition has excellent antifogging properties, antibacterial whitening properties and scratch resistance. A layer can be formed. Any drying method of natural drying or forced drying may be adopted as the drying method. When employing the forced drying method, the drying temperature is preferably 30 to 120 ° C, more preferably 50 to 100 ° C. Moreover, heat drying is mentioned as forced drying, As said heat drying, a hot-air drying method, an infrared drying method, a far-infrared drying method, etc. are mentioned.

The contact angle of the antifogging layer formed from the antifogging composition of the present invention is preferably 50 ° or less. By setting the contact angle of the antifogging layer to 50 ° or less, the antifogging property of the antifogging film described later is particularly good. In addition, the said contact angle is the value measured on the measurement conditions computed by the measuring method based on JISR3257, the capacity | capacitance of water droplets 3 microliters, and the (theta) / 2 method.

3. Antifogging film The present invention is also an antifogging film in which the antifogging layer is formed on at least one surface of a synthetic resin film. By forming the anti-fogging layer on the synthetic resin film, an anti-fogging film having excellent anti-fogging and anti-fogging properties and anti-fogging performance and long-lasting anti-fogging performance and excellent transparency and whitening resistance and scratch resistance is obtained. Obtainable.

The resin for forming the synthetic resin film is not particularly limited, but vinyl chloride resin; polyethylene (low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE)), polypropylene, ethylene -Polyolefin resins such as propylene copolymer and ethylene-butene copolymer; ethylene-vinyl acetate copolymer; ethylene-acrylic acid copolymer. In particular, when used as an agricultural film, it is preferable to use a polyolefin resin or an ethylene-vinyl acetate copolymer from the viewpoint of transparency, weather resistance, and economy. These may be used alone or in combination of two or more.

The synthetic resin film may contain an infrared absorber, a light stabilizer, an ultraviolet absorber, an antioxidant, an antiblocking agent, a slip agent, a surfactant, a pigment, and the like.

Examples of the infrared absorber include inorganic fillers.

As the light stabilizer, the same light stabilizer as that used in the antifogging composition can be used.

The application method of the antifogging composition, the application conditions, the thickness of the antifogging layer, and the like when forming the antifogging layer on the synthetic resin film may be the same as described in the antifogging layer.

When the adhesion between the synthetic resin film and the antifogging layer is not sufficient, the surface of the synthetic resin film may be pretreated such as plasma discharge treatment or corona discharge treatment.

The antifogging film is preferably an agricultural film. The anti-fogging film has excellent anti-fogging properties and anti-fogging performance for a long period of time, and has excellent transparency and excellent resistance to whitening and scratching. Suitable for use in etc.

When the antifogging film is used as an agricultural film and is spread on a house, it is preferably spread so that the antifogging layer is formed on the inner surface of the house. By forming the anti-fogging layer on the inner surface of the house, it is possible to suppress the water droplets adhering to the inner surface of the anti-fogging film from falling on the cultivated crop.

The antifogging film may have an antifogging layer formed on both surfaces of the synthetic resin film. When an antifogging film having an antifogging layer formed on both sides of a synthetic resin film is used as an agricultural film and spread on a house, the antifogging layer formed on the inner surface of the house as described above causes water droplets to be formed. In addition to being able to suppress falling to the cultivated crop, further, dirt on the outer surface of the house can be suppressed by the antifogging layer formed on the outer surface of the house.

Hereinafter, examples of the present invention will be described. The present invention is not limited to the following examples.

(Preparation of synthetic resin film)
Linear low density polyethylene (LLDPE: trade name “Elite 5100” manufactured by Dow Chemical Co., Ltd., density 0.920 g / cm ³ , MFR 0.8 g / 10 min), infrared absorber (inorganic filler: manufactured by Kyowa Chemical Industry Co., Ltd.) “DHT-4A”) and a light stabilizer (HALS: trade name “TINUVIN783” manufactured by BASF Japan) are mixed in the formulation shown in Table 1, and a single-layer inflation molding apparatus (manufactured by HAAKE) equipped with a 25 mmφ die is used. A synthetic resin film having a thickness of 150 μm was prepared by extrusion molding under conditions of a molding temperature of 170 ° C. and a blow ratio of 2.0.

Examples 1 to 15 and Comparative Examples 1 to 4
According to the formulation shown in Table 1, the binder resin shown in Table 2, the colloidal silica shown in Table 3, the surfactant shown in Table 4, and the film-forming aid shown in Table 5 were mixed with deionized water as a dispersion medium. Then, an antifogging composition was prepared by stirring.

Binder resins A to D were prepared as follows. That is, 2 parts by mass of polyoxyethylene lauryl ether and 80 parts by mass of water were charged into a four-necked flask and heated to 60 ° C. under a nitrogen gas stream. While maintaining the reaction temperature at 60 to 70 ° C., 0.5 parts by mass of ammonium persulfate was added, and 100 parts by mass of a mixture prepared by mixing the monomers according to the formulation shown in Table 2 was added dropwise over 3 hours. did. After completion of the dropping, the temperature was maintained at 60 to 70 ° C. for 2 hours and then cooled to obtain a dispersion liquid of the binder resin in the dispersion medium. In Table 1, the compounding amounts of the colloidal silica and the binder resin in the antifogging composition indicate the compounding amounts in solid content. In Table 2, the composition of the binder resin indicates the composition in solid content, and the binder resin is used in an emulsion state in which the solid content is dispersed in water.

The antifogging composition prepared as described above was applied onto a synthetic resin film using a # 5 bar coater. The anti-fogging film is obtained by holding the synthetic resin film coated with the anti-fogging composition in an oven at 70 ° C. for 1 minute and volatilizing the liquid dispersion medium of the anti-fogging composition to form an anti-fogging layer. Was prepared. The film thickness of the antifogging layer forming the antifogging film was about 0.8 μm.

The following evaluation was performed on the antifogging compositions and antifogging films of Examples 1 to 15 and Comparative Examples 1 to 4.

<Transparency test> (Haze measurement)
Haze was measured using Nippon Denshoku Industries Co., Ltd .: MDH2000 by a measuring method based on JIS K7105, and evaluated according to the following criteria.
◎: 15% or less ○: Over 15%, 17% or less Δ: Over 17%, 25% or less ×: Over 25%

<Scratch resistance test> (Colloidal silica remaining rate)
The amount of colloidal silica present in the antifogging layer of the test piece (the amount of colloidal silica before peeling) was measured with a fluorescent X-ray apparatus. 0.2 mg of deionized water was sprayed on the anti-fogging layer. The anti-fogging layer sprayed with deionized water was rubbed 100 times with kraft paper under a load of 100 g, and the amount of colloidal silica remaining (the amount of colloidal silica after peeling) was measured with a fluorescent X-ray apparatus. The colloidal silica residual rate was calculated based on the following formula.
[Colloidal silica remaining rate (%)] = ([Amount of colloidal silica after peeling] / [Amount of colloidal silica before peeling]) × 100
Based on the calculated colloidal silica residual ratio, evaluation was performed according to the following criteria.
◎: Over 84% ○: Over 74%, 84% or less △: Over 49%, 74% or less ×: 49% or less

<Folding whitening resistance test>
Measures the haze using Nippon Denshoku Kogyo Co., Ltd .: MDH2000 (haze value before fold) by the measurement method based on JIS K7105, and measures the haze after attaching two folds in the MD and TD directions. (Haze value after folding) and the folding whitening resistance were calculated based on the following formula.
[Folding resistance to whitening (%)] = ([Haze value after folding (%)] − [Haze value before folding (%)])
The calculated folding whitening resistance was evaluated according to the following criteria.
◎: 5% or less ○: Over 5%, 7% or less △: Over 7%, 9% or less ×: Over 9%

<Anti-fogging test> (Anti-fogging property (1): Initial anti-fogging property)
The test piece was installed at an angle of 30 ° with respect to the water surface so that the antifogging layer of the test piece was on the water tank side at the top of the water tank containing water. The distance between the water surface in the water tank and the lower end of the test piece was 30 cm. In this state, the temperature was maintained under the conditions of an outside air temperature of 20 ° C. and a water temperature of 40 ° C., and the time until water droplets adhering to the surface of the test piece flowed was measured and evaluated according to the following criteria.
◎: 15 minutes or less ○: 15 minutes or more, 25 minutes or less △: 25 minutes or more, 35 minutes or less ×: 35 minutes or less

<Anti-fogging property test> (Anti-fogging property (2): Long-term sustainability of anti-fogging performance)
The test piece was installed at an angle of 30 ° with respect to the water surface so that the antifogging layer of the test piece was on the water tank side at the top of the water tank containing water. The distance between the water surface in the water tank and the lower end of the test piece was 30 cm. In this state, the area where water droplets are attached to the surface of the test piece is kept for 120 days under conditions of an outside air temperature of 20 ° C. and a water temperature of 40 ° C., 5 days, 10 days, 20 days, 30 days, 40 days, The measurement was performed at the time point and evaluated according to the following criteria.
◯: Water drop adhesion area is 10% or less of test piece area Δ: Water drop adhesion area exceeds 10% of test piece area, 50% or less ×: Water drop adhesion area is 50% of test piece area Exceed

<Anti-blocking test>
The inclination angle was measured under the following measurement conditions by a method based on JIS P8147 using a tester industry: AB-502 friction angle measuring machine, and evaluated according to the following criteria. The measurement conditions are as follows. That is, both ends of a 13 cm × 20 cm test piece were fixed with tape so that the anti-fogging layer was on the upper side. Further, a 10 cm × 11 cm test piece was attached to a 1000 mg (6.3 cm × 10.2 cm) sliding piece with a tape so that the antifogging layer was located below. The antifogging layers of the two test pieces were set so as to rub against each other, and the inclination angle at which the sliding pieces began to slide was measured.
A: 25 ° or less ○: Over 25 °, 35 ° or less Δ: Over 35 °, 55 ° or less x: Over 55 ° The results are shown in Table 1.

As is clear from Table 1, in Examples 1 to 15, the antifogging composition contains colloidal silica, a binder resin, a film-forming aid, and a surfactant, and (1) the solid content mass of the colloidal silica (Ma ) And the solid content mass (Mb) of the binder resin is 0.5 to 5.0, and (2) the film-forming aid contains carbon atoms and has a boiling point. It is 100 degreeC or more, (3) Mass ratio of the sum (Ma + Mb) of solid content mass (Ma) of colloidal silica and solid content mass (Mb) of the said binder resin, and the mass (Mc) of the said film-forming aid Since (Ma + Mb) / (Mc) is 1.0 to 16.0, it has excellent antifogging and antifogging performance for a long period of time and transparency, and is formed by applying an antifogging composition. The anti-fogging layer exhibited excellent folding whitening resistance and scratch resistance.

On the other hand, from the result of Comparative Example 1, when (Ma + Mb) / (Mc) exceeds 16.0, the amount of the film-forming aid is small relative to the sum of the solid content mass of the colloidal silica and the solid content mass of the binder resin. It was found that the fusion between the binder resin particles was not promoted and the whitening resistance was poor.

Moreover, from the result of Comparative Example 2, when (Ma + Mb) / (Mc) is less than 1.0, the total amount of the solid content mass of the colloidal silica and the solid content mass of the binder resin with respect to the amount of the film-forming aid is It was found that since the amount is small, the dropability is lowered and the antifogging property is inferior, and the amount of the film-forming aid is large, so that the transparency is inferior.

From the result of Comparative Example 3, when (Ma / Mb) exceeds 5.0, the solid content mass of the colloidal silica with respect to the solid content mass of the binder resin is large, so that the transparency is lowered and the colloidal silica is easily dropped. It was found to be inferior in scratch resistance.

Moreover, from the result of Comparative Example 4, when (Ma / Mb) is less than 0.5, the solid content mass of colloidal silica relative to the solid content mass of the binder resin is small, so that the antifogging property can be sufficiently exhibited. In addition, it has been found that the long-term sustainability of the antifogging performance is inferior.

DESCRIPTION OF SYMBOLS 1 ... Anti-fogging film, 2 ... Synthetic resin film, 3 ... Anti-fogging layer

Claims

An antifogging composition containing colloidal silica, a binder resin, a film-forming aid and a surfactant,
(1) The mass ratio (Ma / Mb) between the solid content mass (Ma) of the colloidal silica and the solid content mass (Mb) of the binder resin is 0.5 to 5.0,
(2) The film-forming aid contains carbon atoms and has a boiling point of 100 ° C or higher.
(3) The mass ratio (Ma + Mb) / (total mass (Mb) of the colloidal silica and the total mass (Mb) of the binder resin and the mass (Mc) of the film-forming aid. Mc) is 1.0-16.0,
An antifogging composition characterized by the above.
The antifogging composition according to claim 1, wherein the binder resin has a glass transition point of 0 to 100 ° C.
The antifogging composition according to claim 1 or 2, wherein the content of the film-forming auxiliary is 0.1 to 10.0% by mass with respect to 100% by mass of the antifogging composition.
An antifogging film having an antifogging layer formed of the antifogging composition according to any one of claims 1 to 3 on at least one surface of the synthetic resin film.