CN113045975B

CN113045975B - Antifogging agent composition and antifogging product

Info

Publication number: CN113045975B
Application number: CN202011412848.7A
Authority: CN
Inventors: 木谷直
Original assignee: NOF Corp
Current assignee: NOF Corp
Priority date: 2019-12-26
Filing date: 2020-12-04
Publication date: 2023-05-12
Anticipated expiration: 2040-12-04
Also published as: TW202124665A; KR20210083177A; JP2021105073A; CN113045975A; JP7360090B2

Abstract

An antifogging agent composition comprising a polyisocyanate (A), a polyol (B), a surfactant, and a solvent, wherein (A) is a polyisocyanate compound selected from at least one of the group consisting of a diisocyanate and a derivative thereof, (B) comprises a polyether polyol (B1) and a polycaprolactone polyol (B2), and in a chromatogram obtained by gel permeation chromatography, (B1) has a molecular weight of 300 to 1,800 at the maximum refractive index intensity point, and the mass ratio of (B1) to (B2) is 5 to 15, wherein S1 is the peak area from the elution start point to the elution time point corresponding to the maximum refractive index intensity point, and S2 is the peak area from the elution time point corresponding to the maximum refractive index intensity point to the elution end point, and S2/S1 is 1.5 to 2.0. The antifogging agent composition can form an antifogging film with excellent transparency and touch.

Description

Antifogging agent composition and antifogging product

Technical Field

The invention relates to an antifogging agent composition and an antifogging product.

Background

Condensation may occur on the surface of an article in places where moisture is large. In particular, in the case of transparent articles such as window glass and lenses and reflective articles such as mirrors, if the progress of light is blocked due to the occurrence of fog caused by condensation, it is difficult to provide a normal view to the user. Therefore, such an article preferably has a function of preventing fogging.

For example, an article using a heating wire for preventing fogging is known. A heating wire is wound around the surface of the article, and when the heating wire generates heat by energization, the temperature of the surface of the article increases. This makes it difficult for dew condensation to occur on the surface of the article. However, since a power source is required for driving such an article, the structure is complicated and running costs are required. Therefore, a method capable of simply preventing fog is required.

Patent documents 1 and 2 disclose an antifogging film provided on the surface of an article. By coating the surface of the article with a hydrophilic coating film, fogging on the surface of the article can be prevented simply and effectively.

Prior art literature

Patent literature

Patent document 1: japanese patent application laid-open No. 2018-150471

Patent document 2: japanese patent application laid-open No. 2018-165305

Disclosure of Invention

Technical problem to be solved by the invention

However, the antifogging films described in patent documents 1 and 2 exhibit tackiness of the antifogging film in a high humidity environment, and have a problem of reduced feeling of use for users. Further, there is a need in the market for an antifogging film having a coating film appearance excellent in transparency.

The present invention has been made in view of the above circumstances, and an object thereof is to provide an antifogging agent composition capable of forming an antifogging film excellent in transparency and touch.

Technical means for solving the technical problems

Specifically, the present invention relates to an antifogging agent composition comprising a polyisocyanate (a) which is a polyisocyanate compound selected from at least one of the group consisting of a diisocyanate and a derivative thereof, a polyol (B) which comprises a polyether polyol (B1) and a polycaprolactone polyol (B2), wherein the molecular weight of the polyether polyol (B1) at the point of maximum refractive index intensity is 300 to 1,800, and the peak area from the elution start point to the point of elution time corresponding to the point of maximum refractive index intensity is S1, and the peak area from the point of elution time corresponding to the point of maximum refractive index intensity to the elution end point is S2, and wherein the ratio of S2/S1 to the mass of the polyether polyol (B1) to the mass of the polycaprolactone polyol (B2) is 1.5 to 2.0 in the chromatogram obtained by gel permeation chromatography using a differential refractive index detector is not less than 15 ((B1) to not more than 15).

Furthermore, the present invention relates to an antifogging product having an antifogging film formed from the antifogging composition on a substrate.

Effects of the invention

The action mechanism of the effect of the antifogging agent composition of the present invention is not yet explained in detail, but is presumed as follows. However, the understanding of the present invention is not limited by this mechanism of action.

The antifogging agent composition of the present invention contains a polyisocyanate (a), a polyol (B) containing a polyether polyol (B1) and a polycaprolactone polyol (B2) having a specific molecular weight distribution, and a mass ratio ((B1)/(B2)) of the polyether polyol (B1) to the polycaprolactone polyol (B2) is a specific ratio, and thus it is presumed that the balance between hydrophilicity and hydrophobicity of a polyurethane resin formed from the polyisocyanate (a) and the polyol (B) can be optimized, and therefore, an antifogging film formed from the antifogging agent composition of the present invention has excellent transparency and touch feeling.

Drawings

FIG. 1 is a schematic diagram of a chromatogram of the polyether polyol (b 1) obtained by gel permeation chromatography.

Detailed Description

The antifogging agent composition of the present invention contains a polyisocyanate (A), a polyol (B), a surfactant and a solvent.

< polyisocyanate (A) >

The polyisocyanate (a) of the present invention is a polyisocyanate compound of at least one selected from the group consisting of diisocyanate and derivatives thereof. Examples of the polyisocyanate include aliphatic diisocyanates such as 1, 6-hexamethylene diisocyanate; alicyclic diisocyanates such as 1, 3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, and 4,4' -diisocyanate dicyclohexylmethane; aromatic diisocyanates such as xylylene diisocyanate, toluene-2, 6-diisocyanate, and diphenylmethane diisocyanate. Examples of the derivative of the diisocyanate include a compound synthesized from the aliphatic diisocyanate, alicyclic diisocyanate and/or aromatic diisocyanate as a starting material, a biuret, an adduct with trimethylolpropane, an isocyanurate, an allophanate, and other derivatives of aliphatic diisocyanate, an alicyclic diisocyanate, and an aromatic diisocyanate. The polyisocyanate (a) may be used alone or in combination of two or more.

The polyisocyanate (a) is preferably an aliphatic diisocyanate derivative, an alicyclic diisocyanate derivative or an aromatic diisocyanate derivative, more preferably an alicyclic diisocyanate derivative, even more preferably a 1, 3-bis (isocyanatomethyl) cyclohexane derivative or an isophorone diisocyanate derivative, from the viewpoint of improving the crosslinking density of the antifogging film and improving the strength of the antifogging film. Furthermore, the derivative is preferably an adduct with trimethylolpropane. In particular, from the viewpoint of improving the strength and antifogging property of the antifogging film, it is preferable to use the polyisocyanate (a) as an adduct of 1, 3-bis (isocyanatomethyl) cyclohexane and trimethylolpropane, and an adduct of isophorone diisocyanate and trimethylolpropane at the same time.

Examples of the polyisocyanate (A) that are commercially available include trimethylolpropane adducts of isophorone diisocyanate (manufactured by SUMIKA BAYER URETHANE KK, product name: desmodur Z4470 BA), trimethylolpropane adducts of 1, 3-bis (isocyanatomethyl) cyclohexane (manufactured by Mitsui Chemicals, inc., product name: takenate D-120N), isocyanurate bodies of 1, 3-bis (isocyanatomethyl) cyclohexane (manufactured by Mitsui Chemicals, inc., product name: takenate D-127N), trimethylolpropane adducts of isophorone diisocyanate (manufactured by Mitsui Chemicals, inc., product name: takenate D-140N), and the like.

< polyol (B) >

The polyol (B) of the present invention contains a polyether polyol (B1) and a polycaprolactone polyol (B2).

< polyether polyol (b 1) >)

In a chromatogram obtained by gel permeation chromatography using a differential refractive index detector, the molecular weight of the polyether polyol (b 1) at the point of maximum refractive index intensity is 300 to 1,800, and when the peak area from the elution start point to the elution time point corresponding to the point of maximum refractive index intensity is S1 and the peak area from the elution time point corresponding to the point of maximum refractive index intensity to the elution end point is S2, the peak area ratio (S2/S1) is 1.5 to 2.0.

The peak area ratio (S2/S1) is a molecular weight distribution determined by a chromatogram obtained by using a differential refractive index detector in Gel Permeation Chromatography (GPC). The chromatogram is a graph showing the relationship between refractive index intensity and elution time.

Here, fig. 1 is a schematic diagram of a chromatogram obtained by gel permeation chromatography of the polyether polyol (b 1), in which the horizontal axis represents elution time and the vertical axis represents refractive index intensity obtained by using a differential refractive index detector.

When a sample solution is injected into Gel Permeation Chromatography (GPC) and developed, elution starts from the molecule with the highest molecular weight, and the elution profile increases with increasing refractive index intensity. Then, after passing through the refractive index intensity maximum point K where the refractive index intensity is maximum, the elution curve decreases.

The refractive index maximum point of the chromatogram of the polyether polyol (b 1) in the gel permeation chromatograph is usually one, and is a unimodal peak. In this case, a peak due to a developing agent or the like used in the gel permeation chromatography and a false peak due to a baseline fluctuation of a column or a device used are not included.

Here, the peak area from the elution start point O to the elution time point C corresponding to the refractive index intensity maximum point K is set to S1. The elution time point C is located at the intersection of the base line B and the perpendicular line P drawn from the refractive index intensity maximum point K to the base line B. The peak area from the elution time point C to the elution end point E was set to S2. The peak area S1 corresponds to the amount of the component on the relatively high molecular weight side, and the peak area S2 corresponds to the amount of the component on the relatively low molecular weight side. In addition, an S2/S1 of 1.5 to 2.0 means that the component on the low molecular weight side is somewhat more than the component on the high molecular weight side, and the molecular weight balance is favorable for the touch of the antifogging film.

As a Gel Permeation Chromatograph (GPC) for obtaining the peak area ratio (S2/S1), TOSOH HLC-8320GPC was used as a GPC system, and 2 pieces of TOSOH TSKgel Super Multipore HZ-M and 1 piece of TOSOH TSKgel Super H-RC were installed in series as a chromatographic column. The column temperature was set to 40 ℃, and polystyrene was used as a standard, and tetrahydrofuran was used as a developing agent. The developing agent was flowed at a flow rate of 1ml/min, and 0.1ml of a sample solution having a sample concentration of 0.5 mass% was injected. The molecular weight at the maximum point of the refractive index intensity is a molecular weight converted from the number average molecular weight of standard polystyrene, which is obtained based on a chromatogram expressed by the refractive index intensity and elution time obtained by using the EcoSEC-Work Station GPC calculation program. On the other hand, the number average molecular weight of the polyether polyol (b 1) can be calculated under the above conditions.

In the chromatogram, the peak area ratio S2/S1 is 1.5 to 2.0, but the molecular weight at the maximum refractive index intensity point of the polyether polyol (b 1) is less than 300, and the compatibility with the polyisocyanate (A) compound is lowered. From this point of view, the molecular weight of the polyether polyol (b 1) at the point of maximum refractive index strength is preferably 400 or more, more preferably 500 or more, and still more preferably 700 or more. Further, the peak area ratio S2/S1 is preferably 1.5 to 2.0, but when the molecular weight at the point of maximum refractive index strength of the polyether polyol (b 1) is more than 1,800, the strength of the antifogging film tends to be lowered, and therefore the molecular weight at the point of maximum refractive index strength of the polyether polyol (b 1) is preferably 1,500 or less, more preferably 1,200 or less.

In the chromatogram, the molecular weight at the maximum refractive index intensity point of the polyether polyol (b 1) is 300 to 1,800, but the transparency of the antifogging film is lowered when the peak area S2/S1 is more than 2.0 (when the proportion of the polyether polyol having a small molecular weight is high). Further, when the peak area S2/S1 is less than 1.5 (when the proportion of the polyether polyol having a large molecular weight is high), the touch feeling of the antifogging film is lowered, and the tackiness of the antifogging film is exhibited.

Examples of the polyether polyol (b 1) include polymers obtained by adding at least one selected from the group consisting of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran to polyfunctional alcohols such as glycerin and pentaerythritol. In this addition reaction, the reaction temperature, the moisture content in the reaction system, and the like are important factors for changing the molecular weight distribution. The alkylene oxide preferably contains ethylene oxide, and more preferably only ethylene oxide is added. The polyether polyol (b 1) may be used alone or in combination of two or more.

Examples of the polyether polyol (b 1) include polyethylene glycol, polypropylene glycol polyethylene glycol/polypropylene glycol copolymer polyol, polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene trimethylolpropane, polyoxyethylene diglycerol ether (polyoxydiglyceryl ether), pentaerythritol polyoxyethylene ether, polyoxyethylene polyoxypropylene pentaerythritol ether, and the like. In particular, from the viewpoint of improving the hardness and antifogging property of the antifogging film, the polyether polyol (b 1) is preferably polyoxyethylene glyceryl ether.

< polycaprolactone polyol (b 2) >)

The polycaprolactone polyol (b 2) can improve the strength of the antifogging film. The polycaprolactone polyol (b 2) may be used alone or in combination of two or more. The number average molecular weight can be calculated from the hydroxyl value of the polycaprolactone polyol (b 2).

The polycaprolactone polyol (b 2) is a compound obtained by ring-opening polymerization of a polyfunctional alcohol such as glycerin, pentaerythritol, etc. with epsilon-caprolactone, and examples thereof include polycaprolactone diol, polycaprolactone triol, polycaprolactone tetrol, polycaprolactone hexaol, etc.

The number average molecular weight of the polycaprolactone polyol (b 2) is preferably 300 or more, more preferably 400 or more, further preferably 450 or more, from the viewpoint of improving the compatibility with each component in the urethane (urethane) coating composition, and the number average molecular weight of the polycaprolactone polyol (b 2) is preferably 1,800 or less, more preferably 1,500 or less, further preferably 1,000 or less, from the viewpoint of improving the scratch resistance of the antifogging film. The number of hydroxyl groups per molecule of the polycaprolactone polyol (b 2) is preferably 3 or more from the viewpoint of improving the strength of the antifogging film, and the number of hydroxyl groups per molecule of the polycaprolactone polyol (b 2) is preferably 6 or less from the viewpoint of improving the compatibility with each component in the urethane coating composition.

The polyol (B) may contain a polycarbonate polyol, a polyester polyol, an acrylic polyol, or the like.

< surfactant >

The surfactant of the present invention is a component for improving the antifogging property by reducing the surface tension of moisture adhering to the surface of the antifogging film and forming a water film on the surface of the antifogging film.

The surfactant may be any conventionally known surfactant, and examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, and zwitterionic surfactants. Among them, the anionic surfactant is preferable from the viewpoint of affinity with the polyurethane resin formed from the polyisocyanate (a) and the polyol (B). The surfactant may be used alone or in combination of two or more.

Examples of the anionic surfactant include fatty acid salts such as sodium oleate and potassium oleate; higher alcohol sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate and sodium alkylnaphthalene sulfonate, and alkylnaphthalene sulfonates; and polyoxyethylene sulfate such as naphthalene sulfonic acid formaldehyde condensate, dialkyl sulfosuccinate, dialkyl phosphate, and sodium polyoxyethylene alkylphenyl ether sulfate. Further, compounds in which part of hydrogen atoms of hydrocarbon residues of these surfactants are replaced with fluorine atoms can also be used.

< solvent >

The solvent of the present invention is not particularly limited as long as it is an organic solvent capable of dissolving or dispersing the components such as the polyisocyanate (a) and the polyol (B) and volatilizing at the drying temperature, and is used for improving the viscosity and the coatability of the antifogging agent composition and the smoothness of the antifogging film.

Examples of the solvent include alcohol solvents, carboxylic acid ester solvents, ketone solvents, amide solvents, ether solvents, aliphatic and aromatic hydrocarbon solvents, and the like. Examples of the alcohol solvent include methanol, isopropanol, n-butanol, diacetone alcohol, 2-methoxyethanol (methyl cellosolve), 2-ethoxyethanol (ethyl cellosolve), 2-butoxyethanol (butyl cellosolve), t-amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, and the like. Examples of the carboxylic acid ester solvents include ethyl acetate, n-propyl acetate, butyl acetate, and butyl formate. Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, acetone, and cyclohexanone. Examples of the amide-based solvent include dimethylformamide and dimethylacetamide. Examples of the ether solvent include diethyl ether, methoxytoluene, 1, 2-dimethoxyethane, 1, 2-dibutoxyethane, 1-dimethoxymethane, 1-dimethoxyethane, 1, 4-dioxane, and tetrahydrofuran. Examples of the aliphatic and aromatic hydrocarbon solvents include hexane, pentane, xylene, toluene, benzene, and the like. The solvent may be used alone or in combination of two or more.

The proportion of the polyisocyanate (a) is preferably 20 mass% or more and 70 mass% or less with respect to the total amount of the polyisocyanate (a) and the polyol (B). The proportion of the polyisocyanate (a) is preferably 30 mass% or more relative to the total amount of the polyisocyanate (a) and the polyol (B) from the viewpoint of improving the strength of the antifogging film, and the proportion of the polyisocyanate (a) is preferably 60 mass% or less from the viewpoint of improving the flexibility of the antifogging film.

The polyisocyanate (a) and the polyol (B) are preferably blended so that the equivalent ratio of isocyanate groups of the polyisocyanate (a) to hydroxyl groups of the polyol (B) is 0.3 to 3, more preferably the equivalent ratio is 0.5 to 2.

In the polyol (B), the total amount ratio of the polyether polyol (B1) and the polycaprolactone polyol (B2) is preferably 70 mass% or more, more preferably 80 mass% or more, and still more preferably 90 mass% or more, from the viewpoint of improving the strength of the antifogging film.

The mass ratio ((b 1)/(b 2)) of the polyether polyol (b 1) to the polycaprolactone polyol (b 2) is 5 to 15. The mass ratio ((b 1)/(b 2)) of the polyether polyol (b 1) to the polycaprolactone polyol (b 2) is preferably 9 or more from the viewpoint of improving the antifogging property of the antifogging film, and (b 1)/(b 2) is preferably 12 or less from the viewpoint of the touch feeling of the antifogging film.

The surfactant is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the total amount of the polyisocyanate (a) and the polyol (B).

The solvent is generally used in an amount of about 0.5 to 1000 parts by mass based on 100 parts by mass of the solid content of the antifogging agent composition.

The antifogging agent composition of the present invention may contain silicone oil. By containing the silicone oil, the smoothness of the antifogging film can be improved. The HLB of the silicone oil is preferably 10 or more, more preferably 12 or more from the viewpoint of improving the antifogging property of the antifogging film, and the silicone oil is preferably 18 or less, more preferably 16 or less from the viewpoint of improving the compatibility with each component in the urethane coating composition. The HLB (Hydrophilic-lipophilic balance) is a value indicating the molecular weight of the Hydrophilic group portion of the total molecular weight of the surfactant. HLB can be calculated by the formula of Griffin (Griffin). The silicone oil may be used in combination of two or more.

The silicone oil is preferably a compound having a structure in which a hydrocarbon group at a side chain and/or a terminal of the silicone oil is substituted with an organic group. Examples of the organic group include a polyether group, a long-chain alkyl group, and a higher fatty acid ester group. Among them, polyether groups are preferable.

Examples of the polyether group include a polyethylene oxide group, a polypropylene oxide group, and a polyalkylene oxide group in which Ethylene Oxide (EO) and propylene oxide (trimethoxy or Propane-1,2-diyloxy group; PO) are added in a block or random manner.

Examples of the silicone oil include polyether-modified organopolysiloxane (HLB value=12, shin-Etsu Chemical co., ltd. Manufactured, product name: KF-642), polyether-modified organopolysiloxane (HLB value=14, shin-Etsu Chemical co., ltd. Manufactured, product name: KF-640), polyether-modified organopolysiloxane (HLB value=12, shin-Etsu Chemical co., ltd. Manufactured, product name: KF-351A), and the like.

When the silicone oil is used, the silicone oil is preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the total amount of the polyisocyanate (a) and the polyol (B).

When the silicone oil is used, the mass ratio of the surfactant to the silicone oil (surfactant/silicone oil) is preferably 3 to 50, more preferably 10 to 45.

< reaction retarder >

The antifogging agent composition of the present invention may further contain a reaction retarder. The reaction retarder may be used in combination of two or more.

Examples of the reaction retarder include organic acids such as formic acid, acetic acid, propionic acid, benzoic acid, phthalic acid, oxalic acid, and succinic acid; inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid.

When the reaction retarder is used, the reaction retarder is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total amount of the polyisocyanate (a) and the polyol (B).

< other ingredients >

As other components, various additives commonly used such as a catalyst, a leveling agent, an antioxidant, an ultraviolet absorber, and a light stabilizer may be blended into the antifogging agent composition of the present invention as required. The addition amount of the other components may be blended in a usual addition amount of each additive, but is usually 10 parts by mass or less with respect to 100 parts by mass of the total amount of the polyisocyanate (a) and the polyol (B).

< antifogging product >

The antifogging product of the present invention is a product obtained by applying the antifogging composition onto a substrate by a coating method for a usual coating material, and forming an antifogging film on the surface of the substrate by heat curing.

The substrate may be any type, and examples thereof include films or sheets of glass, silicon wafers, metals, plastics, and the like, and three-dimensional molded articles, and the shape of the substrate is not particularly limited. Examples of the plastic include polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, and polyamide resin.

When the substrate is coated, it is preferable to remove the adhering foreign matter on the surface of the substrate before coating, in order to improve the wettability of the substrate with the antifogging agent composition and prevent shrinkage (cissing). Examples of the method include dust removal by high-pressure gas or ionized gas, ultrasonic cleaning by aqueous detergent or alcoholic solvent, wiping by alcoholic solvent, and cleaning by ultraviolet light or ozone. Examples of the coating method include gravure coating, roll coating, dip coating, brush coating, spray coating, bar coating, doctor blade coating, die coating, and spin coating. In addition, a drying step may be provided before the heat curing step for the purpose of evaporating and drying the solvent contained in the antifogging agent composition immediately after application.

The heat curing temperature is usually from 60 to 150℃for 5 to 60 minutes, preferably from 70 to 130℃for 10 to 40 minutes. In addition, the drying is generally carried out at a temperature of 20 to 50℃for 0.5 to 50 minutes. However, when the base material is plastic, the curing temperature is preferably set to be less than the heat distortion temperature of the plastic.

The film thickness of the antifogging film is preferably 1 μm or more, more preferably 5 μm or more from the viewpoint of improving the antifogging property, and is preferably 100 μm or less, more preferably 50 μm or less from the viewpoint of improving the smoothness.

The antifogging product is preferably used for spectacles, windows, mirrors, etc. Specific examples of the glasses include glasses for vision correction, goggles, and face masks.

The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Examples

Example 1 ]

< preparation of antifogging agent composition >

69 parts by mass (52 parts by mass as an effective component) of a trimethylolpropane adduct of 1, 3-bis (isocyanatomethyl) cyclohexane as polyisocyanate (a) (product name: manufactured by Takenate D-120N,Mitsui Chemicals,Inc, effective component 75% by mass), 40 parts by mass of a polyoxyethylene glyceryl ether as polyether polyol (b 1) (molecular weight 750, S2/s1=1.5), 8 parts by mass of polycaprolactone triol as polycaprolactone polyol (b 2) (product name: manufactured by placel 308,Daicel Corporation, hydroxyl number per molecule of 3, number average molecular weight of 800), 3 parts by mass of sodium bis-2-ethylhexyl sulfosuccinate as surfactant (product name: manufactured by isol a-90,NOF CORPORATION, effective component 90% by mass), 0.2 parts by mass of a polyether modified organopolysiloxane as silicone oil (product name: KF-642, shin-etco., ltd. Manufactured by HLB value=12), 1 part by mass of acetic acid as a reaction retarder, and 50 parts by mass of acetic acid as a solvent for the anti-fogging agent were mixed.

< production of antifogging agent product >

The antifog composition obtained above was coated on a polycarbonate substrate (5 cm. Times.5 cm. Times.1 mm, product name: iupilon sheet NF-2000,MGC Filsheet Co, manufactured by Ltd.) using a bar coater. Then, the polycarbonate substrate was kept at 100℃for 3 minutes and dried, whereby an antifogging product (test piece) having an antifogging film having a thickness of about 10 μm on the polycarbonate substrate was produced.

Using the test pieces obtained above, the following evaluations (1) to (3) were performed. The results are shown in Table 1.

(1) evaluation of transparency

Determination was performed by measuring the haze (%) of an antifogging product (test piece) having an antifogging film using a haze meter (Nippon Denshoku Industries co., ltd. NDH 5000). The decision criteria are as follows.

And (3) the following materials: a haze value difference from the substrate of less than 1

O: a difference in haze value from the substrate of 1 or more and less than 3

X: a difference in haze value from the substrate of 3 or more

Evaluation of touch feeling (2)

After the test piece was left standing at 30℃under 60% RH for 24 hours or more, the tackiness of the surface of the antifogging film was determined by finger touch. The decision criteria are as follows.

And (3) the following materials: non-adhesive

O: exhibit slight tackiness

X: exhibit significant tackiness

(3) evaluation of antifogging Property

The test piece obtained above was fixed to a constant temperature water tank at 50℃at a position 1cm from the water surface so that the antifogging film faced downward, and the hazing state was visually determined. The decision criteria are as follows.

O: the test piece is fixed for more than 5 minutes and does not generate fog

X: immediately after fixing the test piece, fogging occurred.

< examples 2 to 6 and comparative examples 1 to 3>

< preparation of antifogging agent composition and production of antifogging product >

In each of examples and comparative examples, an antifogging composition was produced in the same manner as in example 1 except that the types of the raw materials and the blending amounts thereof were changed as shown in table 1, and an antifogging product (test piece) having an antifogging film on a polycarbonate substrate was further produced.

Using the test piece obtained above, transparency, touch and antifogging property were evaluated by the above evaluation method.

The results are shown in Table 1.

/>

In Table 1, takenate D-120N represents a trimethylolpropane adduct of 1, 3-bis (isocyanatomethyl) cyclohexane (product name: takenate D-120N,Mitsui Chemicals,Inc. Manufactured, active ingredient 75 mass%);

takenate D-140N represents a trimethylolpropane adduct of isophorone diisocyanate (product name: takenate D-140N,Mitsui Chemicals,Inc. Manufactured, active ingredient 75 mass%);

PLACCEL 308 represents polycaprolactone triol (product name: PLACCEL 308,Daicel Corporation, number of hydroxyl groups per molecule 3, number average molecular weight 800);

PLACCEL 312 represents polycaprolactone triol (product name: PLACCEL 312,Daicel Corporation, number of hydroxyl groups per molecule 3, number average molecular weight 1250);

UNIOX G750 represents polyoxyethylene glyceryl ether (product name: UNIOX G750, manufactured by NOF CORPORATION, molecular weight at maximum refractive index intensity point is 730, s2/s1=1.3);

RADISOL A-90 represents sodium bis-2-ethylhexyl sulfosuccinate (product name: 90% by mass of active ingredient, manufactured by RADISOL A-90,NOF CORPORATION);

KF-642 represents a polyether-modified organopolysiloxane (product name: KF-642, shin-Etsu Chemical co., ltd., manufacture, HLB value=12);

KF-640 represents polyether-modified organopolysiloxane (product name: KF-640, shin-Etsu Chemical Co., ltd., HLB value=14).

The number average molecular weight of the polyether polyol in terms of the GPC measurement is as follows. Polyoxyethylene glyceryl ether (number average molecular weight 630, molecular weight at maximum refractive index intensity of 730, s2/s1=1.5), polyoxyethylene glyceryl ether (number average molecular weight of 510, molecular weight at maximum refractive index intensity of 730, s2/s1=1.8), polyoxyethylene glyceryl ether (product name: UNIOX G750, manufactured by NOF CORPORATION, number average molecular weight of 710, molecular weight at maximum refractive index intensity of 730, s2/s1=1.3).

The antifogging films formed from the antifogging compositions of examples 1 to 6 were confirmed to exhibit transparency, touch and antifogging properties. In particular, examples 2 and 6 obtained excellent effects in transparency, touch feeling and antifogging property.

On the other hand, in comparative example 1, since the peak area ratio (S2/S1) of the polyether polyol (b 1) was small, a decrease in touch was exhibited.

In comparative example 2, since the mass ratio ((b 1)/(b 2)) of the polyether polyol (b 1) to the polycaprolactone polyol (b 2) is large, the decrease in transparency is exhibited.

In comparative example 3, the mass ratio ((b 1)/(b 2)) of the polyether polyol (b 1) to the polycaprolactone polyol (b 2) was small, and therefore, the antifogging property was reduced.

Claims

1. An antifogging agent composition comprising a polyisocyanate (A), a polyol (B), a surfactant and a solvent, characterized in that,

the polyisocyanate (A) is a polyisocyanate compound selected from at least one of the group consisting of diisocyanates and derivatives thereof,

the polyol (B) contains a polyether polyol (B1) and a polycaprolactone polyol (B2),

in a chromatogram obtained by gel permeation chromatography using a differential refractive index detector, the molecular weight of the polyether polyol (b 1) at the point of maximum refractive index intensity is 300 to 1,800, and when the peak area from the elution start point to the elution time point corresponding to the point of maximum refractive index intensity is S1 and the peak area from the elution time point corresponding to the point of maximum refractive index intensity to the elution end point is S2, S2/S1 is 1.5 to 2.0,

the mass ratio ((b 1)/(b 2)) of the polyether polyol (b 1) to the polycaprolactone polyol (b 2) is 5 to 15.

2. The antifogging agent composition according to claim 1, wherein the proportion of the polyisocyanate (a) is 20 mass% or more and 70 mass% or less with respect to the total amount of the polyisocyanate (a) and the polyol (B).

3. The antifogging agent composition according to claim 1 or 2, wherein the number average molecular weight of the polycaprolactone polyol (b 2) is 300 to 1,800.

4. An antifogging agent composition according to claim 1 or 2, characterized in that it contains silicone oil.

5. An antifogging agent composition according to claim 1 or 2, characterized by containing a reaction retarder.

6. An antifogging product comprising an antifogging film formed from the antifogging composition according to any one of claims 1 to 5 on a substrate.