JP4539117B2 - UV curable antifogging composition - Google Patents

Description

  The present invention is an ultraviolet curable antifogging composition, particularly an ultraviolet curable antifogging composition having excellent antifogging performance, excellent durability of the antifogging performance, thermoforming, and excellent wear resistance. Related to things.

  Various plastic materials are used for personal protective equipment such as sports goggles, helmet shields, safety glasses, safety shields, etc. from the viewpoint of lightness, transparency, processability and safety when cracked. For industrial use such as various display devices, instrument covers, lenses, sensor covers, housing use such as partitions and showcases in residential stores, and transportation related uses such as partitions and shelves for automobiles, railway vehicles, instrument covers, window glass, etc. It is used. The plastic materials used in these applications are subject to condensation or cloudiness on the surface when used in the vicinity of breathing, in high-temperature and high-humidity environments, or in environments with a large temperature difference between the front and back surfaces. There is a drawback that convenience and safety are likely to be lowered, such as deterioration of performance and malfunction of sensors.

  In order to eliminate this drawback, various studies on anti-fogging treatment have been made. For example, there is a method of forming an antifogging film by applying a composition containing a surfactant as a main component on the surface of a substrate. However, the surfactant is easily eluted only by contact with water, and the antifogging property is lowered in a short period of time, which is impractical in terms of durability. Moreover, the coating film which has surfactant had the problem that the movement to the interface and a protective film occurred during storage, and the external appearance of the product was remarkably impaired.

  Therefore, in order to improve the antifogging durability, a method of applying a hydrophilic polymer such as polyhydroxyalkyl (meth) acrylate and providing antifogging properties by a film cured by heat curing has been proposed. Although improvement in the properties is observed, it cannot be said that the anti-fogging performance is sufficient, and the mechanical strength such as wear resistance is practically insufficient, or if it is thermoformed into goggles or the like, it is prevented by the heat during molding. There is a problem that haze decreases.

In order to improve the abrasion resistance, a method of forming an antifogging film by a combination of a hydrophilic polymer and a crosslinking agent has been proposed, but the antifogging durability and wear resistance are not sufficient, and the heat resistance There was a problem that the antifogging property was extremely lowered during molding. Furthermore, an anti-fogging composition containing organic silicon has also been proposed, and although it has relatively high wear resistance and anti-fogging properties and durability, thermoforming itself cannot be performed, and goggles and the like There was a problem that it could not be applied to processed products.
JP-A-56-090876 Japanese Patent Publication No.53-018347 JP 53-028587 Japanese Patent Publication No.52-047754 JP 08-176466 A

  The present invention provides an ultraviolet curable antifogging composition that solves the above-mentioned problems, has excellent antifogging performance, is excellent in durability of the antifogging performance, can be thermoformed, and has excellent wear resistance. The purpose is to do.

In the first invention, at least one of each component of ethoxylated bisphenol A di (meth) acrylate (a), hydrophilic monofunctional monomer (b), polar diluting solvent and photopolymerization initiator represented by the following formula (1): The gist of the present invention is an ultraviolet curable antifogging composition characterized in that the solid content weight ratio (a) / (b) is 60/40 to 85/15.
(Chemical formula 1)
CH ₂ ═CR ₁ CO (OC ₂ H ₄ ) _m —O—C ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₄ —O— (C ₂ H ₄ O) _n OCR ₁ ═CH ₂ (1)
(R ₁ represents a hydrogen atom or a methyl group, m and n represent the average number of moles added of ethylene oxide, and m + n is 10 to 30)

  Further, the second invention provides the ethoxylated bisphenol A di (meth) acrylate (a), the hydrophilic monofunctional monomer (b), the polar dilution solvent and the photopolymerization initiator described in the above-mentioned claim 1, and further ethylene. It consists of at least one type of each component to which an ethoxylated polyfunctional acrylate (c) having an average added mole number of oxide of 6 to 20 is added, and the solid content weight ratio ((a) + (b)) / (c) is 100. / 30 to 100/1 (where (a) / (b) is 60/40 to 85/15). The gist of the ultraviolet curable antifogging composition is as follows.

  Further, the third invention further includes an ethoxylated bisphenol A di (meth) acrylate (a), a hydrophilic monofunctional monomer (b), a polar diluent solvent and a photopolymerization initiator described in the above-mentioned claim 1. It consists of at least one kind of each component to which a functional acrylate (d) is added, and the solid content weight ratio ((a) + (b)) / (d) is 100/10 to 100/1 (where (a) The gist of the ultraviolet curable antifogging composition is that / (b) is 60/40 to 85/15).

  The ultraviolet curable antifogging composition of the present invention comprises ethoxylated bisphenol A di (meth) acrylate (a) and a hydrophilic monofunctional monomer (b) as main components, and further ethoxylated polyfunctional acrylate (c), Alternatively, polyfunctional acrylate (d) is added, and their weight ratio (a) / (b), or ((a) + (b)) / (c), ((a) + (b)) / (d ) Within a specific range has excellent anti-fogging performance, excellent durability of the anti-fogging performance, thermoforming, and excellent wear resistance.

  The ethoxylated bisphenol A di (meth) acrylate (a) of the present invention has a structure having an ethylene oxide chain and bisphenol A as a central skeleton. The ethylene oxide chain which is a hydrophilic portion has a good antifogging property and does not lose its antifogging performance due to elution unlike a surfactant. However, since this ethylene oxide chain has a flexible molecular structure, it has an effect of softening the coating film and reducing strength such as wear resistance. In addition, the ethylene oxide chain has a structure in which adhesion with many resin substrates is difficult to obtain. Complementing this defect is a bisphenol A skeleton with a central structure that is rigid in molecular structure, improves the wear resistance, hardness, heat resistance, etc. of the coating film, and easily obtains adhesion to many resin substrates. The balance between the ethylene oxide chain and the bisphenol A skeleton can provide coating strength such as antifogging properties and abrasion resistance, antifogging properties, durability of the coating itself, and adhesion.

  The (meth) acrylate of the component (a) needs to be bifunctional. In the case of monofunctional, the crosslinking density of the cured coating film is too low, and a coating film having sufficient abrasion resistance cannot be obtained. In the case of three or more functions, the crosslinking density of the cured coating film becomes too high. This is because it is difficult to obtain sufficient antifogging properties.

  In the formula (1), the average added mole number of ethylene oxide, that is, m + n needs to be in the range of 10-30. When m + n is less than 10, the length of the ethylene oxide chain is insufficient and sufficient antifogging properties cannot be obtained. Conversely, when m + n exceeds 30, the flexible ethylene oxide chain becomes too long, and the abrasion resistance of the coating film is inferior.

Examples of the hydrophilic monofunctional monomer (b) include 2-hydroxyethyl vinyl ether (HEVE), 4-hydroxybutyl vinyl ether (HBVE), 4-hydroxybutyl acrylate (HBA), 4-hydroxybutyl acrylate glycidyl ether (HBAGA), and diethylene glycol. Monovinyl ether (DEGV), N-vinylpyrrolidone (NVP), cyclohexanedimethanol monoacrylate, N-vinylformamide (NVF), acryloylmorpholine (ACMO), methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, below Examples thereof include ethoxy mono (meth) acrylate and acrylamide represented by the formula (2), and acrylic acid amide compounds represented by the following formula (3).
(Chemical formula 2)
_{CH 2 = CR 1 CO (OC} 2 H 4) l -O-R 2 (2)
(R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a methyl group or a phenyl group, and l represents 5 to 20)
(Chemical formula 3)
CH ₂ = CHCONHR ₁ (3)
(R ₁ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or an alkyl ketone group)

  The weight ratio (a) / (b) between the ethoxylated bisphenol A di (meth) acrylate (a) and the hydrophilic monofunctional monomer (b) needs to be 60/40 to 85/15. When the proportion of the component (a) is less than 60% by weight, the wear resistance of the coating film is remarkably lowered and the appearance is also deteriorated. On the other hand, when the proportion of the component (a) exceeds 85% by weight, that is, when the proportion of the component (b) is less than 15% by weight, the initial antifogging property is extremely lowered. Moreover, adhesiveness with a base material may fall.

  The ethoxylated polyfunctional acrylate (c) used in the second invention is ethoxylated trimethylolpropane triacrylate, ethoxylated glycerin triacrylate, ethoxylated pentaerythritol tetraacrylate, and an average added mole number of ethylene oxide of 6 to What is 20 can be mentioned. When this average added mole number is less than 6, the length of the ethylene oxide chain is insufficient, and sufficient antifogging properties cannot be obtained. Conversely, when it exceeds 20, the flexible ethylene oxide chain becomes too long, and the abrasion resistance of the coating film is inferior.

  The solid content weight ratio in this second invention, that is, ((a) + (b)) / (c) is 100/30 to 100/1 (where (a) / (b) is 60 / 40-85 / 15). When the proportion of the component (c) exceeds 30% by weight, the crosslinking density becomes too high and the initial antifogging property is lowered. If the component (c) is less than 1% by weight, the effect of improving the crosslinking density of the component (c) is not exhibited. At the same time, if the ratio of the component (a) to the component (b) is less than 60% by weight, the strength that is characteristic of the component (a) is insufficient and the strength of the coating film is significantly reduced. In addition, when the proportion of the component (a) exceeds 85% by weight, that is, when the proportion of the component (b) is less than 15% by weight, the antifogging property is extremely lowered. This is the same as the case of the invention.

  As the polyfunctional acrylate (d) used in the third invention, trimethylolpropane triacrylate, glycerol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, ethoxylated trimethylolpropane triacrylate, ethoxy Examples thereof include glycerinated glycerol triacrylate and ethoxylated pentaerythritol tetraacrylate, wherein the average added mole number of ethylene oxide is 3-4.

  In this third invention, the solid content weight ratio, that is, ((a) + (b)) / (d) is 100/10 to 100/1 (where (a) / (b) is 60 / 40-85 / 15). When the ratio of the component (d) exceeds 10% by weight, the crosslinking density becomes too high, and the ratio of the hydrophilic group decreases too much, resulting in a decrease in initial antifogging property. When the component (d) is less than 1% by weight, the effect of improving the crosslinking density of the component (d) is not exhibited. At the same time, if the ratio of the component (a) to the component (b) is less than 60% by weight, the strength that is characteristic of the component (a) is insufficient and the strength of the coating film is significantly reduced. In addition, when the proportion of the component (a) exceeds 85% by weight, that is, when the proportion of the component (b) is less than 15% by weight, the antifogging property is extremely lowered. This is the same as the case of the invention.

The polar dilution solvent used in the present invention must be a good solvent for the ethoxylated bisphenol A di (meth) acrylate (a) and the hydrophilic monofunctional monomer (b), and is based on the antifogging composition. When the coating film formed by heating is dried by heating, it needs to be sufficiently dried at an appropriate speed capable of maintaining smoothness without deteriorating the appearance.

Examples of the polar dilution solvent include methanol, ethanol, isopropanol, n-propanol, and isobutanol, which have a relatively high drying rate, such as methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl, which have a moderate drying rate. Ether, n-butanol, diacetone alcohol, butyl cellosolve, etc., which have a relatively slow drying rate, can be used alone or in combination. It is also possible to mix a small amount of ketones, esters and aromatic hydrocarbon nonpolar solvents to the extent that they do not affect the solubility of (a) and (b). . Examples of nonpolar solvents for ketones, esters, and aromatic hydrocarbons include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, xylene, and toluene.

  The photopolymerization initiator used in the present invention has a function as a polymerization initiator when the photopolymerizable compound is cured by ultraviolet rays, and known ones can be used. For example, benzoin or benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, aromatic ketones such as benzophenone or benzoylbenzoic acid, alpha-dicarbonyls such as benzyl, benzyldimethyl ketal, benzyl Benzyl ketals such as diethyl ketal, acetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl -1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino Professional Acetophenones such as non-1; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone and 2-t-butylanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2-isopropylthioxanthone and 2,4-diisopropylthioxanthone , Alpha-acyl oximes such as 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, amines such as ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, etc. Can be used. Of these, acetophenones such as 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one and aromatic ketones such as benzophenone are particularly preferable.

  For the purpose of slightly improving the initial antifogging performance, a surfactant may be supplementarily added to the antifogging composition of the present invention. The surfactant that can be added can be selected from general nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, and the like. Among these, nonionic surfactants or anionic surfactants are particularly preferable, and combinations thereof are also preferable.

  Further, in the present invention, in order to obtain wettability and uniformity of the coating film on the base material at the time of coating, surface smoothness and surface slip property of the cured coating film, a silicone system, an acrylic copolymer system, etc. It is preferable to add the surface conditioner.

  As the silicone-based surface conditioner, polydimethylsiloxane or a modified silicone-based one obtained by modifying it is used. As the modified silicone, a polyether-modified product, an alkyl-modified product, a polyester-modified product and the like are preferable, and a polyether-modified product is particularly preferable. Moreover, it is also possible to use these in combination.

  The anti-fogging coating film which consists of an anti-fogging composition of this invention can be obtained in the process of mixing-dilution-application-drying-hardening of a composition. The thickness of the coating film is 60 μm or less. From the viewpoint of anti-fogging properties, the thicker the coating film, the better. However, when it exceeds 60 μm, the wear resistance is inferior. As a coating method, a roll coater, a spray coater, a curtain flow coater, a slit die coater or the like having a horizontal coating and conveying facility is suitable.

  After the antifogging composition of the present invention is applied to the substrate, the temperature of the substrate and the atmosphere is raised, and after sufficiently diluting the diluting solvent, ultraviolet rays are irradiated to cure the coating film. For the ultraviolet irradiation, a general electroded or electrodeless high-pressure ultraviolet lamp or metal halide lamp can be used.

  Although general transparent plastics can be used as the base material, it is assumed to be used in the present invention, such as sports goggles, helmet shields, safety glasses, and safety shields for human bodies, and various display devices and instrument covers. Polycarbonate resin is used in industrial applications such as lenses and sensor covers, residential applications such as partitions and showcases in residential stores, and transportation-related applications such as partitions and shelves, instrument covers, and window glass. It is most preferable to use a material from the viewpoints of lightness, transparency, workability, and resistance to cracking and safety when cracked. Other common transparent resins such as polymethyl methacrylate, polyethylene terephthalate, and polyvinyl chloride can also be used.

  First, the first invention will be specifically described with reference to examples and comparative examples.

<Example 1>
Each component used is as follows.
(A): Ethoxylated bisphenol A diacrylate having an average addition mole number of ethylene oxide of 10 (b): N vinyl-2 pyrrolidone (NVP)
Polar diluent solvent: 1: 1 solution of isopropyl alcohol and methyl cellosolve Photopolymerization initiator: 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 1- [4- (2-hydroxy) -phenyl] A 1: 1 mixture of 2-hydroxy-2-methyl-1-propan-1-one;

  In addition, a polyether-modified polydimethylsiloxane solution (manufactured by BYK Chemie, trade name BYK-306) was used as a silicon-based surface conditioner.

  The solid content weight ratio (a) / (b) was blended so as to be 60/40, and further diluted with the above polar diluent solvent so that these components became 40% by weight in the solution. At this time, a photopolymerization initiator previously dissolved in methyl cellosolve was added as a part of the polar diluent solvent so that the solid content ratio was 4%. Further, 0.1 part by weight of a silicon-based surface conditioner was added to 100 parts by weight of the composition. The composition was sufficiently stirred and mixed, and then stored in a sealed container.

  A transparent polycarbonate sheet having a plate thickness of 1.5 mm (“Polyca Ace” manufactured by Chuchu Plastic Industry Co., Ltd.) was prepared as a base material, and the composition was applied using a metal bar coater so that the dry film thickness was 30 μm. Next, the coated polycarbonate sheet was placed in a hot air circulation oven at 50 ° C. and dried. After drying for 10 minutes, a polycarbonate sheet is placed on a conveyor of 5 m / min using a 160 W / cm high-pressure mercury lamp (USHIO Inc.), and the polycarbonate sheet is irradiated with ultraviolet rays at a distance of 15 cm between the mercury lamp and the polycarbonate sheet. And the composition was cured. About the sheet | seat in which the anti-fogging coating film was formed, performance was evaluated as follows, and the result is shown in Table 1.

<Appearance>
The cured coating film was visually observed and evaluated as follows.
◎: The surface of the coating is smooth and transparent from any angle ○: The surface of the coating is smooth. △: The coating film surface is not smooth, or appears to be cloudy when viewed from an angle, and has practical problems. ×: The coating film surface is rough, or even when the flat surface is viewed from the front, it is cloudy, and is completely practical. Something without.
<Anti-fogging property 1>
The antifogging time was measured according to European standard EN168 and evaluated as follows.
A: Antifogging time longer than 10 seconds (excellent antifogging property)
○: Antifogging time over 5 seconds to 10 seconds or less (practical antifogging property)
Δ: Anti-fogging time more than 2 seconds to 5 seconds or less (weak anti-fogging property, limited use)
X: Antifogging time 0 second to 2 seconds or less (no antifogging property or very low antifogging property)
<Anti-fogging property 2>
Expiration was blown on the surface of the sheet 5 times, and the degree of cloudiness was visually observed and evaluated as follows.
◯: No cloudiness is observed even if the exhalation is blown three times or more. Δ: Exhalation is not observed even if the exhalation is blown once or twice, but clouding is observed if the exhalation is blown three times or more.
X: Clouding is observed when exhalation is blown once.

<Initial adhesion of coating film>
A cross-cut tape method (based on JIS K5400) was performed, and the following evaluation was performed according to the number of squares that were not peeled off.
A: 100 (very strong adhesion)
○: 90 to 99 (adhesion having no practical problem)
Δ: 60-89 (highly likely to cause practical problems)
X: 10 to 59 (adhesion is weak and there is no practicality at all)
XX: Largely peeled to the outside of 0-9 or grid (no adhesion)
<Boiling water adhesion of coating film>
After immersing the sample in boiling water for 30 minutes, the moisture was wiped off and dried at room temperature for 2 hours or more, and then evaluated by the cross-cut tape method as follows.
A: 100 (very strong adhesion)
○: 90 to 99 (adhesion having no practical problem)
●: 60 to 89 (Practical use requires some restrictions)
Δ: 30 to 59 (highly likely to cause practical problems)
X: 0 to 29 (problematic problem)
XX: The whole or part of the coating film does not exist due to natural peeling, or peels greatly to the outside of the grid (poor adhesion is not practical at all)
<Warm water resistant adhesion of coating film>
After immersing the sample in warm water at 60 ° C. for 100 hours, the moisture was wiped off and dried at room temperature for 2 hours or more, and then evaluated by the cross-cut tape method as follows.
A: 100 (very strong adhesion)
○: 90 to 99 (adhesion having no practical problem)
●: 70 to 89 (Practical use requires some restrictions)
Δ: 40 to 69 (highly likely to cause practical problems)
X: 0 to 39 (problematic problem)
XX: All or a part of the coating film is naturally peeled off or does not exist or peels off to the outside of the grid (no adhesion, no practicality)
<Heat-resistant adhesion of coating film>
The sample was allowed to stand in a hot air circulation oven at 80 ° C. for 100 hours, then allowed to stand at room temperature for 2 hours or more and cooled, and then evaluated by the cross-cut tape method as follows.
A: 100 (very strong adhesion)
○: 90 to 99 (no problem in practical use)
Δ: 40 to 89 (highly likely to cause practical problems)
X: 0 to 39 (adhesion is weak and not practical at all)
XX: All or part of the coating is peeled off spontaneously, or peels off to the outside of the grid (no adhesion)
<Abrasion resistance>
In accordance with ASTM D1044, a Taber abrasion test (CS10F wear wheel, load 500 g) was performed and evaluated as follows according to the generated haze.
A: Change in haze (ΔH) is less than 10% (very excellent wear resistance)
○: ΔH is 10% or more and 15% or less (excellent wear resistance)
●: ΔH is more than 15% and 20% or less (anti-fogging property without any practical problems)
Δ: ΔH is more than 20% and 25% or less (practically insufficient wear resistance)
×: ΔH is more than 25% and 35% or less (no wear resistance)
XX: ΔH is over 35% (low wear resistance and cannot be used at all)
<Moldability>
The sample was softened by heating in a hot air circulation oven set at 170 ° C. for 7 minutes, and immediately after removal, the sample was cooled to near room temperature by attaching it to a wooden cylinder with a radius of 30 mm through a flannel cloth with the coating surface facing outward. The single curved surface was molded by keeping it as it was, and then the appearance was observed and evaluated as follows.
○: No occurrence of cracks or peeling of coating film or change in appearance (excellent moldability)
X: Changes in appearance such as occurrence of cracks or peeling of the coating film, white turbidity or rough skin (no formability)
<Anti-fogging property of molded products>
The molded article is evaluated for the antifogging property 1 described above. However, this evaluation was not performed for those having an anti-fogging property evaluation result of Δ or ×.
A: The same anti-fogging property as before heat forming (good anti-fogging durability and can fully support thermoforming)
○: Anti-fogging property one rank lower than before heat forming (a certain degree of anti-fogging durability, application is limited by thermoforming conditions)
×: Antifogging property lower than rank 2 or lower than before heat molding (not antifogging durability corresponding to thermoforming)
<Durability of anti-fogging performance>
After immersing the sample in warm water at 60 ° C. for 100 hours, the antifogging property 1 is evaluated. However, this evaluation was not performed for those having an anti-fogging property evaluation result of Δ or ×.
A: The same anti-fogging property as the initial one (good anti-fogging durability)
○: Anti-fogging property one rank lower than the initial level (the degree of anti-fogging durability may limit the use)
X: Two or more ranks lower than the initial level or the lowest rank antifogging property (inferior in antifogging durability)

<Example 2>
Same as Example 1 except that (a) / (b) is 70/30.

<Example 3>
Same as Example 1 except that (a) / (b) was 85/15.

<Comparative Example 1>
Same as Example 1 except that (a) / (b) was 90/10.

<Comparative example 2>
Same as Example 1 except that (a) / (b) was 55/45.

<Comparative Example 3>
The same as Example 1 except that ethoxylated bisphenol A diacrylate having an average added mole number of ethylene oxide of 4 was used instead of (a).

<Comparative example 4>
In place of (a), polyethylene glycol diacrylate which is a bifunctional acrylate represented by the following formula (4) and having an average added mole number of ethylene oxide of 9 but containing no bisphenol A skeleton in the skeleton is: Same as Example 1 except that N vinylformamide was used as b).
(Chemical formula 4)
_{CH 2 = CHCO-O (OC} 2 H 4) 9 O-CO-CH = CH 2 (4)

<Comparative Example 5>
Instead of (a), ethoxylated glycerin triacrylate, which is a trifunctional acrylate represented by the following formula (5) and having an average added mole number of ethylene oxide of 20 but not containing a bisphenol A skeleton, As in Example 1, except that N-vinylformamide was used.

  As shown in Table 1, in Examples 1 to 3, where the weight ratio of ethoxylated bisphenol A di (meth) acrylate (a) to hydrophilic monofunctional monomer (b) is within the scope of the present invention, It can be seen that the antifogging property 2 by the breath test as well as the antifogging property 1 by the more strict antifogging test of EN168 has excellent antifogging property. In addition, it can be seen that the anti-fogging property has durability that is not lost in heat and humidity, and is excellent in sufficient adhesion to the substrate, moldability, and abrasion resistance. On the other hand, in Comparative Example 1 or Comparative Example 2 in which the weight ratio of the above (a) and (b) deviates from the scope of the present invention, the initial antifogging property is lowered and the adhesion is insufficient (Comparative Example 1). ), Appearance and wear resistance are reduced (Comparative Example 2).

  In Comparative Example 3 using ethoxylated bisphenol A diacrylate in which the average added mole number of ethylene oxide deviated from the scope of the present invention, the initial antifogging property was not obtained.

  Although the average added mole number of ethylene oxide is within the range of the present invention, in Comparative Example 4 using a diacrylate not containing bisphenol A, although initial antifogging property was obtained, it was obtained under high temperature and high humidity. There is no adhesion, the antifogging durability is inferior, and there is no wear resistance and moldability. Moreover, although the average added mole number of ethylene oxide is within the range of the present invention, Comparative Example 5 using trifunctional acrylate has a poor initial antifogging property.

  Next, the second invention will be described. The evaluation method is the same as in the first invention.

<Example 4>
The following components (a) to (c) were used, except that (a) / (b) was 75/25 and ((a) + (b)) / (c) was 100/5. Is the same as in Example 1. The evaluation results are shown in Table 2.

(A): Ethoxylated bisphenol A diacrylate having an average addition mole number of ethylene oxide of 30 (b): acryloylmorpholine (ACMO)
(C): Ethoxylated glycerol triacrylate having an average addition mole number of ethylene oxide of 9 (in the above formula (5), l + m + n is 9)

<Example 5>
Example 4 is the same as Example 4 except that ((a) + (b)) / (c) is set to 100/15.

<Example 6>
Example 4 is the same as Example 4 except that ((a) + (b)) / (c) is set to 100/25.

<Comparative Example 6>
Example 4 is the same as Example 4 except that ((a) + (b)) / (c) is 100/40.

<Comparative Example 7>
Example 6 is the same as Example 6 except that (c) is an ethoxylated glycerin triacrylate having an average addition mole number of ethylene oxide of 3 (in formula (5), l + m + n is 3).

  As shown in Table 2, Examples 4 to 6, which are the scope of the present invention, are excellent in antifogging property, antifogging durability, wear resistance, and moldability. On the other hand, in Comparative Example 7 in which the component (c) was added beyond the range of the present invention, or in Comparative Example 8 in which the average added mole number of ethylene oxide exceeded the range of the present invention, the initial antifogging property was obtained. It has been extremely lowered.

The third invention will be described. The evaluation method is the same as in the first invention.

<Example 7>
Using the following components (a), (b) and (d), blending so that (a) / (b) is 75/25 and ((a) + (b)) / (d) is 100/5 The same as in Example 1 except that. The evaluation results are shown in Table 3.

(A): Ethoxylated bisphenol A diacrylate having an average addition mole number of ethylene oxide of 30 (b): acryloylmorpholine (ACMO)
(D): Ethoxylated glycerol triacrylate having an average addition mole number of 3 of ethylene oxide (in the above formula (5), l + m + n is 3)

<Example 8>
Example 7 is the same as Example 7 except that ((a) + (b)) / (d) is set to 100/10.

<Example 9>
As (d) component, it is the same as that of Example 8 except having used the glycerol triacrylate represented by following formula (6).
(Chemical formula 6)
_{CH 2 = CHCO-O-CH} 2 -CH (OCOCH = CH 2) -CH 2 -O-CO-CH = CH 2 (6)

<Comparative Example 8>
As component (d), glycerin triacrylate represented by the above formula (6) was used, and ((a) + (b)) / (d) was set to 100/20.

  As shown in Table 3, Examples 7 to 9, which are the scope of the present invention, are excellent in antifogging property, antifogging durability, wear resistance, and moldability. On the other hand, in Comparative Example 9 in which the component (d) was added beyond the scope of the present invention, the initial antifogging property was lost.

Claims (3)

The ethoxylated bisphenol A di (meth) acrylate (a) represented by the following formula (1), a hydrophilic monofunctional monomer (b), a polar diluting solvent, and a photopolymerization initiator, and comprising at least one kind of each component, solid content weight The ultraviolet curable antifogging composition, wherein the ratio (a) / (b) is 60/40 to 85/15.
(Chemical formula 1)
CH ₂ ═CR ₁ CO (OC ₂ H ₄ ) _m —O—C ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₄ —O— (C ₂ H ₄ O) _n OCR ₁ ═CH ₂ (1)
(R ₁ represents a hydrogen atom or a methyl group, m and n represent the average number of moles added of ethylene oxide, and m + n is 10 to 30)   In addition to the ethoxylated bisphenol A di (meth) acrylate (a), the hydrophilic monofunctional monomer (b), the polar diluting solvent and the photopolymerization initiator described in claim 1, the average addition mole number of ethylene oxide is 6 to It consists of at least one type of each component to which ethoxylated polyfunctional acrylate (c) of 20 is added, and the solid content weight ratio ((a) + (b)) / (c) is 100/30 to 100/1 (however, Here, (a) / (b) is 60/40 to 85/15), an ultraviolet curable antifogging composition.   The polyfunctional acrylate (d) is further added to the ethoxylated bisphenol A di (meth) acrylate (a), the hydrophilic monofunctional monomer (b), the polar diluent solvent and the photopolymerization initiator described in claim 1. Each component consists of at least one kind, and the solid content weight ratio ((a) + (b)) / (d) is 100/10 to 100/1 (where (a) / (b) is 60/40 UV curable antifogging composition characterized in that it is ~ 85/15).