JPS63273668A - Hydrophilic film-forming composition, hydrophilic film thereof and production of said hydrophilic film - Google Patents

Abstract

PURPOSE:To obtain the titled composition useful for mirrors for bathrooms, glasses and lenses, having initial non-fogging properties, mechanical strength and hardness, forming a hydrophilic film by irradiation with electron beam, containing a polymer, a hydrophilic monomer and a hydrophilic crosslinkable monomer. CONSTITUTION:The aimed composition containing (A) 100pts.wt. polymer [preferably containing (meth)acryloyl, allyl or epoxy group], (B) preferably 5-200pts. wt. hydrophilic monomer (preferably containing OH, carboxyl, a metallic salt thereof, amido, imido, sulfonic group, ammonium salt or phosphate group) and (C) preferably 1-300pts.wt. hydrophilic crosslinkable monomer [preferably containing carboxyl, metallic salt thereof, amido, imido, sulfonic group, metallic salt thereof, ammonium salt or phosphate group and (meth)acryloyl, allyl or epoxy].

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a hydrophilic film having antifogging properties, a composition for forming the same, and a method for producing the hydrophilic film.

[Prior Art] Bathroom mirrors, sunglasses, eyeglass lenses, watch cover glasses, ski goggles, etc. are prone to fogging because they are often exposed to moisture, and various attempts have been made to prevent these from fogging. Ta.

JP-A-55-69678 discloses an antifogging agent comprising a photocurable ethylenically unsaturated compound containing a hydrophilic group, a photocurable ethylenically unsaturated compound not containing a hydrophilic group, and a photocuring initiator. is disclosed. However, in this antifogging agent, hydrophilic groups are not selectively present on the surface, so the antifogging property is low, and since it contains a photocuring initiator, the light resistance is poor.

JP-A No. 57-163568 is characterized in that at least a portion of an ultraviolet-resistant polyvinyl chloride resin film containing a large amount of ultraviolet absorber is coated with a cationically polymerized energy ray-curable resin composition. Discloses an agricultural film having antifogging properties. Cationic polymerizable energy ray curable resin compositions are cationic polymerizable resin compositions that are polymerized or crosslinked to form a coating film by irradiation with energy rays (ultraviolet rays), such as epoxy resins, cyclic ethers, and lactones. , vinyl compounds, etc.

However, this method prevents or suppresses surface migration and outflow scattering of surfactants, etc. in polyvinyl chloride resin films by forming a coating film of a cationically polymerized energy ray-curable resin composition on the surface. Therefore, I was not necessarily satisfied with the anti-fog properties.

JP-A-58-103533 discloses a method in which an ultraviolet curable paint is applied to one side of an anti-fog film and cured by ultraviolet irradiation.
Disclosed is a method characterized in improving the anti-fog persistence of a film. Since the coating film of this paint is crosslinked by ultraviolet irradiation, it is possible to prevent the heat protectant from oozing out from the antifogging film. However, since the coating film itself does not have a hydrophilic group, its initial antifogging properties are particularly poor, and since it is an ultraviolet curing type, it contains a sensitizer, so it deteriorates due to sunlight and ultraviolet rays from fluorescent lamps. The problem is that there is a significant

Other JP-A-80-100914 and 60-1010
No. 42 is a heat protection product that is characterized by bonding a transparent acetyl cellulose film to a base material made of a highly transparent synthetic resin film or sheet using an S heat adhesive, and then treating the surface to make it hydrophilic with an aqueous NaOH solution or the like. Discloses a method for manufacturing a synthetic resin sheet.

However, since this sheet-like material is not crosslinked, its strength is insufficient, and the antifogging effect due to the surfactant gradually seeping out from inside the film cannot be expected. Moreover, this hydrophilic treatment process itself complicates the entire process, making it impractical.

In addition, with the conventional method of kneading surfactants into resin,
Since the leaching of the surfactant is significant, the durability of the antifogging property is poor.

[Problem to be Solved by the Invention 1] As mentioned above, no material has yet been proposed that has sufficient anti-fog properties and is excellent in durability (anti-fog durability), deterioration resistance, mechanical strength, etc.

Therefore, an object of the present invention is to provide a novel hydrophilic film that has sufficient antifogging properties and is excellent in durability, deterioration resistance, mechanical strength, etc.

Another object of the invention is to provide a composition for forming such a hydrophilic membrane.

Yet another object of the invention is to provide a method for manufacturing such hydrophilic membranes.

[Means for solving the problem] In view of the above objectives, as a result of intensive research, the present inventors irradiated a coating film of a mixture of a polymer skeleton, a hydrophilic monomer, and a hydrophilic crosslinking monomer with an electron beam. Then, they discovered that the two bonded together through a crosslinking reaction, and the hydrophilic membrane particles floated to the surface, thereby turning the membrane with many hydrophilic groups on the surface blue, and they came up with the present invention.

That is, the hydrophilic film-forming composition of the present invention, which forms a hydrophilic film by electron beam irradiation, is characterized by containing a polymer, a hydrophilic monomer, and a hydrophilic crosslinkable monomer. The composition of the present invention may contain a surfactant and may further contain a solvent if necessary.

Further, the hydrophilic film of the present invention is obtained by irradiating a film-like material of a mixture containing a polymer, a hydrophilic monomer, and a hydrophilic crosslinkable monomer with an electron beam, and the hydrophilic monomer and the hydrophilic crosslinkable monomer are It is characterized by being crosslinked with a monomer. Similarly, the hydrophilic membrane of the present invention may contain a surfactant.

Furthermore, the method for producing a hydrophilic film of the present invention is characterized in that a polymer, a hydrophilic monomer, and a hydrophilic crosslinking monomer are mixed, coated in a film form, and then irradiated with an electron beam of 0.5 to 2" OMrad. Also in this method, a surfactant may be added to the mixture.

Since the polymer used in the present invention forms the skeleton of the hydrophilic membrane, it must have purulent properties.

In addition, in order for a hydrophilic film to have sufficient longevity (durability), it must have good water resistance, and for this purpose, it is desirable that the polymer have hydrophobicity.

The above polymer may be either a non-functional polymer or a functional polymer.

As the non-functional polymer, polyacrylic acid alkyl ester, polymethacrylic acid alkyl ester, polyurethane, polyester, polyamide, polyvinyl acetate, polyvinyl chloride, polystyrene, polyacrylonitrile, polyvinylpyrrolidone, etc. can be used.

Furthermore, in order to improve compatibility with hydrophilic monomers, a hydrophilic group may be introduced into the non-functional polymer in advance.

For this purpose, a copolymer with a monomer having a hydrophilic group (hydrophilic monomer), which will be described later, is used.

The ratio of the hydrophilic monomer to the non-functional polymer is 50 mol% or less, and if it exceeds this, the water resistance of the resulting membrane will decrease.

Furthermore, derivatives of polyvinyl alcohol such as partially saponified polyvinyl alcohol, polyvinyl butyral, and polyvinyl acecool, and cellulose derivatives such as nitrocellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and hydroxypropyl cellulose can also be used. can.

On the other hand, a functional polymer is a polymer having a functional group that causes a crosslinking reaction by ultraviolet rays, and examples of the functional group include the following.

Acryloyl group -0C-〇-CH2! 1 CH3 Methacryloyl group -QC-C=CH2 Allyl group -CH-CH=CH2 Functional group is desirably present at a ratio of one per molecular weight of 300 to ioooo of the polymer, and less than one per 10,000 molecular weight? In the case of J coupling, there is almost no crosslinking effect due to the functional group, and 1/300 molecular weight.
If the ratio exceeds one, the crosslinking density will become too high.

Examples of functional polymers include urethane acrylate, polyester acrylate, epoxy acrylate, etc., and acrylic acid chloride or 2-hydroxyethyl acrylate on the hydroxyl group of a copolymer of acrylic acid alkyl ester and 2-hydroxyethyl acrylate. Copolymers with acryloyl groups introduced by adding a 1:1 adduct of diisocyanate, copolymers with glycidyl methacrylate added to the carboxyl group of a copolymer of acrylic acid alkyl ester and acrylic acid, and polyvinyl Acrylic acid chloride or acrylic acid-2 is added to the remaining hydroxyl group of butyral.
-A 1:1 adduct of hydroxyethyl and diisocyanate can be used.

The above-mentioned polymer may be in the form of an oligomer, but from the viewpoint of film-forming properties, the molecular weight is preferably from 1,000 to 300,000 (weight average).

Hydrophilic monomers include hydroxyl groups, carboxyl groups (metal salts),
Amide group, imide group, sulfone group, ammonium base,
A monomer containing a hydrophilic group such as a phosphoric acid group, such as 2-hydroxyethyl acrylate, methacryl 111
2-hydroxyethyl, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylic acid, methacrylic acid, metal acrylate, gold lI methacrylate salt, acrylamide, methacrylamide, dimethylaminopropylacrylamide, dimethylaminopropyl methacrylate amide, N-acryloylmorpholine,
N-methacryloylmorpholine, N-methylol acrylamide, N-methylol methacrylamide, t-
Butylacrylamide, t-butylmethacrylamide,
N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-n-butoxyacrylamide,
N,N-dimethylacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, glycerol monomethacrylate, 2-
Examples include acrylamide 2-methylpropanesulfonic acid, methacrylamide propyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, and mono(2-methacryloyloxyethyl) acid phosphate.

Hydrophilic crosslinking monomers include hydroxyl groups, carboxyl groups (metal salts), amide groups, imide groups, sulfonic acid groups (metal salts),
A monomer that has a hydrophilic group such as an ammonium base or a phosphate group, and two or more crosslinkable functional groups that easily become radicals when irradiated with electron beams, such as an acryloyl group, a methacryloyl group, an allyl group, or an epoxy group.

Examples of such hydrophilic crosslinking monomers include those having a hydroxyl group such as glycerol di(meth)acrylate and glycerol methacrylate acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, and polyethylene glycol diglycidyl ether di(meth)acrylate. ) acrylate, polypropylene glycol diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)
1:2 of diol/diglycidyl ether such as acrylate, glycerin diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, trimethylolpropane triglycidyl ether di(meth)acrylate and acrylic acid.
Adducts, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tetracrylate pentaerythritol derivatives such as dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, methylene bis(meth)acrylamide, acrylamide/glyoxal adduct, acrylamide/methyloethylene urea condensate, 1,3゜5- triacryloyl hexahydro s
-triazine, N,N-diallylacrylamide,
Examples include acrylamide derivatives such as acrylamide/methylolmelamine condensate, acrylamide/methyloltriazone condensate, acrylamide/methylolhydantoin condensate, acrylamide/methylolurea, and N,N-diallylacrylamide.

The hydrophilic film-forming composition of the present invention can also contain a surfactant. The surfactant has the effect of imparting antifogging properties by gradually exuding from the hydrophilic film to the surface.

If the compatibility with the hydrophilic film-forming composition is good, it is anionic;
Both nonionic and cationic surfactants can be used.

As anionic surfactants, fatty acid salts, alkyl 1i
il ester salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, dialkyl sulfosuccinate ester salt, alkyl phosphate ester salt, naphthalene sulfonic acid-formalin condensate, polyoxyethylene alkyl sulfate ester salt, etc. Examples of activators include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester,
Examples include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene-oxypropylene block polymer, and examples of cationic surfactants include alkylamines and quaternary ammonium salts.

The composition of the present invention may contain a solvent if necessary. The solvent not only adjusts the fluidity of the composition but also has the effect of lifting the hydrophilic monomer onto the surface of the coating film, and is therefore preferred for forming the hydrophilic film of the present invention. Usable solvents include alcohols such as methanol, ethanol, isopropanol, methyl cellosolve, and ethyl cellosolve, ethers such as tetrahydrofuran, ketones such as methyl ethyl ketone, acetone, and methyl isobutyl ketone, ethyl acetate, and butyl acetate. and aromatic hydrocarbons such as toluene and xylene, and mixed solvents thereof.

In the hydrophilic film-forming composition of the present invention, polymer 10
0 parts by weight, the hydrophilic monomer is 5 to 200 parts by weight. If it is less than 5 parts by weight, sufficient hydrophilicity will not be imparted, and if it exceeds 200 parts by weight, the water resistance of the membrane will decrease. The preferred content of hydrophilic monomer is 20 to 150 parts by weight.

The hydrophilic crosslinking monomer is 1 to 100 parts by weight of the polymer.
It is a 300 turbulent part. If it is less than 1 part by weight, sufficient hydrophilicity and crosslinking properties will not be imparted, whereas if it exceeds 300 parts by weight, the water resistance of the membrane will decrease and the crosslinking density will become too high. The content of unfavorable hydrophilic crosslinking monomers is 1 to 100
This is a heavy lifting section.

When a surfactant is added, the amount is 100 parts by weight or less per 100 parts by weight of the polymer. If it exceeds 100 parts by weight, too much surfactant leaches out. The preferred content is 1 to 50 parts by weight.

The amount of solvent added varies depending on the film formation method, but when forming a coating film by coating, the solid content in the composition is 5 to sow.
m%, preferably 5 to 30% by weight. Generally, the amount of solvent added is 600 parts per 100 parts by weight of polymer.
The amount shall be 0 parts by weight or less.

A hydrophilic film can be formed by the following method using the composition of the present invention.

First, a composition adjusted to an appropriate viscosity is applied by a roll coating method such as a gravure reverse method, a three-line reverse method, a gravure direct method, or a four-line reverse method. Depending on the application, the coating is preferably carried out on a support such as a base film. Transparent plastic is generally used as the base film, but colored or opaque films can also be used for decorative purposes. Furthermore, in order to improve adhesion to the coating film, a film that has been subjected to easy-to-apply treatment can also be used. Base film materials include polyester, polyethylene, polypropylene, polycarbonate, polyacrylate, polystyrene, polyamide,
Polyimide, polyvinyl chloride, etc. can be used.

The composition formed on the base film etc.? The coating film of No. 0 is dried while being heated with a dryer etc. in order to remove the solvent by evaporation. If the heating temperature is too high, the monomers will also evaporate, so the maximum heating temperature is about 140°C.

It has been found that in the coating film of the composition of the present invention formed as described above, the monomer tends to float to the surface and consists of a monomer-rich phase and a polymer-rich phase. This is an important feature of the invention. That is,
Due to such "orientation", a relatively large number of hydrophilic groups are present on the surface, and a hydrophilic membrane structure supported by a polymer skeleton having water resistance, mechanical strength, etc. can be obtained.

Next, this coating film is irradiated with an electron beam. As the irradiation method, any method such as an electron curtain method or a beam scanning method can be used. Irradiation with electron beams makes the polymer crosslinkable with or without functional groups, and hydrophilic monomers and hydrophilic crosslinkable monomers crosslink to the polymer in the form of graft or block polymerization.

This point is markedly different from crosslinking by ultraviolet irradiation.

The energy of the irradiated electron beam is about 150 to 200kcV, and it is very bright! The amount of 11 varies depending on the composition of the composition, the desired degree of crosslinking density, etc. The more functional groups there are in the polymer, the smaller the irradiation dose is required, and the higher the crosslinking density, the more the irradiation dose needs to be increased. In particular, when a surfactant is contained, controlling the irradiation amount is important because if the crosslinking density is too high, the leaching of the surfactant will be insufficient and the antifogging effect will be reduced. Considering the above, the irradiation dose is generally 5 to 20 Mrad,
If it is less than 0.5 M rad, unreacted monomers may remain, and if it exceeds 20 M rad, the crosslink density becomes too high.

In particular, regarding the individual compositions, (a) 0.5 to 15 Mrad is preferable in the case of a non-functional polymer and a hydrophilic monomer, and (b) 0.5 to 15 Mrad is preferable in the case of a functional polymer and a hydrophilic monomer and a hydrophilic crosslinkable monomer. 5 to 15 M rad is preferable, and in the case of (C) non-functional polymer + hydrophilic monomer + hydrophilic crosslinking monomer + surfactant, 0.5 to 10 M r
ad is preferable or unfavorable, and in the case of (d) functional polymer + hydrophilic monomer + hydrophilic crosslinking monomer + surfactant, 0.5 to I
OM rad is preferred.

The hydrophilic membrane thus prepared has a polymer skeleton crosslinked with a hydrophilic monomer and a hydrophilic crosslinking monomer, and the hydrophilic groups of the hydrophilic monomer and hydrophilic crosslinking monomer are concentrated on the membrane surface. It has a unique II4 structure. Furthermore, since the entire film is crosslinked, it has sufficient hardness and strength.

In particular, in the present invention, the hydrophilic monomer and the hydrophilic crosslinking monomer have good compatibility, and the resulting hydrophilic film has very good antifogging properties.

Because of the hydrophilic groups present on the surface, it has excellent antifogging properties, especially in applications where it is exposed to water vapor for a short period of time. Therefore, it is not particularly necessary to contain a surfactant in those used for such purposes.

On the other hand, for those used in applications that are exposed to water vapor for a long period of time, it is necessary to contain a surfactant. In this case, the hydrophilic groups on the surface exhibit initial antifogging properties, and the surfactant present in the film oozes out to the surface due to moisture adhering to the membrane surface, thereby exhibiting long-term antifogging properties. Here, since the hydrophilic film of the present invention is crosslinked, the surfactant leaches out gradually, and the antifogging property can be maintained for a very long period of time. Furthermore, by changing the electron beam irradiation conditions, the crosslinking density can be adjusted to control the exudation rate of the surfactant.

Since the hydrophilic film of the present invention can be formed as a coating film on a base film, it can be attached to a desired location such as a mirror or window by applying an adhesive to the base film. Furthermore, since it can be made flexible, it can be attached to curved objects such as glasses and goggles.

In addition, when the hydrophilic film of the present invention is formed as a coating film on a base film, it has a thickness of 0.1 to 30 μm. If the thickness is less than 0.1 μm, not only will the film strength be weak, but the antifogging property will not last long, and even if the thickness exceeds 30 μm, further improvement in effectiveness cannot be expected.

[Example] The present invention will be explained in further detail by the following examples.

Example 1 300 parts by weight of acrylic polymer solution and 1001f of 2-hydroxyethyl methacrylate as a hydrophilic monomer
Part i, 10 parts by weight of pentaerythritol triacrylate as a hydrophilic crosslinking monomer, 5 parts by weight of Emulgen 106 (manufactured by Kao Corporation) as a surfactant, and 300 parts by weight of Methyl Celsolve as a solvent were uniformly added. mix,
The composition of the present invention was prepared in a.

Note that the acrylic polymer solution was prepared according to the following procedure. That is, 700 parts by weight of methyl methacrylate and 2
-390 parts by weight of hydroxyethyl methacrylate, 1.5 parts by weight of azobisisobutyronitrile, and 2210 parts by weight of methyl cellosolve, 31! The mixture was placed in a separable flask equipped with a flow tube and a stirrer and purged with nitrogen, and reacted at 85°C for 5 hours in a N2 stream. Thereafter, 1.5 parts by weight of azobisisobutyronitrile was further added, and the mixture was reacted for 3 hours. The resulting acrylic polymer clear liquid had a concentration of 33% by weight, and as measured by gel permeation chromatography (GPC), the average molecular weight (MW) was 7.
．． It was 5x10'. Moreover, no monomer peak was observed.

The above composition was uniformly coated to a thickness of 5 μm on a polyester film (Lumirror T type) with a thickness of 50 μm using a roll coater, and after drying with a dryer, it was heated at 175 keV using an electron curtain type EB device (manufactured by ES 1).
The coating film was cured by irradiating with an electron beam of 5 M rad.

The antifogging property of the obtained hydrophilic film was evaluated by the following test.

(1) Water contact angle test.

(2) Breath test (to check whether cloudiness occurs with exhaled breath). Test evaluation O: No clouding, ×: Cloudy occurrence (3) Ice water breath test (A film is pasted on a beaker containing ice water, and 1 minute later, exhalation is applied to check whether or not clouding occurs).

(4) 60°C steam test (examine whether clouding occurs by exposing the film to steam at 60°C).

(5) 96°C steam test (examine whether clouding occurs by exposing the film to steam at 96°C).

In the tests (4) to (5) above, the results are shown in Table 1 below.

Friend 1 and -12 Using the compositions shown in Table 1, hydrophilic films were prepared in the same manner as in Example 1, and the same tests were conducted. The results are also shown in Table 1.

100 parts by weight of urethane acrylate as a large 1U1 functional polymer, 50 parts by weight of N,N-dimethylacrylamide as a hydrophilic monomer, glycerin diglycidyl ether diacrylate as a hydrophilic crosslinking monomer, and [Rheodol TW-] as a surfactant. 5 parts by weight of 01064 (manufactured by Kao Corporation) and 500 parts by weight of methyl ethyl ketone as a solvent were mixed to prepare a composition for forming a hydrophilic film of the present invention.

Note that m'th of urethane acrylate was determined as follows. That is, using the same apparatus as in Example 1, 650 g of butylene adipate ("Niraboran N-45 F04 manufactured by Nippon Polyurethane Co., Ltd."), 300 q of methyl ethyl ketone, and 444 q of isophorone diisocyanate were placed therein, and stirred at 60 ° C. While stirring, 1 q of diptyltin dilaurate dissolved in 10 g of methyl ethyl ketone was added dropwise.

232q of 2-hydroxyethyl acrylate was added dropwise with stirring in a nitrogen stream for 5 hours, and after the completion of the addition, an additional 70
Stirring was continued for 3 hours at °C. The reaction was terminated when it was confirmed by infrared absorption spectrum that the peak of the -NGO group had disappeared. Weight average molecular weight (Mw) of the obtained polymer
was 1700 by GPC.

The above composition was applied onto an easily adhesive polyester film (Toyobo K-1522) in the same manner as in Example 1, and after drying, it was cured under the same electron beam irradiation conditions. Regarding antifogging properties, the same test as in Example 1 was conducted.The results are shown in Table 2.

K1 Rat Nuyu In the same manner as in Example 11, hydrophilic coating films were formed from the compositions shown in Table 2, and the same antifogging test was conducted for each hydrophilic film. The results are shown in Table 2.

Example 13 In the composition prepared in Example 1, the amount of surfactant was varied from 0 to 30 parts.

Each of the obtained compositions was subjected to the same test as in Example 1, and also to a water immersion test to evaluate long-term antifogging properties. The water resistance immersion test was conducted by immersing the film in water at 25°C for 24 hours, and after taking it out from the water at 60°C.
A steam test is conducted to determine whether the product maintains its anti-fogging properties.If it does not fog up after being exposed to steam at 60℃ for 1 minute (if it maintains its anti-fogging properties), it is ○, otherwise it is ×.
And so. The results are shown in Table 3.

Using the same composition as in Example 1, coating was carried out in the same manner to a thickness of 5 μm and dried with a dryer. The obtained coating films were irradiated with an electron beam of 175 keV at various doses to obtain hydrophilic coating films with various cross-ta densities. The antifogging property of the obtained hydrophilic coating film was measured. The results are shown in Table 4 along with the electron beam irradiation amount.

The same experiment as in Example 14 was conducted on the composition shown in Example 2. The results are shown in Table 5.

Comparative Example 1 A coating film was formed in exactly the same manner as in Example 3 except that glycerol monomethacrylate as the hydrophilic monomer was not used, and the antifogging properties of the resulting coating film were evaluated.

The results are shown in Table 6.

Comparative Example 2 A coating film was formed in exactly the same manner as in Example 3 except that dipentaerythritol pentaacrylate as the hydrophilic crosslinking monomer was not used, and the antifogging properties of the resulting coating film were evaluated. The results are shown in Table 6.

The results shown in Table 6 show that the hydrophilic monomer and the hydrophilic crosslinking monomer exhibit a synergistic effect, and if either one is lacking, the antifogging effect of the present invention cannot be obtained.

Comparative Example 3 After applying the composition shown in Example 1, l”usi o
Ultraviolet irradiation was performed for 10 minutes using nDR8-120LIVli[t (manufactured by Somar). However, no curing reaction occurred. This shows that the composition of the present invention is crosslinked (cured) only by electron beams.

[Effects of the Invention] As described above, the hydrophilic film-forming composition of the present invention has the property of curing by precipitating hydrophilic monomers and hydrophilic crosslinking monomers on the surface, so that it can form a hydrophilic film with initial antifogging properties. Furthermore, since crosslinking is performed by electron beams, the crosslinking density can be adjusted more freely than in the case of thermosetting.

Therefore, leaching of the surfactant (long-term antifogging agent) can be controlled. Furthermore, since it can be cured (crosslinked) without heating, anti-fog properties can be imparted to heat-sensitive materials. Furthermore, since no sensitizing agent is used as in crosslinking with ultraviolet rays, weather resistance is good and there is little deterioration even after long-term use.

In addition, the hydrophilic film of the present invention formed from such a composition has initial antifogging properties due to the hydrophilic groups on the surface, and when it contains a surfactant, it gradually oozes out through the crosslinked structure. As a result, anti-fog properties can be maintained for a long period of time. Furthermore, since it is crosslinked, it has sufficient mechanical strength and hardness. Furthermore, it also has the advantage of having excellent antifogging properties at high temperatures.

Furthermore, since the production method of the present invention irradiates the coating film of the composition with a desired amount of electron beams, the degree of curing (crosslinking density) of the hydrophilic film can be adjusted appropriately, thereby improving long-term antifogging properties. can be controlled.

Claims (47)

[Claims] (1) A composition for forming a hydrophilic film by electron beam irradiation, characterized by containing a polymer, a hydrophilic monomer, and a hydrophilic crosslinkable monomer. (2) The hydrophilic film-forming composition according to claim 1, wherein the polymer has substantially no functional group. (3) The hydrophilic film-forming composition according to claim 1, wherein the polymer has a functional group. (4) In the hydrophilic film-forming composition according to claim 3, the functional group of the polymer is an acryloyl group,
A hydrophilic film-forming composition comprising one or more of methacryloyl groups, allyl groups, and epoxy groups. (5) In the hydrophilic film-forming composition according to any one of claims 1 to 4, the hydrophilic monomer includes a hydroxyl group, a carboxyl group, a metal salt thereof, an amide group,
A hydrophilic film-forming composition characterized by containing one or more of an imide group, a sulfonic acid group, an ammonium base, and a phosphoric acid group. (6) In the hydrophilic film-forming composition according to any one of claims 1 to 5, the hydrophilic crosslinkable monomer includes a hydroxyl group, a carboxyl group, a metal salt thereof, an amide group, an imide group, Crosslinking of one or more hydrophilic groups of sulfonic acid groups and their metal salts, ammonium bases, and phosphoric acid groups with one or more of acryloyl groups, methacryloyl groups, allyl groups, and epoxy groups. 1. A hydrophilic film-forming composition characterized by containing a functional group. (7) In the hydrophilic film-forming composition according to any one of claims 1 to 6, the polymer 100
A hydrophilic film-forming composition, wherein the hydrophilic monomer is 5 to 200 parts by weight, and the hydrophilic crosslinking monomer is 1 to 300 parts by weight. (8) The hydrophilic film-forming composition according to any one of claims 1 to 9, further comprising a solvent. (9) In the hydrophilic film formation according to claim 8, the solvent is 6 parts by weight based on 100 parts by weight of the polymer.
1,000 parts by weight or less of a hydrophilic film-forming composition. (10) A composition for forming a hydrophilic film by electron beam irradiation, which contains a polymer, a hydrophilic monomer, a hydrophilic crosslinking monomer, and a surfactant. (11) The hydrophilic film-forming composition according to claim 10, wherein the polymer has substantially no functional group. (12) The hydrophilic film-forming composition according to claim 10, wherein the polymer has a functional group. (13) In the hydrophilic film-forming composition according to claim 12, the functional group of the polymer is one or more of an acryloyl group, a methacryloyl group, an allyl group, and an epoxy group. A hydrophilic film-forming composition characterized by: (14) In the hydrophilic film-forming composition according to any one of claims 10 to 13, the hydrophilic monomer includes a hydroxyl group, a carboxyl group, a metal salt thereof, an amide group, an imide group, and a sulfonic acid group. A hydrophilic film-forming composition characterized by containing one or more of a group and a metal salt thereof, an ammonium base, and a phosphoric acid group. (15) In the hydrophilic film-forming composition according to any one of claims 10 to 14, the hydrophilic crosslinkable monomer includes a hydroxyl group, a carboxyl group, a metal salt thereof, an amide group, an imide group, sulfonic acid group and its metal salt,
Contains one or more hydrophilic groups selected from ammonium bases and phosphoric acid groups, and one or more crosslinkable functional groups selected from acryloyl groups, methacryloyl groups, allyl groups, and epoxy groups. A hydrophilic film-forming composition characterized by: (16) In the hydrophilic film-forming composition according to any one of claims 10 to 15, the hydrophilic monomer is contained in an amount of 5 to 200 parts by weight based on 100 parts by weight of the polymer.
The hydrophilic crosslinking monomer is 1 to 300 parts by weight.
A hydrophilic film-forming composition characterized in that parts by weight. (17) The hydrophilic film-forming composition according to claims 10 to 16, wherein the surfactant is present in an amount of 100 parts by weight or less based on 100 parts by weight of the polymer. Film-forming composition. (18) The hydrophilic film-forming composition according to claim 17, wherein the surfactant is contained in an amount of 1 to 50 parts by weight. (19) The hydrophilic film-forming composition according to any one of claims 10 to 18, further comprising a solvent. (20) The hydrophilic film-forming composition according to claim 19, wherein the amount of the solvent is 6000 parts by weight or less based on 100 parts by weight of the polymer. (21) A film-like material of a mixture containing a polymer, a hydrophilic monomer, and a hydrophilic crosslinkable monomer is irradiated with an electron beam, and the polymer crosslinks with the hydrophilic monomer and the hydrophilic crosslinkable monomer. A hydrophilic membrane characterized by: (22) The hydrophilic membrane according to claim 21, wherein the polymer has substantially no functional groups. (23) The hydrophilic membrane according to claim 21, wherein the polymer has a functional group. (24) The hydrophilic membrane according to claim 23, wherein the functional group of the polymer is one or more of an acryloyl group, a methacryloyl group, an allyl group, and an epoxy group. hydrophilic membrane. (25) In the hydrophilic membrane according to any one of claims 21 to 24, the hydrophilic monomer includes hydroxyl groups, carboxyl groups, metal salts thereof, amide groups, imide groups, sulfonic acid groups, and A hydrophilic membrane characterized by containing one or more of a metal salt, an ammonium base, and a phosphoric acid group. (26) In the hydrophilic membrane according to any one of claims 21 to 25, the hydrophilic crosslinking monomer includes a hydroxyl group, a carboxyl group, a metal salt thereof, an amide group, an imide group, and a sulfonic acid group. and a metal salt thereof, one or more hydrophilic groups of an ammonium base and a phosphoric acid group, and one or more crosslinkable functionalities of an acryloyl group, a methacryloyl group, an allyl group, and an epoxy group. A hydrophilic membrane characterized by containing a group. (27) In the hydrophilic membrane according to any one of claims 21 to 26, the hydrophilic monomer is present in an amount of 5 to 200 parts by weight based on 100 parts by weight of the polymer, and the hydrophilic crosslinking 1. A hydrophilic membrane characterized in that the content of the hydrophilic monomer is 1 to 300 parts by weight. (28) The hydrophilic membrane according to any one of claims 21 to 27, wherein the mixture further contains a solvent. (29) In the hydrophilic membrane according to claim 28, the solvent is 6 parts by weight based on 100 parts by weight of the polymer.
1,000 parts by weight or less. (30) The hydrophilic membrane according to any one of claims 21 to 29, characterized in that many of the hydrophilic groups are present on the surface. (31) The hydrophilic membrane according to any one of claims 21 to 30, characterized in that the membrane-like material is a coating coated on a support. (32) The hydrophilic membrane according to claim 31, wherein the hydrophilic membrane has a thickness of 0.1 to 30 μm. (33) A film-like material of a mixture containing a polymer, a hydrophilic monomer, a hydrophilic crosslinkable monomer, and a surfactant is irradiated with an electron beam, and the polymer is A hydrophilic membrane characterized by being crosslinked with a crosslinking monomer. (34) The hydrophilic membrane according to claim 33, wherein the polymer has substantially no functional groups. (35) The hydrophilic membrane according to claim 33, wherein the polymer has a functional group. (36) The hydrophilic membrane according to claim 35, wherein the functional group of the polymer is one or more of an acryloyl group, a methacryloyl group, an allyl group, and an epoxy group. hydrophilic membrane. (37) In the hydrophilic membrane according to any one of claims 33 to 36, the hydrophilic monomer includes hydroxyl groups, carboxyl groups, metal salts thereof, amide groups, imide groups, sulfonic acid groups, and A hydrophilic membrane characterized by containing one or more of a metal salt, an ammonium base, and a phosphoric acid group. (38) In the hydrophilic membrane according to any one of claims 33 and 37, the hydrophilic crosslinking monomer includes a hydroxyl group, a carboxyl group, a metal salt thereof, an amide group, an imide group, and a sulfone group. and a metal salt thereof, one or more hydrophilic groups selected from ammonium bases and phosphorus groups, and one or more crosslinkable functionalities selected from acrylloyl groups, methacryloyl groups, allyl groups, and epoxy groups. A hydrophilic membrane characterized by containing a group. (39) In the hydrophilic membrane according to any one of claims 33 to 38, the hydrophilic monomer is present in an amount of 5 to 200 parts by weight based on 100 parts by weight of the polymer, and the hydrophilic crosslinking 1. A hydrophilic membrane characterized in that the content of the hydrophilic monomer is 1 to 300 parts by weight. (40) In the hydrophilic membrane according to claims 33 to 39, the surfactant is
A hydrophilic membrane characterized in that the amount is 100 parts by weight or less relative to 0 parts by weight. (41) The hydrophilic membrane according to claim 40, wherein the surfactant is contained in an amount of 1 to 50 parts by weight. (42) The hydrophilic membrane according to any one of claims 33 to 41, characterized in that many of the hydrophilic groups are present on the surface. (43) In the hydrophilic film according to any one of claims 33 to 42, the hydrophilic group present on the surface exhibits initial antifogging properties, and the surfactant exudes from within the film. A hydrophilic film characterized by a long-term antifogging agent. (44) The hydrophilic membrane according to any one of claims 33 to 43, wherein the film-like material is a coating film applied on a support. (45) In the hydrophilic film according to any one of claims 33 to 44, the film thickness is 0.1 to 30 μm.
A hydrophilic membrane characterized by: (46) Mix a polymer, a hydrophilic monomer, and a hydrophilic crosslinking monomer, apply it in a film, and apply 0.5 to 20 Mr.
A method for producing a hydrophilic film, the method comprising irradiating an ad electron beam. (47) Mix a polymer, a hydrophilic monomer, and a hydrophilic crosslinking monomer surfactant, apply it in a film form, and
A method for producing a hydrophilic membrane, comprising irradiating with an electron beam of ~20 Mrad.