JPH1143614A - Antifogging film and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film which has persistent antifogging performance, transparency and practical film strength, wherein on a hydrophobic polymer segment comprising a hydrophobic monomer and being situated on the side of the substrate, a hydrophilic polymer segment comprising at least one hydrophobic monomer having a specified composition is bonded to the hydrophobic polymer segment through an organic peroxide fragment. SOLUTION: The hydrophilic monomer is selected among those containing a carboxy group, a hydroxyl group, a sulfo group, a phospho group, an alkali metal or ammonium salt thereof, an alkylene oxide group, an amino group, a cyano group, an acid anhydride group or a quat. ammonium salt. It is desirable that the hydrophobic polymer comprises a monomer having an organic peroxide bond of any one of formulas I to V or a hydrophilic monomer in which the hydrophilic polymer segment has an amide group. In the formulae, R<1> , R<2> , R<6> , R<7> , R<11> , R<15> and R<19> are each H methyl; R<3> , R<4> , R<8> R<9> , R<12> , R<13> , R<16> , R<17> , R<20> and R<21> are each 1-4C alkyl; R<5> , R<10> , R<14> , R<18> and R<22> are each a 1-12C alkyl, phenyl or the like; and n is 0-5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifogging film for preventing fogging and adhesion of water droplets due to dew condensation on the surface of a substrate such as a lens or a mirror made of a transparent material such as glass or plastic molding material or film, and the like. It relates to a manufacturing method. More specifically, the present invention relates to an antifogging film capable of effectively imparting antifogging performance to a substrate and maintaining the performance for a long period of time, and a method for producing the same.

[0002]

2. Description of the Related Art In general, when a temperature of a transparent base material becomes lower than the dew point, dew condensation occurs on the surface and the transparency is reduced. Several proposals have conventionally been made as a method for preventing such fogging of the transparent substrate.

For example, a method of applying a hydrophilic substance such as a surfactant or a hydrophilic polymer to the surface of a substrate, a method of forming a coating film containing a surfactant on the surface of a substrate, and a method of applying a hydrophilic film to a substrate. Laminating method (JP-A-62-1825)
No. 3) and a method in which a hydrophilic curable resin is applied to a substrate and cured (JP-A-63-251401).

[0004]

However, since various substrates provided with anti-fogging properties are often used under conditions where water comes into contact with the anti-fogging film, surfactants and hydrophilic In the method of applying the hydrophilic polymer to the surface of the base material, there is a problem that the anti-fogging film dissolves in water and flows down from the surface of the base material, and the anti-fogging durability is lacking.

In the method using a cured product of a hydrophilic resin or a hydrophilic film as an antifogging film, the hardness of the coating film is reduced due to moisture absorption, and the coating film is damaged, and the coating film is peeled off, resulting in durability. There was a problem that it was inferior. In addition, there is a problem that the antifogging film is whitened due to moisture absorption.

The present invention has been made by focusing on the problems existing in the prior art as described above. The purpose is to maintain the anti-fogging performance for a long period of time, have good transparency, have a practical coating film strength, and have good adhesion to the substrate to which anti-fogging property is to be imparted. And a method for producing the same. Another object of the present invention is to provide an antifogging film that can be easily manufactured while preventing the possibility of being restricted by usable substrates, and a method for manufacturing the same.

[0007]

Means for Solving the Problems In order to achieve the above object, the present inventors have made intensive studies and as a result, completed the present invention.

[0008] That is, the antifogging film of the first invention is an antifogging film formed on a substrate, wherein the hydrophobic polymer segment (I) formed from a hydrophobic monomer is provided on the substrate side. Located in
At least one selected from the group consisting of the following hydrophilic monomers:
Polymer segment formed from two kinds of monomers (I
I) is composed of a polymer bonded to the hydrophobic polymer segment (I) via the organic peroxide bonding group fragment on the hydrophobic polymer segment (I).

Hydrophilic monomers: carboxyl group, hydroxyl group,
At least one functional group selected from the group consisting of sulfonic acid groups, phosphoric acid groups, alkali metal salts or ammonium salts thereof, alkylene oxide groups, amino groups, amide groups, cyano groups, acid anhydride groups and quaternary ammonium bases Monomer having a group.

The antifogging film of the second invention is the antifogging film according to the first invention, wherein the hydrophobic polymer segment (I) is formed of a monomer having an organic peroxide bonding group, and the hydrophilic polymer segment (II) ) Is formed from a hydrophilic monomer having an amide group.

In a third aspect of the present invention, there is provided a method for producing an anti-fogging film, wherein a hydrophobic polymer having an organic peroxide bonding group formed on a substrate is selected from the group consisting of the above hydrophilic monomers. At least one type is contacted and heated to 60 to 150 ° C.

In a fourth aspect of the present invention, there is provided a method for producing an antifogging film according to the third aspect, wherein the hydrophobic polymer having an organic peroxide bonding group is an organic polymer having the following general formula (1) to (5). A polymer segment formed from a monomer having at least one selected from the group of monomers having an oxidative bonding group,
This is a method in which a hydrophilic monomer uses a monomer having an amide group. General formula (1)

[0013]

Embedded image(Where R¹ Is a hydrogen atom or a methyl group, R^Two Is a hydrogen atom
Or a methyl group, R^Three , R ^Four Is alkyl having 1 to 4 carbon atoms
Group, R^Five Is an alkyl group having 1 to 12 carbon atoms, and 3 to 1 carbon atoms
2 cycloalkyl group, phenyl group, alkyl group substituted
And n represents 1 to 5. ) General formula (2)

[0014]

Embedded image(Where R⁶ Is a hydrogen atom or a methyl group, R⁷ Is a hydrogen atom
Or a methyl group, R⁸ , R ⁹ Is alkyl having 1 to 4 carbon atoms
Group, R^TenIs an alkyl group having 1 to 12 carbon atoms, and 3 to 1 carbon atoms
2 cycloalkyl group, phenyl group, alkyl group substituted
And n represents 0 to 4. ) General formula (3)

[0015]

Embedded image (Wherein, R ¹¹ is a hydrogen atom or a methyl group, R ¹² and R ¹³ are an alkyl group having 1 to 4 carbon atoms, R ¹⁴ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, A phenyl group or an alkyl-substituted phenyl group.) General formula (4)

[0016]

Embedded image (Wherein, R ¹⁵ is a hydrogen atom or a methyl group, R ¹⁶ and R ¹⁷ are an alkyl group having 1 to 4 carbon atoms, R ¹⁸ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, A phenyl group or an alkyl group-substituted phenyl group.) General formula (5)

[0017]

Embedded image (Wherein, R ¹⁹ is a hydrogen atom or a methyl group, R ²⁰ and R ²¹ are an alkyl group having 1 to 4 carbon atoms, R ²² is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, Represents a phenyl group or an alkyl-substituted phenyl group.)

[0018]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. The antifogging film is characterized by its structure,
A hydrophobic polymer segment (I) formed on a substrate,
The hydrophilic polymer segment (II) formed thereon is chemically bonded via an organic peroxide bonding group fragment. More specifically, the anti-fogging film is composed of a graft copolymer composed of a hydrophobic polymer segment (I) and a hydrophilic polymer segment (II), and the hydrophilic polymer segment (II) is Hydrophobic polymer segment (I)
It is a graft polymer chain (side chain) of the graft copolymer bonded to the (main chain) via an organic peroxide bonding group fragment. Note that the hydrophobic polymer and the hydrophilic polymer are respectively a hydrophobic polymer segment (I) or a hydrophilic polymer segment (I
As I), homopolymers that do not bond to each other may be contained. That is, it is sufficient that the intended purpose can be achieved even when the graft ratio is low. Incidentally, the graft ratio of the hydrophobic polymer increases as the film thickness decreases, and the graft ratio of the hydrophilic polymer increases by removing the homopolymer and unreacted monomers.

The hydrophobic polymer segment (I) is a polymer obtained by polymerizing a monomer having an organic peroxide bonding group and having a structure in which the organic peroxide bonding group is cleaved. . Here, the monomer having an organic peroxide bonding group is a group that generates a radical by heating, that is, a monomer having at least one organic peroxide bonding group and at least one polymerizable unsaturated double bond in one molecule. Say.

The monomers having an organic peroxide bonding group are specifically listed below. Specific examples of the monomer having a peroxide bond represented by the general formula (1) include t
-Butylperoxy (meth) acryloyloxyethyl carbonate, t-butylperoxy (meth) acryloyloxyethoxyethyl carbonate, t-butylperoxy (meth) acryloyloxyisopropyl carbonate, t-amylperoxy (meth) acryloyloxyethyl carbonate, t- Amyl peroxy (meth) acryloyloxy isopropyl carbonate, t
-Hexylperoxy (meth) acryloyloxyethyl carbonate, t-hexylperoxy (meth) acryloyloxyisopropyl carbonate, t-octylperoxy (meth) acryloyloxyethyl carbonate, cumylperoxy (meth) acryloyloxyethyl carbonate, p-isopropyl Cumyl peroxy (meth) acryloyloxyethyl carbonate, p
-Menthylperoxy (meth) acryloyloxyethyl carbonate, 1-cyclohexyl-1-methylethylperoxy (meth) acryloyloxyethyl carbonate and the like.

Specific examples of the monomer having a peroxide bond represented by the general formula (2) include t-butylperoxy (meth) allylcarbonate and t-butylperoxy (meth) allyloxyethyl. Carbonate, t-
Butylperoxy (meth) allyloxyethoxyethyl carbonate, t-amylperoxy (meth) allyl carbonate, t-hexylperoxy (meth) allylcarbonate, t-octylperoxy (meth) allylcarbonate, cumyl (meth) allylcarbonate, etc. Can be

Specific examples of the monomer having a peroxide bond represented by the general formula (3) include t-butyl peroxymethyl fumarate, t-butyl peroxyethyl fumarate, and t-butyl peroxy. -N-propyl fumarate, t-butyl peroxyisopropyl fumarate, t-butyl peroxy-n-butyl fumarate, t
-Butyl peroxy-t-butyl fumarate, t-butyl peroxy-n-octyl fumarate, t-butyl peroxy-2-ethylhexyl fumarate, t-butyl peroxyphenyl fumarate, t-butyl peroxy-m-toluyl fumarate T-butyl peroxycyclohexyl fumarate, t-amyl peroxy-n-propyl fumarate, t-amyl peroxyisopropyl fumarate, t-amyl peroxy-n-butyl fumarate, t-amyl peroxyphenyl fumarate, t-amyl peroxyphenyl fumarate
Hexyl peroxyethyl fumarate, t-hexyl peroxyisopropyl fumarate, t-hexyl peroxy-t-butyl fumarate, t-hexyl peroxy-2-ethylhexyl fumarate, t-octyl peroxymethyl fumarate, t-octyl peroxyisopropyl fumarate Rate, t-octyl peroxy-n-octyl fumarate, t-octyl peroxycyclohexyl fumarate, cumyl peroxyisopropyl fumarate, p-menthyl peroxyisopropyl fumarate and the like.

Specific examples of the peroxide-containing monomer represented by the general formula (4) include t-butylperoxy (meth) acrylate, t-amylperoxy (meth) acrylate, and t-amylperoxy (meth) acrylate. Hexylperoxy (meth) acrylate, t-octylperoxy (meth) acrylate, cumylperoxy (meth) acrylate,
Examples include p-menthyl peroxy (meth) acrylate, 1-cyclohexyl-1-methylethyl peroxy (meth) acrylate, and the like.

Specific examples of the monomer having a peroxide bond represented by the general formula (5) include t-butylperoxy (meth) acryloyloxyethylcarbamate and t-amylperoxy (meth) acryloyl Oxyethyl carbamate, t-hexyl peroxy (meth)
Acryloyloxyethyl carbamate, t-octylperoxy (meth) acryloyloxyethyl carbamate, cumylperoxy (meth) acryloyloxyethyl carbamate, p-menthylperoxy (meth) acryloyloxyethyl carbamate, 1-cyclohexyl-1-methylethylperoxy ( (Meth) acrylate and the like.

Among these monomers containing a peroxide bond, preferred monomers are t-butylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, and t-hexylperoxymethacryloyloxyethyl carbonate. , T-butyl peroxyallyl carbonate, t-butyl peroxyisopropyl fumarate and t-butyl peroxymethacryloyloxyethyl carbamate. This is because these peroxide-containing monomers have a thermal decomposition temperature of 60 ° C. or higher, are easily available, and are economical.

In the hydrophobic polymer segment (I), in addition to a monomer having an organic peroxide bonding group, one or more monomers having no organic peroxide bonding group may be used in combination. It may be formed. Such a monomer having no organic peroxide bonding group is not particularly limited, and specifically, alkyl (meth) acrylates such as methyl (meth) acrylate and butyl (meth) acrylate, 2-hydroxyethyl ( Hydroxyl group-containing (meth) acrylates such as (meth) acrylate and 2-hydroxypropyl (meth) acrylate, (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, and N, N-dialkylaminoalkyl (meth) acrylate , Fumaric acid esters, glycidyl (meth) acrylate, maleic acid esters, itaconic acid esters, (meth) acrylic acid, maleic anhydride, styrene, vinyl acetate, N-vinylpyrrolidone, N-vinylpyrudine, fluorine-containing monomer Body, silicon-containing monomer, phosphorus-containing monomer, etc. It is.

The amount of the monomer having no organic peroxide bonding group is preferably 95% by weight or less in order to maintain the polymerization efficiency of the hydrophilic monomer by heating. The organic peroxide bonding group fragment is formed by radical cleavage of the group bonded to the hydrophobic polymer segment (I) described above,
It refers to a group bonded to the hydrophobic polymer segment (I).

Next, the hydrophilic polymer segment (II)
Is a group consisting of a carboxyl group, a hydroxyl group, a sulfonic acid group, a phosphoric acid group, an alkali metal salt or an ammonium salt thereof, an alkylene oxide group, an amino group, an amide group, a cyano group, an acid anhydride group and a quaternary ammonium base. It is a polymer segment formed from at least one kind of monomer selected from hydrophilic monomers having at least one kind of functional group.

Specific examples of the hydrophilic monomer include the following monomers (1) to (15), and one of these monomers may be used alone or as appropriate. A mixture of more than one species can be used. (1) Unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid and β- (meth) acryloyloxyethyl hydrogen succinate. (2) Unsaturated carboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride and 4-methacryloxyethyl trimellitic anhydride. (3) Hydroxyphenoxyethyl (meth) acrylate, the addition mole number of ethylene oxide is 2 to 90, and the addition mole number of hydroxyphenoxy polyethylene glycol (meth) acrylate and propylene oxide is 2 to 9
And phenol group-containing monomers such as hydroxyphenoxypolypropylene glycol (meth) acrylate, vinylphenol, and hydroxyphenylmaleimide.

(4) Sulfonic acid group-containing monomers such as sulfoxyethyl (meth) acrylate, styrene sulfonic acid, acrylamide-t-butyl sulfonic acid and (meth) allyl sulfonic acid. (5) Phosphoric acid group-containing monomers such as mono 2- (meth) acryloyloxyethyl acid phosphate. (6) N, N-dimethyl (meth) acrylamide, N, N
-Diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, acryloylmorpholine,
N, N-dimethylaminopropyl (meth) acrylamide, (meth) acrylamide, N-methylol (meth)
(Meth) acrylamides such as acrylamide.

(7) Aminoalkyl (meth) acrylates such as N, N-diethylaminoethyl (meth) acrylate and N, N-dimethylaminoethyl (meth) acrylate. (8) 2-hydroxyethyl (meth) acrylate, 2-
Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate and 2,3-dihydroxypropyl (meth) acrylate; (9) Polyethylene glycol mono (meth) acrylate having an addition mole number of ethylene oxide of 2 to 98, methoxypolyethylene glycol mono (meth) acrylate having an addition mole number of ethylene oxide of 2 to 98, and an addition mole number of ethylene oxide of 2 to 98 Polyoxyethylene mono (meth) such as phenoxy polyethylene glycol mono (meth) acrylate of 98, nonylphenol monoethoxylate (meth) acrylate, methoxyethyl acrylate and ethoxydiethylene glycol (meth) acrylate having an ethylene oxide addition mole number of 1 to 4 Acrylates.

(10) sodium salt of (meth) acrylic acid,
Sodium styrenesulfonate, sodium sulfonate ethoxy (meth) acrylate, acrylamide-t-
Alkali metal salts of acid group-containing monomers such as the sodium salt of butylsulfonic acid. (11) Quaternary ammonium base-containing (meth) acrylates such as hydroxyethyltrimethylammonium (meth) acrylate chloride and hydroxypropyltrimethylammonium (meth) acrylate chloride. (12) Allyl glycol, (meth) allyl compounds such as polyethylene glycol mono (meth) allyl ether and methoxypolyethylene glycol monoallyl ether having 3 to 32 ethylene oxide addition moles.

(13) Cyclic heterocycle-containing compounds such as N-vinylpyrrolidone and N-vinylcaprolactam. (14) Vinyl cyanides such as acrylonitrile, methacrylonitrile and vinylidene cyanide. (15) Reactive emulsifiers exemplified by the following chemical formulas (6) to (12).

[0034]

Embedded image (However, Ф is an aromatic ring, (OA) and (AO) are oxyalkylene groups, m and n are each a number of 1 to 20, R ²³ and R
²⁴ is an alkyl group having 1 to 20 carbon atoms. )

[0035]

Embedded image (However, R ²⁵ is an alkyl group having 1 to 20 carbon atoms.)

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image (However, Φ is an aromatic ring.)

[0039]

Embedded image (However, Φ is an aromatic ring.)

[0040]

Embedded image (However, Φ is an aromatic ring.)

As the hydrophilic monomer, specifically,
Lapisol AIS-112 and AIS-212 manufactured by Nippon Yushi Co., Ltd., and Latemul S manufactured by Kao Corporation
-180, 180-A, trade name A manufactured by Nippon Emulsifier Co., Ltd.
ntox-MS-2N, Antox-MS-60, RA
-4211, trade name Eleminor J manufactured by Sanyo Kasei Co., Ltd.
S-2, RS-30, trade names manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Aqualon HS-20, HS-10, HS-5, New Frontair A-229E, trade name S manufactured by Asahi Denka Kogyo KK
E-10N and the like.

Among these, monomers having an amide group are preferable in that the performance of the antifogging film and the durability thereof are particularly good. Specifically, (meth) acrylamide, N, N
-Dimethyl (meth) acrylamide, (meth) acrylmorpholine, (meth) acrylamide-t-butylsulfonic acid and salts thereof.

As the monomer forming the hydrophilic polymer segment (II), a monomer having no hydrophilic property can be blended in addition to the hydrophilic monomer. Such a monomer is not particularly limited as long as it is capable of radical polymerization. Specifically, alkyl or glycidyl of an unsaturated carboxylic acid such as (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid is used. Examples include esters, styrene, vinyl esters of saturated carboxylic acids, fluorine-containing monomers, and silicon-containing monomers. It is necessary that the compounding amount is within a range that does not lose the properties as a hydrophilic polymer.
% By weight or less is preferred.

Next, a method for producing the antifogging film will be described. The method for producing the antifogging film is such that a hydrophilic monomer is brought into contact with a layer made of a hydrophobic polymer having an organic peroxide bonding group formed on a substrate and heated to 60 to 150 ° C. In this method, thermal graft polymerization is caused on the substrate surface to obtain an antifogging film.

The organic peroxide-bonded group bonded to the hydrophobic polymer generates a radical by heating, and the hydrophilic monomer is graft-polymerized from the radical of the organic peroxide-bonded group fragment generated here. A layer of coalesced segments (II) is formed. At this time, if the heating temperature is lower than 60 ° C., the generation of radicals is reduced and the graft polymerization does not proceed well. On the other hand, if the heating temperature is higher than 150 ° C., the hydrophilic monomer is volatilized and the graft polymerization reaction becomes unstable, which is not preferable. The antifogging film thus obtained is a hydrophilic polymer segment comprising a graft polymer chain of a hydrophilic monomer bonded via an organic peroxide bonding group fragment on the layer of the hydrophobic polymer segment (I). (I
It has a two-layer structure in which the layer I) is formed.

FIG. 1 conceptually shows a method for producing such an antifogging film. In FIG. 1, a solid line A is a main chain of a polymer having an organic peroxide bonding group, -OO- is a peroxide bonding group, -O. Is an organic peroxide bonding group fragment radical in which the organic peroxide bonding group is cleaved,- O- represents an organic peroxide bonding group fragment, and dotted line B represents a graft polymer chain of a hydrophilic polymer obtained by polymerizing a hydrophilic monomer.

Next, a specific method for producing the antifogging film and each component used therein will be described. First, a layer made of a hydrophobic polymer having an organic peroxide bonding group will be described. The layer made of this polymer can be obtained by the following methods. (i) A method of forming a layer by applying a composition containing a homopolymer or a copolymer of a monomer having an organic peroxide bonding group alone or both to a substrate. (ii) A method of applying a composition containing a monomer having an organic peroxide bonding group onto a substrate and then polymerizing the composition with heat. (iii) A method in which an organic peroxide bonding group is introduced into the surface of a polymer having no organic peroxide bonding group and having a functional group by a chemical reaction.

Among them, the method (i) is preferred because it is simple. When applying, the composition may be diluted with a solvent as necessary. The monomer having an organic peroxide bonding group is as described above.

The polymer having an organic peroxide bonding group is as follows:
It is obtained by polymerization using a usual radical polymerization initiator. In this case, the polymer may be obtained by polymerizing one or more of monomers having an organic peroxide bonding group alone, or one of the above-mentioned monomers having no organic peroxide bonding group.
It is obtained by copolymerizing with one or more species.

The amount of the monomer component having an organic peroxide bonding group in the polymer having an organic peroxide bonding group is preferably from 5 to 100% by weight, and if it is less than 5% by weight, the polymerization of the hydrophilic monomer by heating is carried out. Becomes inefficient.

In the layer comprising the polymer having an organic peroxide bonding group, in addition to the polymer having an organic peroxide bonding group, a monomer having an unreacted organic peroxide bonding group, It may contain an additive used for forming a film. Such additives include, for example, other monofunctional or polyfunctional monomers and their polymers, heat polymerization initiators,
Curing agents, ultraviolet absorbers, leveling agents, surfactants,
Examples include inorganic fillers such as colloidal silica.
In addition, a silane coupling agent, a titanate coupling agent, or the like, which is generally used, may be added to improve the adhesion to the substrate.

Next, the layer of the hydrophilic polymer segment (II) formed from the hydrophilic monomer will be described. The hydrophilic monomer for forming the layer of the polymer segment (II) contains the hydrophilic monomer alone or another solvent or additive. Although the concentration of the hydrophilic monomer in the composition containing the hydrophilic monomer may be 100%, a layer of a polymer in which the hydrophilic monomer is dissolved and which has an organic peroxide bonding group can be used. May be diluted with a solvent that does not dissolve the compound. The solvent is not particularly limited, but polar solvents such as water, methanol, acetone, and methyl ethyl ketone are preferred. The hydrophilic monomer may contain other monofunctional and polyfunctional monomers and additives such as a surfactant and a thickener.

When the hydrophilic monomer is brought into contact with the polymer segment (I) having an organic peroxide bonding group, the layer of the polymer segment (I) having an organic peroxide bonding group is If it is dissolved in, it may cause adverse effects. That is, the appearance of the obtained anti-fogging film may be deteriorated by whitening or the like, or the anti-fogging performance may be deteriorated because the surface layer does not become a uniform layer of the hydrophilic polymer. For this reason, it is preferable that the hydrophilic monomer does not dissolve the polymer having an organic peroxide bonding group.

As a method for bringing the hydrophilic monomer into contact with the polymer segment (I) having an organic peroxide-bonding group, the hydrophilic monomer may be provided on a layer comprising the polymer segment (I) having an organic peroxide-bonding group. A monomer may be applied, or a substrate having a layer of the polymer segment (I) having an organic peroxide bonding group on the surface may be immersed in the hydrophilic monomer. Further, in order to prevent oxygen-induced damage, the hydrophilic monomer may be covered with a heat-permeable material, for example, a plate or film made of glass, quartz, transparent plastic, or the like.

As described above, the hydrophilic monomer includes a carboxyl group, a hydroxyl group, a sulfonic acid group, a phosphoric acid group, an alkali metal salt or an ammonium salt thereof, an alkylene oxide group, an amino group, an amide group, and a cyano group. And a monomer having at least one functional group selected from an acid anhydride group and a quaternary ammonium base.

Specific examples include the above-mentioned hydrophilic monomers, and one of these monomers may be used singly or as a mixture of two or more. Among these, monomers having an amide group are preferable in that the performance of the anti-fogging film and the durability thereof are particularly good, and specifically, (meth) acrylamide, N, N-dimethyl (meth) acrylamide , (Meth) acrylmorpholine, (meth) acrylamide-t-butylsulfonic acid and salts thereof.

In the method for producing the antifogging film, when there is a hydrophilic monomer or a homopolymer of the hydrophilic monomer which has not reacted after heating, it is preferable to wash the film with water or the like as necessary.

As the base material, a transparent material such as glass, plastic molding material or film is used. Substrates with an antifogging film formed on the surface are used for optical components such as lenses, mirrors and prisms, or window glasses for vehicles, ships, houses, etc., ski goggles, underwater glasses, helmet shields, instrument covers, agricultural and horticultural products. It is suitably used for applications such as films.

As described above, according to this embodiment, the following effects are exhibited. (1) A hydrophilic polymer segment (I
Since I) is oriented, the antifogging film on the substrate surface can exhibit excellent antifogging properties. (2) The hydrophilic polymer segment (II) is bonded to the hydrophobic polymer segment (I) via an organic peroxide bonding group fragment, and the hydrophobic polymer segment (I) adheres to the substrate. Therefore, the anti-fog performance can be maintained for a long period of time. (3) Since the film formed by the hydrophilic polymer segment (II) has good uniformity, the performance can be expressed by a thin film and the transparency is excellent. (4) Moreover, the anti-fogging film hardly swells,
There is no possibility of peeling, and it has practical coating strength. (5) The hydrophobic polymer segment (I) is oriented on the base material side, and the bonding force between the hydrophobic polymer segment (I) and the base material is good, so that a group to impart antifogging property is provided. Good adhesion to the material. (6) Since the mechanism for initiating the polymerization is not a mechanism in which the organic peroxide bond-type initiator withdraws hydrogen from the substrate to initiate the polymerization, it is possible to suppress the possibility that the usable substrate is limited. (7) A layer of the hydrophobic polymer segment (I) is formed on the surface of the base material, and a hydrophilic monomer is applied thereon, followed by heating to form an antifogging film formed on the surface of the base material. Can be easily manufactured.

[0060]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples, Comparative Examples and Reference Examples, but the present invention is not limited thereto. In addition,% in a text and a table represents weight%. The molecular weight is a value measured by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.

The abbreviations in the text and tables are as follows. PO1: t-butylperoxymethacryloyloxyethyl carbonate PO2: t-hexylperoxymethacryloyloxyethyl carbonate PO3: t-butylperoxyallylcarbonate PO4: t-butylperoxyisopropyl fumarate PO5: t-butylperoxymethacrylate PO6: t-butylperoxy Methacryloyloxyethyl carbamate MMA: Methyl methacrylate BMA: Butyl methacrylate LMA: Lauryl methacrylate

ST: styrene DBF: dibutyl fumarate GMA: glycidyl methacrylate NMAAm: N-methylol acrylamide MAA: methacrylic acid HEMA: 2-hydroxyethyl methacrylate KBM503: 3-trimethoxysilylpropyl methacrylate (“KBM- manufactured by Shin-Etsu Chemical Co., Ltd.) 503 ") PPZ: phosphazene-based 6-functional methacrylate (" Idemitsu PPZ "manufactured by Idemitsu Petrochemical Co., Ltd.) 3002A: Bifunctional epoxy acrylate (" Epolite 3002A "manufactured by Kyoeisha Chemical Co., Ltd.)

DMAEMA: N, N-dimethylaminoethyl methacrylate DMAAm: N, N-dimethylacrylamide AAm: Acrylamide ACMO: Acryloylmorpholine PE350: Polyethylene glycol monomethacrylate (“Blenmer PE-350” manufactured by NOF Corporation) ATBS: Acrylamide t-Butylsulfonic acid ("ATBS" manufactured by Toagosei Co., Ltd.) QA: hydroxypropyltrimethylammonium methacrylate chloride ("Blemmer QA" manufactured by NOF Corporation)

MS2N: Sulfoethyl methacrylate N
a salt ("AntoxMS-2N" manufactured by Nippon Emulsifier Co., Ltd.) DQ100: methacryloyloxyethyltrimethylammonium chloride ("Light Ester DQ-100" manufactured by Kyoeisha Chemical) PME400: Polyethylene glycol monomethacrylate ("Blemmer PME400" manufactured by NOF Corporation) MEK: methyl ethyl ketone PGM: propylene glycol monomethyl ether THF: tetrahydrofuran PVA: saponified polyvinyl acetate (“Gohsenol KH-17” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) OP80: nonionic surfactant (“Nonion OP-80 manufactured by NOF Corporation”) ")

TTA: Triethylenetetramine (“Amicure” manufactured by Ajinomoto Co.) ACS: Colloidal silica (“Snowtex O” manufactured by Nissan Chemical Co., Ltd.) with trimethoxysilylpropyl methacrylate (“KBM-503” manufactured by Shin-Etsu Chemical Co., Ltd.) 20% MEK solution of treated acrylic-modified colloidal silica LPO: Lauroyl peroxide ("Perloyl L" manufactured by NOF Corporation)

Reference Example 1 (Production of Polymer Containing Organic Peroxide Bonding Group) 50 g of MEK was charged into a 1-liter reaction vessel equipped with a stirrer, a thermometer, a purge gas inlet, and a water-cooled condenser. Heated to ° C. Then, while stirring, 90 g of methyl methacrylate, PO11
A mixture of 0 g, 50 g of MEK, and 5 g of LPO was added dropwise over 2 hours. After the completion of the dropwise addition, stirring was continued for 4 hours to complete the polymerization. The resulting solution was poured into petroleum ether to precipitate a polymer, which was then dried to obtain an organic peroxide-bonding group-containing polymer a (described as polymer a in the table). Its weight average molecular weight (described as Mw in the table) is 210
00. From iodometry, it was confirmed that the same amount of peroxide bonding group as that charged was introduced into the polymer.

Reference Examples 2 to 12 Polymerization was carried out in the same manner as in Reference Example 1 except that the monomers were changed to the types and amounts shown in Tables 1 and 2, and an organic peroxide-containing polymer b
To l (described as polymers b to l in the table).

[0068]

[Table 1]

[0069]

[Table 2]

Example 1 (Production of Coating Film) As a coating solution (a), 20% M of the polymer a obtained in Reference Example 1 was used.
Using an EK solution, a 10 cm × 10 cm, 2 mm thick polycarbonate plate was coated with a bar coater so that the dry film thickness was 5 μm, and dried at 50 ° C. for 10 minutes. 20% A as a monomer solution (b) on the obtained coating film
After applying the TBS aqueous solution, put it in a hot air circulating thermostat,
Heat to 130 ° C. and hold for 60 minutes. After heating, wash with water,
By drying, a colorless and transparent antifogging film was obtained.

Next, the physical properties of the obtained antifogging film were evaluated by the following evaluation methods. (1) Graft thickness The thickness before and after the graft polymerization is measured using a digital thickness gauge (Sheen
Instrument Inc.) and the increase was expressed as a graft thickness (μm). (2) Coating film hardness A pencil scratch test was performed in accordance with JIS K-5400, and the coating film hardness was represented by pencil hardness.

(3) Adhesion According to the grid tape method of JIS K-5400, the coating film is cut in the vertical and horizontal directions with a cutter knife to make 100 cross cuts (cut pieces) reaching the base material. Then, a cellophane adhesive tape [manufactured by Nichiban Co., Ltd.] was affixed and peeled in a direction perpendicular to the adhesive surface, and the number of crosscuts remaining without peeling was represented by the following symbol.

：: 100/100, Δ: 80/100 or more, ×: less than 80/100 (4) Anti-fogging property (a) Breath test Blowing the coating film in a constant temperature room at 20 ° C. and 50% relative humidity The cloudiness was visually determined according to the following criteria.

：: no fogging, Δ: slight fogging, x: fogging of the entire surface (b) Steam test A test plate was fixed at a position 1 cm from the water surface on a 60 ° C. water bath, and after 10 minutes The cloudiness was visually determined according to the following criteria.

◎: no water droplets, ○: no water droplets with a diameter of 5 mm or less, Δ: partial water droplets with a diameter of 5 mm or less, ×: water droplets of 5 mm or less on the entire surface (5) Persistence test plate Was immersed in water for one month, dried, and subjected to the above breath test, steam test, and the following coating film appearance test.

Coating Film Appearance Test (Haze Value) The haze value was measured by a direct-reading haze meter (manufactured by Toyo Seiki Seisaku-sho, Ltd.). In general, the value is preferably 1.0 or less, and if it exceeds 1.0, it is determined that the appearance is poor. Table 4 shows the results.

Examples 2 to 10 As shown in Table 3, reference examples 1 to 1 were used as coating solutions (a).
Using a solution consisting of the polymers a to j obtained in Step 0, various monomers, additives and a solvent, Examples 3, 6, 8,
10 was applied to a glass plate, Example 7 was applied to an acrylic plate, and Examples 2, 4, 5, and 9 were applied to a polycarbonate plate, and was applied using a bar coater so that the dry film thickness became 5 μm. Dry at 10 ° C. for 10 minutes. After a 20% ATBS aqueous solution was applied as a monomer solution (b) on the obtained coating film, the solution was placed in a hot-air circulating thermostat, and Examples 2 to 6 and 8 were performed.
In Examples 10 to 10, the temperature was raised to 130 ° C, and in Example 7, the temperature was raised to 80 ° C, and each was kept for 60 minutes. After completion of the heating, washing with water and drying were performed to obtain a colorless and transparent anti-fogging film, and the physical properties were evaluated in the same manner as in Example 1. Table 5 shows the evaluation results.

Examples 11 to 20 An antifogging film was formed by the method described in Example 1 except that the monomer solution (b) described in Table 4 was used, and the physical properties were evaluated in the same manner as in Example 1. did. Table 6 shows the evaluation results.

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

[Table 5]

[0082]

[Table 6]

Example 21 A mixture of 20 g of the polymer k, 5 g of TTA, and 30 g of PGM was applied to a polycarbonate plate so as to have a dry film thickness of 5 μm, and heated at 120 ° C. for 1 hour. Then, 20
After applying the% ATBS aqueous solution, heating, washing with water and drying were performed in the same manner as in Example 1, and the physical properties were evaluated in the same manner as in Example 1. Table 7 shows the evaluation results.

Example 22 A mixture of 20 g of Polymer 1 and 20 g of MEK was applied to a glass plate so that the dry film thickness became 2 μm, and the mixture was dried at 80 ° C. for 30 minutes.
Heated for a minute. Next, after applying a 20% AAm aqueous solution, heating, washing with water and drying were performed in the same manner as in Example 1, and the physical properties were evaluated in the same manner as in Example 1. Table 7 shows the evaluation results.

Example 23 A mixture of 20 g of the polymer a and 20 g of MEK was mixed with a PET film (“Tetron HP7” manufactured by Teijin Limited, 100 μm thick).
m) was applied so that the dry film thickness became 2 μm, and heated at 80 ° C. for 30 minutes. Then, after applying a 20% ACMO aqueous solution, heating, washing with water and drying were performed in the same manner as in Example 1, and the physical properties were evaluated in the same manner as in Example 1. Table 7 shows the evaluation results.

Example 24 10 g of PO6, 10 g of PPZ, 5 g of 3002A, M
EK 25 g of the mixture was applied to an acrylic plate with a dry film thickness of 5 μm.
m and dried at 60 ° C. for 10 minutes. Then, after applying a 20% ATBS aqueous solution, the solution was placed in a hot-air circulation type thermostat, heated to 80 ° C. and maintained for 60 minutes, washed with water and dried, and the physical properties were evaluated as in Example 1. Table 7 shows the evaluation results.

Example 25 A mixture of 20 g of polymer b and 20 g of MEK was applied to an acrylic plate so that the dry film thickness became 5 μm, and the mixture was heated at 60 ° C. for 1 hour.
Dried for 0 minutes. Put this in a 20% ATBS aqueous solution,
Heated to 80 ° C. and kept for 60 minutes. Then, it was washed with water and dried, and the physical properties were evaluated in the same manner as in Example 1. Table 7 shows the evaluation results.

Example 26 A mixture of 20 g of the polymer a and 20 g of MEK was applied to an acrylic plate so that the dry film thickness became 5 μm, and 1 hour at 60 ° C.
Dried for 0 minutes. Next, a 20% AAm aqueous solution is applied,
After placing the glass plate directly thereon, heating, washing and drying were performed in the same manner as in Example 1, and the physical properties were evaluated in the same manner as in Example 1.
Table 7 shows the evaluation results.

[0089]

[Table 7]

Comparative Example 1 The surfactant OP80 was applied to an acrylic plate, and the physical properties were evaluated in the same manner as in Example 1. Table 8 shows the evaluation results.

Comparative Example 2 MMA / DMAAm (weight ratio 80/20) copolymer 2
A mixture of 0 g, 5 g of PME400, 5 g of NMAAm, 1 g of benzoyl peroxide, and 30 g of MEK was applied to an acrylic plate so as to have a dry film thickness of 5 μm, placed in a hot-air circulating thermostat, heated to 80 ° C., and kept for 60 minutes. This was evaluated for physical properties in the same manner as in Example 1. Table 8 shows the results.
It was shown to.

Comparative Example 3 MMA / HEMA (weight ratio 65/35) copolymer 30
A mixture of 0 g, 100 g of HEMA, 10 g of diethylene glycol dimethacrylate, 5 g of a surfactant ("Emulgen 106" manufactured by Kao Corporation), and 300 g of methylcellosolve was applied to an acrylic plate, dried, and irradiated with an electron beam. This was evaluated for physical properties in the same manner as in Example 1. Table 8 shows the results.

Comparative Example 4 An acetylcellulose film was saponified with sodium hydroxide and then attached to an acrylic plate. About this, physical property was evaluated similarly to Example 1. Table 8 shows the results.

[0094]

[Table 8]

As shown in Tables 5 to 8, the following can be understood from the results of the examples and the comparative examples. That is, Comparative Example 1
The surfactant coated with the surfactant and the cured product containing the surfactant of Comparative Example 3 have good initial performance, but have no water resistance and easily deteriorate in performance. When the copolymer containing the hydrophilic component of Comparative Example 2 was applied and cured, its initial performance was insufficient, and it became white when exposed to water for a long period of time. The cellulose film of Comparative Example 4 has water resistance, but has insufficient antifogging performance.

On the other hand, the anti-fogging films of Examples 1 to 26 were excellent in the initial anti-fogging performance, and the performance was maintained even after immersion in water. It is clear that both antifog performance and durability are excellent.

Example 27 An antifogging film was formed by the method described in Example 1 except that a 20% MEK solution of the polymer a was used as the coating liquid (a) and a 20% AAm aqueous solution was used as the monomer solution (b). Obtained. A polymer obtained by shaving about 10 μm from the surface of the obtained anti-fog film 0.1
g was dissolved in THF, and separated with water and THF by the fractional precipitation method described in “Polymer Solution” (edited by the Editing Committee for Polymer Experiments of Polymer Society, Kyoritsu Shuppan) using water and THF. = 0.06 g of component precipitated at 2 to 5 (weight ratio)
was gotten.

The nuclear magnetic resonance spectrum analysis (NMR) and the infrared absorption spectrum analysis (IR) confirmed that the MMA component and the ATBS component of the polymer a were a graft polymer. In this graft polymer, the peroxide bond existing in the case of the polymer a alone was disappeared by the measurement of iodometry. From these results, it was found that the obtained graft copolymer was a graft copolymer in which a peroxide bonding group was bonded via a cleaved radical.

Example 28 The anti-fogging film obtained in Example 1 was analyzed by XPS [X-ray photoelectron spectrometer ESCA-850 (manufactured by Shimadzu Corporation)].
The N absorption was 7.5% (theoretical 7.7%), and the S absorption was 7.3% (theoretical 7.7%). From this,
It was found that the surface of the anti-fog film was a graft chain of ATBS.

From the results of Examples 27 and 28, it can be seen that the antifogging films of the Examples each have a hydrophilic graft chain bonded through a photoinitiating group fragment on the surface. For this reason, the antifogging film was excellent in antifogging performance, and could maintain its performance without being reduced in hydrophilicity even when it was in contact with water for a long time.

The technical ideas grasped from the embodiment will be described below. (1) The polymer is a hydrophobic polymer segment (I)
The anti-fogging film according to claim 1 or 2, which is a graft copolymer having a main chain as a main chain and a hydrophilic polymer segment (II) as a side chain.

In the case of such a configuration, it is possible to surely exhibit performance such as adhesion of the anti-fogging film to the substrate, anti-fogging performance of the anti-fogging film, its persistence, transparency, and film strength. (2) The hydrophobic polymer segment (I) according to claim 2, wherein the hydrophobic polymer segment (I) is formed from a monomer having an organic peroxide bonding group and a monomer having no organic peroxide bonding group. Anti-fog film.

In the case of such a constitution, the adhesion of the anti-fogging film to the base material and the other properties of the anti-fogging film can be adjusted so that each performance can be exhibited in a well-balanced manner. (3) A polymer having an organic peroxide bonding group is applied to the surface of a substrate, and then a hydrophilic monomer is applied to the surface,
The method for producing an anti-fogging film according to claim 3, wherein the substrate is heated after being immersed in a hydrophilic monomer. According to this structure, the antifogging film can be easily manufactured by a simple operation.

[0104]

As described above in detail, according to the present invention, the following excellent effects can be obtained. In the antifogging film of the first invention, a layer of the hydrophilic polymer segment (II) chemically bonded to the hydrophobic polymer is formed on the hydrophobic polymer segment (I) on the substrate side. It is a film having a structure. The surface side of this film is composed of a hydrophilic polymer segment (II), which is chemically bonded to the hydrophobic polymer segment (I) on the substrate side. Therefore, the hydrophilic film on the surface can prevent clouding of the substrate surface due to the attachment of water droplets, and even if a large amount of water droplets adhere to the substrate surface, there is no possibility that the hydrophilic film will fall off, The anti-fog performance can be maintained over a long period of time.

Further, since the surface of the anti-fogging film is a film having good uniformity of the hydrophilic polymer segment (II), a thin film can sufficiently exhibit performance, and the water absorption of the anti-fogging film can be reduced. can do. Accordingly, a decrease in performance due to water absorption is suppressed, and there is no danger that the hardness of the antifogging film is reduced due to swelling of the antifogging film, and the antifogging film is not damaged or peeled off. In addition, it has good transparency, practical coating strength, and good adhesion to a substrate.

In addition, since the polymerization initiation mechanism is not a mechanism in which the initiator starts hydrogenation by extracting hydrogen from the base material, it is possible to suppress the possibility that the applicable base material is restricted. As described above, the anti-fog film can be suitably applied to the surface of an optical component or a molded product made of a transparent material such as glass or plastic, and is industrially useful. According to the antifogging film of the second invention, the performance of the antifogging film such as antifogging property, its persistence, transparency and film strength is excellent, and the effect of the first invention can be further enhanced. According to the method for manufacturing an anti-fogging film of the third invention, the anti-fogging film having excellent performance of the first invention can be easily manufactured. According to the method for manufacturing an anti-fogging film of the fourth invention, an anti-fogging film having better performance can be easily manufactured.

[Brief description of the drawings]

FIG. 1 is an explanatory view conceptually showing a method for producing an antifogging film formed on a substrate.

[Explanation of symbols]

 A hydrophobic polymer segment (I) B hydrophilic polymer segment (II)

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 216: 14) (C08F 291/00 220: 26) (72) Inventor Shuji Suyama 4-132, Kusu, Taketoyo-cho, Chita-gun, Aichi Prefecture address

Claims (4)

[Claims] 1. An anti-fogging film formed on a substrate, wherein a hydrophobic polymer segment (I) formed from a hydrophobic monomer is located on the substrate side, and a hydrophilic monomer A hydrophilic polymer segment (II) formed from at least one monomer selected from the group consisting of: a hydrophobic polymer on the hydrophobic polymer segment (I) via an organic peroxide bonding group fragment; An antifogging film composed of a polymer bonded to the segment (I). Hydrophilic monomer: carboxyl group, hydroxyl group, sulfonic acid group, phosphoric acid group, alkali metal salt or ammonium salt thereof, alkylene oxide group, amino group, amide group, cyano group, acid anhydride group and quaternary ammonium base A monomer having at least one functional group selected from the group consisting of: 2. The hydrophobic polymer segment (I) is formed from a monomer having an organic peroxide bonding group, and the hydrophilic polymer segment (II) is formed from a hydrophilic monomer having an amide group. The antifogging film according to claim 1. 3. At least one member selected from the group consisting of the hydrophilic monomers is brought into contact with a layer of a hydrophobic polymer having an organic peroxide-bonding group formed on a substrate, and
The method for producing an antifogging film according to claim 1, wherein the method is heated to 50 ° C. 4. A hydrophobic polymer having an organic peroxide bond,
Organic peroxide bonds represented by the following general formulas (1) to (5)
At least one selected from the group of monomers having a group
Is a polymer segment formed from
4. The method according to claim 3, wherein the aqueous monomer is a monomer having an amide group.
A method for producing the anti-fogging film according to the above. General formula (1)(Where R¹ Is a hydrogen atom or a methyl group, R^Two Is a hydrogen atom
Or a methyl group, R^Three , R ^Four Is alkyl having 1 to 4 carbon atoms
Group, R^Five Is an alkyl group having 1 to 12 carbon atoms, and 3 to 1 carbon atoms
2 cycloalkyl group, phenyl group, alkyl group substituted
And n represents 1 to 5. ) General formula (2)(Where R⁶ Is a hydrogen atom or a methyl group, R⁷ Is a hydrogen atom
Or a methyl group, R⁸ , R ⁹ Is alkyl having 1 to 4 carbon atoms
Group, R^TenIs an alkyl group having 1 to 12 carbon atoms, and 3 to 1 carbon atoms
2 cycloalkyl group, phenyl group, alkyl group substituted
And n represents 0 to 4. ) General formula (3)(Where R¹¹Is a hydrogen atom or a methyl group, R¹², R¹³Is charcoal
An alkyl group having a prime number of 1 to 4, R¹⁴Is an alkyl having 1 to 12 carbons
Kill group, cycloalkyl group having 3 to 12 carbon atoms, phenyl
Represents a phenyl group substituted with an alkyl group. ) General formula (4)(Where R^FifteenIs a hydrogen atom or a methyl group, R¹⁶, R¹⁷Is charcoal
An alkyl group having a prime number of 1 to 4, R¹⁸Is an alkyl having 1 to 12 carbons
Kill group, cycloalkyl group having 3 to 12 carbon atoms, phenyl
Represents a phenyl group substituted with an alkyl group. ) General formula (5)(Where R¹⁹Is a hydrogen atom or a methyl group, R²⁰, R^{twenty one}Is charcoal
An alkyl group having a prime number of 1 to 4, R^{twenty two}Is an alkyl having 1 to 12 carbons
Kill group, cycloalkyl group having 3 to 12 carbon atoms, phenyl
Represents a phenyl group substituted with an alkyl group. )