JPH02255854A - Composition for forming antifogging resin coating - Google Patents

Abstract

PURPOSE:To provide the title composition excellent in initial antifogging properties, retentivity of the properties, film strength, etc., by adding a surfactant to a block or graft copolymer comprising a hydrophilic polymer part and a hydrophobic polymer part. CONSTITUTION:At least one copolymer selected from a block copolymer comprising a hydrophilic polymer part and a hydrophobic polymer part and a graft copolymer comprising these parts is prepared. An example of the copolymer is a copolymer having a hydrophilic polymer part formed from 6-25wt.% N- methylolacrylamide, 90-43wt.% hydroxyalkyl acrylate and 4-32wt.% acrylamide and a hydrophobic polymer part formed from 50-85wt.% lower alkyl acrylate and 50-15wt.% acrylic acid. A surfactant (e.g. polyoxyethylene sorbitan monostearate; is added to this copolymer to produce a composition for forming an antifogging resin coating.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is directed to forming an antifogging resin coating film that protects the surfaces of various materials, permanently maintains antifogging properties, and has excellent coating strength. The present invention relates to a composition.

(Prior art) Various plastic materials, glass, transparent ceramics, mirror materials, etc. can be used to make helmet shields, disaster prevention facepieces, underwater goggles, mirror surfaces, eyeglass lenses, films for agricultural greenhouses, etc. by utilizing their transparency and specularity. They are used for a variety of purposes, such as food packaging films and window glass for houses.However, one major drawback of these various materials is that they cannot be used in high temperature, high humidity locations, or indoors where the outside temperature is low. Water vapor condenses finely on the surface, resulting in a cloudy surface.

There are several solutions to this drawback.

(1) One method is to apply an anti-fog treated polyester film, a so-called composite film, or a saponified film surface made of acetyl cellulose, for example, to the windows of buildings and buildings, and the mirrors of bathrooms and washrooms. . (Japanese Patent Publication No. 60-44147, Japanese Patent Publication No. 60-44148, Japanese Patent Publication No. 60-44], Japanese Patent Publication No. 49, and Japanese Unexamined Patent Application Publication No. 6254733) Another method is to provide anti-fog properties on the surface of a transparent material. There is a method of forming a coating film. For example, (2)
A method in which a hydrophilic polymer such as a polymer of methacrylic acid 2-hydroxyethyl ester or a hydrophilic polymer such as polyvinylalnylene ester is used as a main component and a coating film (JP-A-59-217
783 and JP-A No. 60-223855) In addition, in order to maintain membrane strength against water, (3) a random copolymer in which part of the hydrophilic polymer portion is replaced with a hydrophobic portion (1) , a method of forming a coating film by combining a hydrophilic polymer and a crosslinking agent (Japanese Patent Publication No. 52-47754), and (4) a method of forming a coating film by adding a surfactant to a hydrophilic random copolymer. Method for forming a coating film (Unexamined Japanese Patent Publication No. 5
6-62856 and Japanese Patent Laid-Open No. 57-98518). As a more specific example, after coating the surface of a polyester film with anti-fog paint,
There is a method of curing the antifogging coating for a short period of about 10 seconds to 3 minutes. In this case, for example, (5
) The main component is a hydrophilic polymer such as a polymer of 2-hydroxyethyl methacrylate or polyvinyl alcohol, in the presence of an ion-curable crosslinking agent, and if necessary, a surfactant is added thereto, and heat treatment is performed after coating. (6) A method of forming an anti-fogging coating film by using a radical-reactive polyfunctional oligomer having a polyethylene oxide chain in the molecule, methacrylic acid-2-hydroxyethyl ester, etc. as the main component. Then, if necessary, a surfactant may be added thereto, and an antifogging coating film may be formed by radiation irradiation or ultraviolet ray irradiation treatment after coating (many methods such as JP-A-60-156731).

(Problem to be Solved by the Invention) However, in the conventional method (1) above, the hydrophilized cellulose film is weak in terms of water resistance, heat resistance, and brittleness resistance, and these cellulose films and polyester films are not suitable for practical use. There was a problem that wrinkles and air bubbles easily formed at the laminate interface, making it unusable. (
Method 2) is somewhat good in terms of anti-fogging properties, but
There were problems in that the coating film was not easily scratched, the coating film strength was poor, and the adhesion to the material surface was poor, resulting in easy peeling of the coating film.Method (3) Although the adhesion and adhesion are improved, the essential anti-fogging properties deteriorate.For (4), the initial anti-fogging properties are good, but the effectiveness decreases over time.
If added in large amounts, the strength and adhesion of the coating will decrease, so
This is not a satisfactory method.The problem is that method (5) cannot achieve both anti-fog performance and coating strength under the limited short-time curing conditions that are unique to anti-fog processing of polyester films. There was a point. That is, the lower the crosslinking functional group concentration and crosslinking agent concentration of the hydrophilic polymer, the better the antifogging performance, but due to the short curing time, sufficient crosslinking of the coating film is not achieved.
The strength and adhesion are extremely weak, and it cannot be put to practical use at all. Also, improve the strength of the coating! If the concentration of cross-linked functional groups in the hydrophilic polymer is increased in order to increase the concentration of cross-linked functional groups, the anti-fog performance will be extremely reduced. The initial anti-fogging effect is achieved because the surfactant bleeds into the surface, but
When the surface of the coating film is immersed in water, the surfactant on the surface flows, but because the concentration of the crosslinking agent is high, the surfactant cannot bleed from the inside to the surface, resulting in a decrease in antifogging performance.

Furthermore, although the method (6) cures in a short time, it has the problem that the radical curing is a chain reaction, so the curing progresses easily, the crosslinking density becomes too high, and the antifogging performance is low. As described above, a satisfactory method for antifogging processing of various transparent materials has not yet been found.

An object of the present invention is to provide an antifogging resin coating film-forming composition that exhibits not only initial antifogging performance but also long-lasting antifogging performance and excellent coating film performance.

(Means for Solving the Problems) The present inventors have developed a composition that has long-lasting wettability and adhesion to the material surface by combining a hydrophilic polymer portion and a hydrophobic polymer portion. We are proposing a block copolymer consisting of (Patent application No. 58-74959). Subsequently, as a result of further intensive studies, it was found that block copolymers consisting of a hydrophilic polymer part and hydrophobic polymer parts; or graft copolymers consisting of a hydrophilic polymer part and a hydrophobic polymer part have surfactant By using the agent in combination, the coating formed on the transparent material from the composition has dramatically higher long-lasting wettability than expected with conventional technology, and also has excellent adhesion and abrasion resistance to the material surface. The present invention has been completed based on the discovery that the conventional problems are greatly improved.

That is, the present invention provides at least one type of copolymer selected from a block copolymer consisting of a hydrophilic polymer part and a hydrophobic polymer part, and a graft copolymer consisting of a hydrophilic polymer part and a hydrophobic polymer part. The present invention relates to an antifogging resin film-forming composition characterized in that the polymer contains a surfactant.

The vinyl monomer forming the hydrophilic polymer constituting one molecular chain of the block copolymer and graft copolymer used in the present invention is, for example, (meth)acrylic acid (acrylic acid, methacrylic acid (hereinafter the same shall apply), radically polymerizable unsaturated carboxylic acids such as itaconic acid and 1"1tonic acid, and alkali metal salts of these unsaturated carboxylic acids, ammonium salts, organic amine salts, styrene sulfonic acid and sulfopropyl Radically polymerizable unsaturated monomers having a sulfonic acid group such as (meth)acrylic acid ester and sulfopropyl itaconate, and their alkali metal salts, ammonium salts, organic amine salts, and methacryloyloxyethyltrimethyl Ammonium chloride, quaternary ammonium salts derived from (meth)acrylic acid such as 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride, alcohols with tertiary amino groups such as methacrylic acid diethylamino ester methacrylic acid ester,
and their quaternary ammonium salts, radically polymerizable unsaturated monomers containing amide groups such as (meth)acrylamide and dimethylacrylamide, and quaternary ammonium salts derived from amidoamines obtained from methacrylic acid and diamines. Hydroxy esters of (meth)acrylic acid, such as (meth)acrylic acid hydroxyethyl ester, (meth)acrylic acid hydroxypropyl ester, (meth)acrylic acid 3-chloro-2-hydroxypropyl ester, Polyethylene glycol and polypropylene glycol of (meth)acrylic acid, such as (meth)acrylic acid diethyl glycol ester, (meth)acrylic acid triethylene glycol ester, (meth)acrylic acid dipropylene glycol ester, Polyhydric alcohol esters of (meth)acrylic acid such as acrylic acid monoglyceride, mono (2.
Phosphates of (meth)acrylic acid, such as hydroxyethyl acrylic I/-h) acid phosphate, N-
(3-sulfopropyl) -Nmethacryloyloxyethyl-N,N-di,methylammoniumvequin,N-(
3-sulfopropyl) N-methacryloylamidopropyl-N, N dimethylammonium betaine, 1-(
3-Sulfopropyl)-2-vinyl-pyridinium・-
These include hetain-type radically polymerizable unsaturated monomers such as \tine, vinylpyridine, its salts, and vinylpyrrolidone. It is also possible to add other vinyl type monomers to the extent that the function as a hydrophilic polymer is not impaired.

The vinyl monomer that forms the hydrophobic polymer that constitutes the other molecular chain of the block copolymer and graft copolymer used in the present invention has a high coating strength and adhesion to the target transparent material. Appropriately selected from the following aspects. In particular, when the transparent material is a polymeric material, it is selected in consideration of its compatibility with the base range. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isopropyl (meth)acrylate, glycidyl (meth)acrylate, n-(meth)acrylate. Butyl, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate,
(Meth)acrylic acid esters such as 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate, methane, vinyltoluene, α- Aromatic vinyl monomers such as methylstyrene, carboxylic acid vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl stearate, bucdiene, vinyl chloride, vinylidene chloride, (meth)acrylonitrile, (meth)allylglycidyl Ether, etc.

The block copolymer and graft copolymer comprising a hydrophilic polymer portion and a hydrophobic polymer portion of the present invention can be produced by various conventionally known methods including radical polymerization, cationic ring-opening polymerization, anionic living polymerization, and cationic living polymerization. Although block copolymers and graft copolymers can be produced by various methods, polymerization of polymeric peroxides, polyazo compounds, and radical copolymerizable group-containing peroxides is particularly preferred from the viewpoint of ease of industrial productivity and versatile performance. Preferred are block copolymers and graft copolymers produced by radical polymerization. The radical polymerization initiator used in this case is a conventionally known compound having two or more ber]oxy bonds or azo bonds in one molecule, or a compound having a radical copolymerizable group and a peroxy bond in one molecule. can be easily obtained by ordinary bulk polymerization, suspension polymerization, solution polymerization, and emulsion polymerization.

A typical production example of the block copolymer of the present invention will be described below using polymeric peroxide as a polymerization initiator. First, when a vinyl monomer that forms a hydrophilic polymer is polymerized using polymeric peroxide, a peroxy bond-containing hydrophilic vinyl polymer with peroxy bonds introduced into the chain is obtained, which has hydrophobic properties. When a vinyl monomer forming a polymer is added and polymerized, the peroxy bonds are cleaved at the peroxy bonds contained therein, and a block copolymer can be efficiently obtained. Further, a typical production example of the Graph I copolymer of the present invention will be explained below using a radical copolymerizable group-containing peroxide as a polymerization initiator.

First, under conditions that the peroxy bond of vermexide containing a radical copolymerizable group is not cleaved, by copolymerizing a vinyl type monomer that forms a parent, aqueous polymer using an ordinary '1JJ leaving group polymerization initiator. , a hydrophilic copolymer containing peroxy bonds is obtained, and then polymerization is carried out by adding a vinyl monomer that forms a hydrophobic polymer under conditions where the peroxy bonds are cleaved. The bonds are cleaved at the peroxy bonds they contain, and a graft copolymer can be efficiently obtained. In the flock copolymer and graft copolymer obtained in this manner, the molecular weights of the hydrophilic polymer portion and the hydrophobic polymer portion can be freely adjusted.

B in the present invention: hook copolymer and graph I.
The preferred weight ratio of the hydrophilic polymer portion and the hydrophobic polymer portion of the copolymer is 1/19 to 19/1, more preferably 179 to 9/1. If the hydrophilic polymer portion is less than 5% by weight, it will not be compatible with the surfactant of the present invention,
There is a possibility that the surfactant easily separates from the formed coating film, reducing the sustained effect of the antifogging property of the coating film. Furthermore, if the hydrophobic polymer portion is less than 5% by weight, not only the adhesion between the surface of the material to be modified and the coating may be impaired;
There is a risk that the water resistance and mechanical strength of the coating film will also deteriorate, and it may be difficult to obtain two results in practical use.

The film-forming resin composition of the present invention further comprises a block copolymer comprising a hydrophilic copolymer portion into which a specific crosslinkable functional group is introduced and a hydrophobic copolymer portion into which a specific crosslinkable functional group is introduced. By using a block copolymer with a specific weight ratio of hydrophilic polymer portion and hydrophobic polymer portion in combination with a surfactant, the material surface can be effectively treated even in environments where the material surface is subject to thermal history. It has the characteristics of adhesion, excellent coating strength, and high anti-fog properties.

Immediately, the antifogging coating composition of the present invention adopts a means of containing a block copolymer consisting of a hydrophilic polymer portion and a hydrophobic polymer portion as described below, and a surfactant. ing.

Block copolymer: at least one of the following N-substituted or unsubstituted (meth)acrylamide compounds represented by Monana (1) or (II) [acrylic and methacrylic are collectively referred to as (meth)acrylic]. A group consisting of monomers having a crosslinkable functional group of 1 to 40%, glycidyl group, N-methylol group, tri-4-medylol ether group, carboxyl group, acid anhydride (hereinafter referred to as 1 to 20 weight percent of at least one monomer selected from Group A) and 40 to 98 weight percent of at least one hydrophilic monomer that is copolymerizable with the medium listed in J. a hydrophilic polymer portion consisting of a hydrophilic polymer portion, at least one monomer selected from the monomers of the above group A, 1-40% by weight, and a hydrophobic monomer having copolymerizability with the monomers of the above group A. The weight is small and the strength is 60~60~
It consists of a hydrophobic polymer part consisting of 99% by weight, and the weight ratio of the hydrophilic polymer part and the hydrophobic polymer part is 501%.
50 to 95 i' 5 block copolymer.

General formula (I) CIl□=CR1C0NRJt -h In the formula, R11R2 is a hydrogen atom or a methyl group, R5 is a hydrogen atom, a methyl group, an ethyl group, an n-globyl group, an isopropyl group, an N,N-dimethylaminopropyl group Or -C(CL) represents 2CIIzCOC11.

- Monna (II) In the above formula, R8 is a hydrogen atom or a methyl group, and A is -c
cnz), t- and n is 4 or 5, or -(CH2)
ZO(CHz) represents z-.

Examples of the N-substituted or unsubstituted (meth)acrylamide compound introduced into the hydrophilic polymer moiety constituting one molecular chain of the block copolymer in the present invention include (meth)acrylamide, N-methyl (meth) Acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N.-diethyl(meth)acrylamide, N-n~propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N
, N-dimethylaminopropyl (meth)acrylamide, diacetone (meth)acrylamide, N-(meth)acryloylpyrrolidine, N-(meth)acryloylpiperidine, N-(meth)acryloylmorpholine, etc. are used.

The above (meth)acrylamide compound needs to be in a range of 1 to 40% by weight in the hydrophilic polymer portion.

If it is less than 1% by weight, the durability of antifogging properties and adhesion after being subjected to heat history will be poor, and if it exceeds 40% by weight, the strength of the coating will decrease.

Next, examples of monomers having a crosslinkable functional group in Group A include glycidyl (meth)acrylate, °N"-methylol (meth)acrylamide, N-methyl-xymethylol (meth)acrylamide, N- Phthoxymethylol (meth)acrylamide, (meth)acrylic acid, crotonic acid, itaconic acid, itaconic acid half ester, maleic acid,
Maleic acid half ester, itaconic anhydride, maleic anhydride, etc. are used.

The above-mentioned monomer components need to be present in an amount of 1 to 20% by weight in the hydrophilic polymer portion. If it is less than 1% by weight, the coating film strength will be insufficient, and if it exceeds 20% by weight, the crosslinking density will be too high and the antifogging property will deteriorate.

The hydrophilic monomer that is copolymerizable with the above-mentioned (meth)acrylamide-based compound and the monomer having a crosslinkable functional group of Group A, is not at all susceptible to the crosslinking reaction with the functional group possessed by the monomer of Group A. Monomers that do not participate or are significantly less reactive are preferred. Examples of this monomer include radically polymerizable unsaturated carboxylic acids such as (meth)acrylic acid, itaconic acid, and crotonic acid, their alkali metal salts, ammonium salts, organic amine salts, styrene sulfonic acid, and sulfopropyl ( Radically polymerizable unsaturated monomers having sulfonic acid groups such as meth)acrylic acid esters, and their alkali metal salts, ammonium salts, organic amine salts, methacryloyloxyethyltrimethylammonium flora, etc.
quaternary ammonium salts derived from (meth)acrylic acid, such as 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride, (
meth)acrylic acid hydroxyethyl ester, (meth)
Hydroxy esters of (meth)acrylic acid, such as acrylic acid hydroxypropyl ester, (meth)acrylic acid-3-chloro-2-hydroxypropyl ester,
(meth)acrylic acid diethylene glycol ester, (
meth)acrylic acid triethylene glycol ester, (
Polyethylene glycol or polypropylene glycol esters of (meth)acrylic acid such as dipropylene glycol meth)acrylate, polyhydric alcohol esters of (meth)acrylic acid such as (meth)acrylic acid monoglyceride, mono(2-hydroxyl) Phosphates of (meth)acrylic acid, such as ethyl methacrylate-1.) acid phosphate, N-(3-sulfopropyl)
-N-methacryloyloxyethyl-N,N-dimethylammonium betaine, 1-(3-sulfopropyl)-2
- Betaine type radically polymerizable unsaturated monomers such as vinylpyridinium betaine, vinylpyridine and its salts, vinylpyrrolidone, etc. are used.

The hydrophobic polymer portion constituting the other molecular chain of the block copolymer in the present invention includes 1 to 40% by weight of the monomer component of group A and a hydrophobic monomer copolymerizable with this monomer. 6
It must be comprised of 0 to 99% by weight.

In this case, the monomer selected from Group A is preferably one that has good reactivity with the functional group introduced into the hydrophilic polymer portion. For example, when a glycidyl group is present in the hydrophilic polymer portion, it is preferable that a carboxyl group or an acid anhydride is introduced into the hydrophobic polymer portion. Conversely, when a carboxyl group or an acid anhydride is present in the hydrophilic polymer portion, it is preferred that a glycidyl group is present in the hydrophobic polymer portion. In addition, N-methylol group and N-
- When a functional group with strong self-crosslinking properties, such as a methylol ether group, is present in the hydrophilic polymer portion, an N~methylol group or an N-methylol ether group may be introduced into the hydrophobic polymer portion. , a carboxyl group or an acid anhydride may be introduced.

If the monomer component selected from Group A is less than 1% by weight in the hydrophobic polymer portion, the strength of the coating film will be insufficient;
If it exceeds % by weight, the adhesion to the material surface will decrease.

The hydrophobic monomer having a copolymer with the monomer of Group A is:
Considering the adhesion to the target material, 1. Appropriately selected. Examples of this monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)'acrylate, isopropyl (meth)acrylate,
(meth)acrylic IJ n--butyl, (meth)acrylic acid isobutyl, (meth)acrylic acid t, G r t-
Butyl, (meth)acrylic acid esters such as 2-ethyl-xyl (meth)acrylate, aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, vinyl chloride, vinyl 112, propionic acid Carboxylic acid vinyl esters such as vinyl, butadiene, vinyl chloride, vinylidene chloride, (meth)acrytit nitrile, allyl glycidyl ether, etc. are used.

The floc copolymer in the antifogging coating composition of the present invention is composed of a polymer having a composition corresponding to the above-mentioned blending ratio of each lit body forming the hydrophilic polymer portion and the hydrophobic polymer portion. be done.

Next, it is necessary that the weight ratio of the hydrophilic polymer part and the hydrophobic polymer part in the block copolymer is 50,150 to 9,515. When the weight ratio of the hydrophilic polymer portion 5) is less than 50%, the affinity between the coating film and the surfactant becomes low, and the surfactant easily desorbs from the formed coating film.
The durability of anti-fog properties decreases.

In addition, when the weight ratio of the hydrophobic polymer portion is less than 5%,
The adhesion between the material surface and the coating film will not be left blank.
The strength of the coating film also decreases, making it unusable for practical use.

Furthermore, the coating film-forming resin composition of the present invention has excellent antifogging properties and coating film strength by incorporating a block or graft copolymer having self-crosslinking properties as described below and a surfactant. In particular, in the coating process of polyester film, that is, in the short-time curing process, both the properties of ζ and dirt can be achieved.

Block or graft copolymer = monomer consisting of glycidyl (meth)acrylate or N-methylol acrylamide, 6-25% by weight, 43-90% by weight of hydroxyalkyl (meth)acrylate, acrylamide, N-monomethylacrylamide, N.

Monomer 4 selected from N-dimethylacrylamide, N-acryloylmorpholine, N-beer birX1 nodone
a hydrophilic polymer portion formed from 32% by weight;
meth) lower alkyl acrylate 50-85% by weight, (
A block or graft copolymer consisting of a hydrophobic polymer portion formed from 15.-50 wt. meth)acrylic acid.

The rli m1 body 67 forming the hydrophilic polymer portion of the block or graft copolymer in this case will be explained.

(Meth)glycidyl acrylate or N-methylol acrylamide is N- - Methylolacrylamide is preferably used, and the curing temperature is 120~
When the temperature is about 230°C, glycidyl (meth)acrylate is preferably used. The usage ratio of glycidyl (meth)acrylate or N-methylol acrylamide is 6
~? It is 5%.

As the hydroxyalkyl (meth)acrylate, hydroxy lower alkyl (meth)acrylate, etc. are used.
Hydro-1=diethyl (meth)acrylate is preferred. The proportion of hydroxyalkyl (meth)acrylate used is 43 to 90% by weight.

Acrylamide, N-monomethylacrylamide, N,
N-dimethylacrylamide, N-acryloylmorpholine The monomer selected from N-vinylpyrrolidone is preferably N-monomethylacrylamide, N,N-dimethylacrylamide, or N-acryloylmorpholine. The proportion of this monomer used is 4 to 32% by weight.

Next, the monomers forming the hydrophobic polymer portion of the block or graft copolymer will be explained.

Examples of lower alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, (
n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (meth)
Isobutyl acrylate, tert (meth)acrylate
-butyl etc. are used. Among these, methyl (meth)acrylate is preferred. The proportion of lower alkyl (meth)acrylate used is 50 to 85% by weight.

Further, the proportion of (meth)acrylic acid used is 15 to 50% by weight.

The usage ratio of each monomer forming the hydrophilic polymer part and the usage ratio of each monomer forming the hydrophobic polymer part mentioned above are determined from both the antifogging performance and coating strength of the polyester film. However, outside these ranges, it is not possible to achieve both high antifogging performance and coating film strength.

Since the block or graft copolymer used in the present invention has self-crosslinking properties, the functional group in the hydrophobic polymer portion (h) should have good reactivity with the functional group introduced into the hydrophilic polymer portion. It is preferable to select one that has. For example, when a glycidyl group is present in the hydrophilic polymer portion, it is preferable that a carboxylic acid group or a sulfonic acid group is introduced. Conversely, when a carboxylic acid group or a sulfonic acid group is present in the hydrophilic polymer portion, it is preferable that a glycidyl group is present in the hydrophobic polymer portion. In addition, if a functional group with strong self-crosslinking properties such as an N-methylol group is present in a hydrophilic polymer portion, an N-methylol group may be present in this hydrophobic polymer portion, or a carboxylic acid or a sulfonic acid group.

A copolymer of the hydrophilic polymer portion and the hydrophobic polymer portion of the present invention is obtained.

In the block copolymer and graft copolymer thus obtained, the molecular weights of the hydrophilic polymer portion and the hydrophobic polymer portion can be freely adjusted. Also, graph I
・In copolymers, the hydrophilic polymer portion is the backbone2,
It may be either a graft copolymer having hydrophobic polymer portions as branches or a graft copolymer having hydrophobic polymer portions as a trunk and hydrophilic polymer portions as branches. Furthermore, in the present invention, a block copolymer and a graft copolymer can be used in combination to obtain the same effect.

The preferred weight ratio of the hydrophilic polymer portion/hydrophobic polymer portion of the block copolymer and graft copolymer in the present invention is 1/9 to 9/1, more preferably 175
~5/1. If the hydrophilic polymer portion is less than 10% by weight, the antifogging properties will decrease and at the same time the compatibility with the surfactant will deteriorate, and the surfactant will easily separate from the formed coating film, resulting in the antifogging properties of the coating film. There is a risk that the sustainability of Furthermore, if the hydrophobic polymer portion is less than 10% by weight, not only the adhesion between the surface of the material f′1 to be modified and the coating film may deteriorate, but also the water resistance and mechanical strength of the coating film may deteriorate. It tends to decrease, and there is a possibility that it will not be useful in practical use.

The surfactant of the present invention includes one or more commonly used surfactants selected from nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. It is an activator. In particular, nonionic surfactants and anionic surfactants are preferred from the viewpoint of sustainability of effects. More preferably, it is a monosurfactant consisting of 1L of a combination of a nonionic surfactant and an anionic surfactant.

Examples of nonionic surfactants include polyoxyethylene higher alcohol ethers such as polyoxyethylene lauryl ether, polyoxyethylene lauryl ether, and polyoxyethylene oleyl ether; polyoxyethylene oleyl phenol; Polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenol; polyoxyethylene acyl esters such as polyethylene glycol monostearate; polypropylene glycol ethylene oxide adduct; polyoxyethylene sorbitan monolaurate, polyoxyethylene Examples include polyoxyethylene sorbitan fatty acid esters such as sorbitan monostearate 1; phosphoric acids and esters such as alkyl phosphate esters and polyoxyethylene alkyl ether phosphates; sugar esters; cellulose ethers.

Anionic surfactants and U7 include, for example, aliphatic compounds such as sodium oleate and potassium oleate; higher alcohol sulfate esters such as sodium lauryl sulfate and ammonium lauryl sulfate; sodium dodecylbenzenesulfonate and thorium alkylnaphthalenesulfonate. Alkylhenzene sulfonate and alkyl naphthalene sulfonate; naphthalene sulfonic acid formali 711t5; di'furkylsulfosuccinate; dialkyl phosphate salt; Examples include polyoxyethylene sulfate salts such as sodium oxyethylene alkyl phenyl ether sulfate.

Examples of cationic surfactants include ethanolamines; amine salts such as laurylamine acetate, triethanolamine monostearate formate; stearamide ethyl diethylamine acetate; lauryl trimethylammonium chloride, stearyl trimethylammonium chloride, and dilauryl. Dimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylbenzylammonium t':+
and quaternary ammonium salts such as stearyldimethylbenzyl ammonium chloride.

Examples of amphoteric surfactants include aliphatic type amphoteric surfactants such as dimethyl alkyllaurylhetaine and dimethylalkylstearylhetaine; sulfonic acid type amphoteric surfactants such as dimethylalkylsulfohetaine. , alkylglycine, etc.

The blending ratio of Bronia Co-111 Copolymer, Graph 1 Copolymer and surfactant in the coating film forming composition of the present invention is from 0.1 parts by weight to 20 parts by weight of surfactant per 100 parts by weight of copolymer. Parts by weight are preferred. If the amount of the surfactant is less than 0.1 parts by weight, a coating film-forming composition with high anti-fogging durability, which is the main objective of the present invention, will be obtained (it will be thick). There is a risk that the water resistance and mechanical strength of the paint film will deteriorate.

The method of mixing the surfactant and the block copolymer or graft copolymer of the present invention includes dissolving or dispersing the block copolymer or graft copolymer in an aqueous solvent, water and an organic solvent, or water. A surfactant may be directly added therein, or during the production of the block copolymer or graft copolymer, it may be added together with a vinyl-type interpolant that forms the block copolymer or graft copolymer. A surfactant may also be added.

The coating film-forming composition of the present invention can be applied to the surface of a transparent material or a mirror material, and then dried at room temperature or by heating.
- Boat fishing. As the application method, the application means for ordinary paints, ie, the roll coating method, the spray method, the dipping method, the brush coating method, the spin 1-1 method, etc. are applied. The solvent used in this case is water, methanol, ethanol, n.
Propatool, isopropatool, n-butanol,
2 Alcohol solvents such as diacetone alcohol, alcohol ether solvents such as methylcetone LJ solve, ethyl cellosolve, butyl cellosolve, methyl calpitol, ethyl carpitol, butyl carpitol, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, Examples include ester solvents such as ethyl acetate and butyl acetate, aromatic hydrocarbon solvents such as benzene, toluene and xylene, and amide solvents such as formamide and dimethylformamide. Do you particularly like L2 among these? The container is an alcoholic solvent, a mixture of alnyl 7-lether, and a mixed solvent thereof.

The antifogging resin coating forming composition of the present invention can also be used in combination with conventionally known curing agents and resins in order to further increase coating strength. For example, alkoxymethylol melamine formaldehyde resin, fullkylated benzoguanamine resin, various amino resins such as barron resins, adduct type polyisocyanate made by reacting trimethylolpropane with diisocyanate, and xamethylene diisocyanate. Isocyanate group-containing resins such as bi-let type polyisocyanates and various blocked isocyanates, bisflunol A type epoxy resins, and fiberglass resins, which are produced by reacting trimers of

Polyepoxy compounds such as Nord-F type epoxy resin, trimethylolpupan polyglycidyl ether, neopentyl glycol diglycidyl ether, and compounds containing two or more hydroxyl groups such as polyethylene glycol and polypropylene glycol 1. These include compounds containing two or more carboxyl groups such as dodecanedioic acid. The amount of these curing agents used is determined according to the invention 7. It is preferable that O be 30% by weight of the block copolymer and graft copolymer ζ in this case. If the weight exceeds 30 weight, the effect of the present invention will be inhibited.

C) If necessary, add ultraviolet absorber, leveling...
Various well-known and commonly used additive components such as adhesives, various curing catalysts, and antioxidants can also be blended.

(Function) The reason why the antifogging resin coating film-forming composition of the present invention has good coating performance is not clear, but it is thought to be as follows. When a block copolymer, a graft copolymer, and a surfactant are mixed, the hydrophilic polymer portion of the block copolymer or graph copolymer and the surfactant have an affinity. , the block copolymer, and the graft copolymer uniformly disperse the surfactant. The coating film to be formed from this is that the hydrophilic polymer portion of the block copolymer or graft copolymer acts as an anchor for the surfactant, and
Firmly fixes the surfactant into the coating film. When moisture adheres to the coating film, the surfactant gradually bleeds from inside the coating film, forming a block copolymer,
The synergistic effect of the performance of the hydrophilic polymer portion of the graft copolymer and the Bunod L7 surfactant dramatically increases antifogging performance and antifogging durability. On the other hand, the hydrophobic polymer portion of the block copolymer or graft copolymer adheres closely to the rough surface 5, forming a coating film with excellent water resistance, corrosion resistance, and strength.

(Effects of the Invention) The antifogging resin coating film-forming composition of the present invention has excellent antifogging properties on the surface at the stage of forming a coating film, and can maintain this effect permanently. - It has excellent adhesion to the surface of various plastic materials, glass, transparent materials such as transparent ceramics, and various mirror materials, and has very good water resistance and mechanical properties of the coating film. This completely solves the problems that conventionally existed with various anti-fog paints.

Therefore, various plastic molding materials, vanity mirrors, bathroom mirrors, buildings, car window glass, curved mirrors, reflective mirrors, agricultural mirrors, etc. are now available! 9. Antifogging agents such as Firno for food packaging, Hj2. It is expected to have great effects in all applications.

(Example) Hereinafter, the present invention will be explained using an example and an upper axis example. All copies shown are based on weight.

Example 1 - Production of hydrophilic and hydrophobic block copolymers 11 Production of peroxy bond-containing polymers 5. Charge 90 parts of methoxyl cosolve into a reactor equipped with a thermometer, stirrer and reflux condenser 9. Nitrogen gas 70°C while blowing
Heat it to Q1\Methyl Cellosolve
A mixed solution (+) consisting of : 30 parts of 2Hl'lkoxyethyl methacrylate was charged over 2 hours, and the polymerization reaction was continued for another 2 hours. The properties of the obtained solution were 23.1% U2 containing a peroxy bond-containing polymer.
It was a clear solution with a viscosity of 1.8 voids at 25°C.

1-2 Production of block copolymer In a reactor equipped with a thermometer, stirring and reflux condenser, 1-1
-A mixed solution of 100 parts of methyl cellosolve solution of peroxy bond-containing polymer and 20 parts of methyl methacrylate (n
), heated to 70°C while blowing nitrogen gas, and subjected to block copolymerization reaction for 6 hours to produce a transparent polymer containing 42.8x of block copolymer and having a viscosity of 5.5 voids at 25°C. A solution was obtained.

1111 Production of hydrophilic and hydrophobic block copolymer 2-1 Production of peroxy bond-containing polymer 90 parts of ethyl cellosolve was charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was heated to 70°C while blowing nitrogen gas. Heat to C, add methyl cellosolve
: 60 parts 2-hydroxyethyl methacrylate =
55N-methylolacrylamide: A mixed solution (IIN) consisting of 5 was prepared over 3 hours, and then 3
A time polymerization reaction was performed. The resulting solution was a clear solution containing 3165% of the peroxy bond-containing polymer and having a viscosity of 7.5 voids at 25°C.

2-2 Production of block copolymer In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 2-
A mixture (IV) of 100 parts of the ethyl cellosolve solution of the peroxy bond-containing polymer in step 1, 8 parts of methyl methacrylate and 1 part of acrylic acid was charged, and nitrogen gas was blown into the container.
Block copolymer reaction was carried out at 0°C for 6 hours, then heated to 80''C for 2 hours, and the block copolymer was heated to 40.
A clear solution containing 3% and a viscosity of 7.3 voids at 25°C was obtained.

Production of mainly hydrophilic and hydrophobic graft copolymer 3-1 Production of peroxy bond-containing polymer 150 parts of methyl cellosolve was charged into a reactor equipped with a thermometer, a stirrer and a reflux condenser, and nitrogen gas was blown into the reactor.゛C
and t-butyl peroxyoctanoate (trade name "Barbutyl OJ, manufactured by NOF Corporation, 1
0 hour half-life temperature 72'CH, 5 parts, 6 parts of t-butylberoxymethacryloyloxyethyl carbonate as a radical (co)polymerizable organic peroxide, 2 parts of methacrylic acid.
- It was dissolved in 280 parts of hydroxyethyl, 20 parts of glycidyl methacrylate, and 300 parts of methyl cellosolve, and this mixed solution (V) was poured into an IJ for 2 hours, and the polymerization reaction was further carried out for 7 hours. The obtained solution was a transparent solution having a peroxy bond-containing polymer of 40.1 x and a viscosity of 5.7 voids at 25'C.

3-2 Production of graft copolymer In a reactor equipped with a thermometer, stirrer, and reflux condenser, 3-
Pour 100 parts of the methyl cellosolve solution of the peroxy bond-containing polymer in Step 1, and heat to 110" while blowing nitrogen gas.
A mixture of 28 parts of methyl methacrylate, 28 parts of methacrylic acid, and 50 parts of methyl cellosolve was added thereto over 2 hours, and the graft polymerization reaction was further carried out for 7 hours. The obtained solution contained 31x of black copolymer and had a viscosity of 3 at 25°C.
．． It was a clear solution with 5 voids.

4-1 Production of hydrophobic graft copolymer aimed at Kouko 4-1 Production of peroxy bond-containing polymer 90 parts of isopropanol and 60 parts of water were charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and nitrogen gas was added. was heated to 80°C, and 3.0 parts of 1-butylperoxyoctanoate and 6 parts of t-butylberoxymethacryloyloxyethyl carbonate as a radical (co)polymerizable organic peroxide were added to the mixture.・Hydroxy 3-methacryloyloxypropyltrimethylammonium chloride (
Product name: “Blenmar QAJ, manufactured by NOF Corporation) 50
1 part, 50 parts of ion-exchanged water, and 50 parts of isopropanol, this mixed solution (■) was charged over 2 hours, and the polymerization reaction was further carried out for 7 hours.The properties of the solution obtained were as follows:
There was a clear solution containing 19% polymer containing peroxy bonds and a viscosity of 1.5 poise at 25.degree.

4-2 Production of graft copolymer In a reactor equipped with a thermometer, stirrer and reflux condenser, 4-
A mixed solution (■) of 100 parts of isopropanol/water solution of the peroxy bond-containing polymer of I and 10 parts of butyl methacrylate was charged, nitrogen gas was blown in, and the mixture was heated to 110 parts under pressure.
The graft polymerization reaction was carried out by heating to °C for 7 hours. The properties of the obtained solution contained 26χ of the graft copolymer, and 2
A white translucent material with a viscosity of 1.3 voices at 5°C? A mixture was obtained.

three,,! Ll- Production of hydrophilic and hydrophobic block copolymer 5-1 Production of peroxy bond-containing polymer A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 90 parts of N,N dimethylformamide, and nitrogen gas was blown into the reactor. Heat to 70°C and add N,N dimethylformamide = 30 parts styrene.
:30II ii 11
It-(-C(CH2), C0(C112)20
A mixed solution (IX) consisting of C(C112)4COOt-,2:6 was charged over 2 hours, and then a polymerization reaction was carried out for 3 hours. The resulting solution was a transparent solution containing 23.1% of the peroxy bond-containing polymer and having a viscosity of 2.3 voids at 25°C.

52 Production of block copolymer In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 5-
N,N dimethylformamide of the peroxy bond-containing polymer of No. 1) Volume: 200 parts, 100 parts of dimethylformamide
Part 2 Mixed solution of 30 parts of methacrylic/1-lium mido2-methylpropanesulfonate (X) (a), heated to 70"C while blowing nitrogen gas, and carried out block copolymerization reaction for 8 hours. Including 23χ, 2
A white clear solution was obtained with a viscosity of 0.3 voids at 5°C.

13J ■ - Production of hydrophilic and hydrophobic random copolymer 80 parts of methyl cellosolve was charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and heated to 70°C while blowing nitrogen gas.
= 20 parts methacrylic acid 2/hydroxy J2
Chill: 15 Methyl acrylate:
A mixed solution consisting of 17N methylolacrylamide:3 and abbisisobutyronitrile was charged over 2 hours, and the copolymerization reaction was further carried out for 8 hours. The properties of the obtained solution were 29% of the random copolymer.
．． It was a clear solution containing 5x and a viscosity of 3.0;

1 to 7 and 9 1 to 3 Using each of the polymers obtained in Reference Example 1-6, the first
Various antifogging resin coating film-forming compositions were obtained by mixing the compositions in the proportions shown in the table. Next, each composition was applied so that the jγ of the dried coating film was 5 μm,
It was heated and dried under the respective conditions shown in Table 1. The materials applied under each compounding condition were polymethyl methacrylate in Examples 1 and 4, polycarbonate in Examples 2, 3, and 7, and Comparative Examples 1 to 3, and Bolier lentil thalate in Examples 5 and 6. It is. Examples 14.7 and Comparative Examples 1-3 are transparent sheets, and Examples 5 and 6 are j5 clear Filno.

The results of the comparison tests for each of the coating films obtained by such straining are summarized in Table 2 1.

11 cases 1-2 ■.

Using the blended composition in Table 1, apply it to the surface of each material shown in Table 3 so that the thickness of the coating after drying is 5 μm, and heat under the respective conditions shown in Table 3. Dry. The results of a comparative study conducted on each of the coating films thus obtained are summarized in Table 3.

(Reference Examples 7 to 21) (Production of B1cock copolymer) 100 parts of methyl cellosolve was charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and heated to 70°C while blowing nitrogen gas. 6 and methyl cellosolve
90 parts (meth)acrylamide type compound Monomer selected from the group for S part
T part hydrophilic monomer tJ part (CO(CH2)4C00(C2H40)+1cO(C
H2)4COO)I. A mixed solution consisting of -12 parts was charged over 2 hours, and the polymerization reaction was further carried out for 2 hours. Then, methyl cellosolve 60 parts Monomer selected from Group A V part Hydrophobic monomer
A mixed solution consisting of part W was charged over 30 minutes, and a polymerization reaction was carried out at 75°C for 5 hours. The number of parts of SW and the polymerization results are shown in Tables 4 and 5.

(Reference Examples 22 to 24) (Production of random copolymer) 150 parts of methyl cellosolve was charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and nitrogen gas was blown into the reactor.
Heat to 0°C and add methyl cellosolve to it.
100 parts (meth)acrylamide compound
Monomer selected from S part A group T
Part hydrophilic monomer U part Monomer selected from the group V part Hydrophobic monomer
W part cH, C (COyu) zo
A mixed solution consisting of 3 parts of OcOc(CI'h) x was charged over 2 hours, and a copolymerization reaction was carried out over a further 5 hours. The number of parts of SW and the polymerization results are shown in Table 5.

Table-・4 Table-5 The abbreviations in Tables 4 and 5 above have the following meanings.

■8N,N-dimethylacrylamide■: N,N-dimethylaminopropylmethacrylamideacryloylmorpholinglycidylmethacrylateN-methylol acrylamide2-hydroxyethylmethacrylatemono(2-hydroxyethylmethacrylate)acid phosphateMethyl acrylatemethacrylateisobutylmethacrylate Solid content (wt%) Clay (P) at 25°C (Examples 18-28 and Comparative Examples 4-12) Reference Examples 7-2
After diluting the polymer produced in step 4 with methyl cellosolve so that the solid content of the total °C polymer was 20% by weight, Table 6
An antifogging coating composition was obtained by blending the surfactants shown in 7 and 7. Next, each composition was applied to the substrate using a bar coater so that the dry film thickness was 5 μm, and heat-dried under each condition. Various tests shown in Tables 8 and 11 were conducted on these coatings.

Table-6 Table-7 The abbreviations in Tables 6 and 7 above have the following meanings.

Surfactant (a): Polyoxyethylene nonylphenyl ether, manufactured by NOF Corporation, trade name Nonion NS-212 (b)
): Polyoxyethylene octylphenyl ether, manufactured by NOF Corporation, trade name Nonion H3- (c):
Sodium n-dodecylhenzenesulfonate, manufactured by Nippon Oil & Fats Co., Ltd., trade name Newlex R (d) Sodium Nidioctyl sulfosuccinate, manufactured by Nippon Oil & Fats Co., Ltd., trade name Lavisol B-80 (e): Octadecyltrimethylammonium chloride, Nippon Oil & Fats Co., Ltd. (product name: cation AB) Nidimethylalkyl (coconut) betaine, Nippon Oil & Fats Co., Ltd. (product name: Anon BF) Base material PC: To polycarbonate 〇2 polymethyl methacrylate curing conditions (I) at 120'C for 30 minutes (2 ): At 80'C for 60 minutes The physical properties of each of the coating films thus obtained were evaluated by the evaluation method shown below.

The results are shown in Tables 8 to 11.

(1) Breath test: The coating film was breathed on in a constant temperature room at 20°C, and cloudiness was determined by visual inspection.

◎: Not cloudy at all ○: Water droplets get wet instantly and spread Δ: Slightly cloudy It was exposed to one breath of warm water of C, and the time until it started to cloud was measured.

(3) 60°C Steam Test A coating film in a constant temperature room at 20°C was exposed to hot steam at 60°C, and the time until it started to cloud was measured.

(4) Water resistance (anti-fogging property) The coating film was immersed in water at 30°C for 24 hours, air-dried, and then subjected to the breath test described above.

(5) Adhesive Make 100 cross cuts on the surface of the coating film using a cutter knife to reach the base material, apply cellophane adhesive tape (manufactured by Chiban Co., Ltd.) and peel it in the direction perpendicular to the adhesive surface, leaving it without peeling. It is expressed as the number of crosscuts.

(6) After leaving the heat-resistant coating film in a constant temperature bath at 80°C for 1000 hours,
The adhesion test described above was conducted.

(7) Water Resistance (Adhesion) The coating film was left in a constant temperature bath at 70° C. for 200 hours, air-dried, and then subjected to the adhesion test described above.

(8) Hardness A pencil scratch test according to JIS K5400 was conducted.

0: Pencil lead hardness 2H or more ×: Pencil lead hardness less than 2H (9) Water resistance (paint film strength) Appearance of the paint film after being immersed in water at 30°C for 24 hours. Judgment was made visually.

○: No change in appearance ×: Items with a change in appearance Table-8 Table-9 Table-10 Table-11 The abbreviations in Tables 8 to 11 above have the following meanings.

Adhesion test (a): 100/100 (b): 30/100 (C): 15/100 (d) O/100 (Reference Examples 25 to 34) (Production of block copolymer) Temperature needle, stirrer 230 parts of methyl cellosolve was charged into a reactor equipped with a reflux condenser and heated to 72°C without blowing nitrogen gas.
100 parts (meth)glycidyl acrylate or N-methylolacrylamide Part A (meth)
Hydroxyalkyl acrylate 8 parts acrylamide,
Monomer selected from N-monomethylacrylamide, NN-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone 0 parts -(CO(CH2)JC
OO(C2H,0)ff -CO(C)12)4COO
O) A mixed solution consisting of 1020 parts was prepared for 2 hours, and then for another 2 hours.
A polymerization reaction was performed. Then, 30 parts of a mixed solution consisting of 285 parts of methyl cellosolve, parts D of lower alkyl (meth)acrylate, and parts E of (meth)acrylic acid were added.
The mixture was charged over several minutes and the polymerization reaction was carried out at 75°C for 5 hours. The number of copies of A to E above is as shown in Tables 12 and 13. The polymerization results are also shown in Tables 12 and 13.

(Reference Examples 35 to 40) (Production of graft copolymer) 230 parts of methyl cellosolve was charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and nitrogen gas was blown into the reactor.
Heated to 5°C, and added t-butyl peroxyoctanoate (product name: Perbutyl OJ, manufactured by NOF Corporation).
10 hours half-life temperature 72'C) 2.3 parts, 0 parts of t-butylberoxymethacryloyloxyethycarbonate as radical copolymerizable organic peroxide, 100 parts of methyl cellosolve (meth)acrylic Glycidyl acid or N-methylolacrylamide part A (meth)
Hydroxyalkyl acrylate 3-part acrylamide,
0 parts of a monomer selected from N-monomethylacrylamide, N,N-dimethylacrylamide, acryloylmorpholine, and N-vinylpyrrolidone were mixed, and this mixed solution was charged over 2 hours, and the polymerization reaction was further carried out for 7 hours. Thereafter, the temperature was raised to IIO'C, and a mixed solution consisting of 285 parts of methyl cellosolve, parts D of lower alkyl (meth)acrylate, and parts E of (meth)acrylic acid was added.
A graft copolymer was produced by charging the mixture in portions and conducting a polymerization reaction for 7 hours at IIO'C.

The number of parts of A-E and the polymerization results are shown in Table-13.

(Reference Examples 41 to 44) (Production of random copolymer) 230 parts of methyl cellosolve was charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and nitrogen gas was blown into the reactor.
Heat to 5°C and add 2.3 parts of t-butyl peroxyoctanoate, 370 parts of methyl cellosolve (meth)glycidyl acrylate or N-methylolacrylamide Part A (meth)
Hydroxyalkyl acrylate 3-part acrylamide,
Monomer selected from N-monomethylacrylamide, N,N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone 0 parts lower alkyl (meth)acrylate D parts (meth)acrylic acid
A mixed solution consisting of part E was charged over a period of 3 hours, and the polymerization reaction was further carried out for 7 hours. The number of parts of A-E and the polymerization results are shown in Table-13.

Table-12 table Above table-12 and table represents.

■: Glycidyl methacrylate■: N-methylolacrylic”?mid■: 2-hydroxyethyl methacrylate■2-hydroxyethyl methacrylate■: 2-hydroxypropyl methacrylate■Niacrylamide■2N-monomethylacrylamide■ HN, N-dimethylacrylamide ■: N-acryloylmorpholine [phase]: N-vinylpyrrolidone ■ = methyl methacrylate @ ethyl nitacrylate @: ethyl methacrylate 0: methacrylic acid ■ diacrylic acid *: solid content (wt%) ) *: Clay (P) at 25'C The abbreviations at 13 have the following meanings (Examples 29 to 47 and Comparative Examples 13 to 22) Reference Example 25
2. The surfactants shown in Tables 14 to 16 were blended with the polymer produced in steps 44 to 44, and the composition was coated on a polyester film (polyethylene terephthalate film E-5101 manufactured by Toyobo Co., Ltd.). After construction, also Table-14
It was heat-cured under the conditions shown in ~16. Various tests shown in Tables 17 to 19 were conducted on these coatings.

Table-14 Table-15 Table-16 The approximate month of the surfactant in Table-14-16 above has the following meaning.

(a): Polyoxyethylene 5-nostearate, manufactured by NOF Corporation, trade name Nonion S-4 (b): Polyoxyethylene nonylphenyl ether, manufactured by NOF Corporation, trade name Nonion NS-212 (c
): sodium n-dodecylbenzenesulfonate,
Niwrex R (d): Sodium dioctyl sulfosuccinate (trade name, manufactured by NOF Corporation), Ravisol B-80 (e) (trade name, manufactured by NOF Corporation): Octadecyltrimethylammonium chloride (trade name: Cation AB, manufactured by NOF Corporation) Nidimethylalkyl Resin Co., Ltd., product name: Anon BF ((to): balatoluenesulfonic acid (h): polyoxyethylene-polyoxybrobylene condensate, Asahi Denka Kogyo Co., Ltd., product name: Pluronic F-6
8 (i): polyoxyethylene nonylphenyl ether,
Dai-ichi Kogyo Seiyaku Co., Ltd., product name Neugen EA (j) Nidialkyl sulfosuccinate ester, Dai-ichi Kogyo Seiyaku Co., Ltd. product name Neocol SW (k): Stearyl betaine, Matsumoto Yushi Co., Ltd. product name Vistar MS Table - 17 Table-19 The abbreviations in Tables-17 to 19 above have the following meanings.

(1): The coating film formed in a constant temperature room kept at 20°C was breathed on, and the wet state of the coating film was visually determined.

Table 18゜(2): A paint film formed in a constant temperature room kept at 20"C was exposed horizontally to warm water at 60°C, and the wet state of the paint film was visually judged after leaving it for 1 minute. .

(3): A coating film formed in a constant temperature room kept at 20°C was vertically exposed to hot water at 60°C in a sealed state, and the evaluation was made based on the time until the coating film started to become cloudy.

(4): The coating film formed in a thermostatic chamber kept at 20°C was immersed in water at 30°C, taken out every hour, allowed to dry naturally, and then the same coating film was sprayed with air for 2 coats. The cloudy state of the film was visually determined.

(5): After 1 hour (6): After 3 hours (10 hours after crab) (8): Cross-cut the surface of the coating film formed in a thermostatic chamber kept at 20°C with a cutter knife to remove cellophane. A tape (manufactured by Jiban Co., Ltd.) was applied to the tape, and the cellophane tape was peeled off in a direction perpendicular to the adhesive surface, and the degree of peeling of the coating film was visually determined.

(9): A coating film formed in a thermostatic chamber kept at 20°C was immersed in water at 30°C for 10 hours, and then taken out and rubbed with a finger to visually evaluate the degree of damage and peeling of the coating film.

Moreover, the evaluation criteria for coating film performance are as follows.

◎: No abnormality at all ○: Almost no abnormality Δ: Slightly inferior ×: Completely inferior Instantaneous: It begins to cloud as soon as it is evaluated As shown above, the antifogging resin coating film of the present invention is formed. It was found that the composition exhibited good antifogging durability, coating film strength, and adhesion in a well-balanced manner. On the other hand, when a block copolymer, a graft copolymer, or a random copolymer outside the specific composition range of the present invention is used, there is a drawback in any of these three properties, and the antifogging resin coating forming composition It was found that the performance was insufficient.

Claims (1)

[Claims] 1. A type selected from block copolymers consisting of a hydrophilic polymer portion and a hydrophobic polymer portion, and graft copolymers consisting of a hydrophilic polymer portion and a hydrophobic polymer portion An antifogging resin film-forming composition comprising the above copolymer containing a surfactant. . 2. In the antifogging resin coating forming composition according to claim 1, the block copolymer has the following general formula (I
) or N-substituted or unsubstituted (meta) represented by (II)
At least one acrylamide compound 1-40
Weight %, monomer selected from the group consisting of monomers having a crosslinkable functional group such as glycidyl group, N-methylol group, N-methylol ether group, carboxyl group, or acid anhydride (hereinafter referred to as group A) At least one type of body 1-2
0% by weight and a hydrophilic polymer portion consisting of 40 to 98% by weight of at least one hydrophilic monomer copolymerizable with the above monomers, and a monomer selected from the monomers of Group A above. a hydrophobic polymer portion consisting of 1 to 40% by weight of at least one type of monomer and 60 to 99% by weight of at least one type of hydrophobic monomer copolymerizable with the monomers of Group A above. , an antifogging resin coating-forming composition characterized in that the weight ratio of the hydrophilic polymer portion to the hydrophobic polymer portion is from 50/50 to 95/5. General formula (I) CH_2=CR_1CONR_2R_3 In the above formula, R_1 and R_2 are hydrogen atoms or methyl groups, and R_3 is hydrogen atoms, methyl groups, ethyl groups, n-propyl groups, isopyrrobyl groups, N,N-dimethylaminopropyl groups, or -C(CH_3)_2CH_2COCH_3. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above formula, R_1 is a hydrogen atom or a methyl group, and A is -
(CH_2)_n- where n is 4 or 5, or -(CH
_2)_2-O-(CH_2)_2-. 3. In the antifogging resin coating forming composition according to claim 1, the block or graft copolymer contains 6 to 25 weight monomers consisting of glycidyl (meth)acrylate or N-methylolacrylamide. %, hydroxyalkyl (meth)acrylate 43-90% by weight, acrylamide, N-monomethylacrylamide, N,N-dimethylacrylamide, N-acryloylmorpholine, N
-4 to 32% by weight of a monomer selected from vinylpyrrolidone
and a hydrophobic polymer portion formed from 50 to 85% by weight of lower alkyl (meth)acrylate and 15 to 50% by weight of (meth)acrylic acid. Antifogging resin coating forming composition. 4. The antifogging resin coating forming composition according to claim 1, wherein the surfactant is a nonionic surfactant or an anionic surfactant. Resin film forming composition. 5. The antifogging resin coating forming composition according to claim 1, wherein the surfactant is a combination of a nonionic surfactant and an anionic surfactant. Cloudy resin film forming composition. 6. The antifogging resin coating forming composition according to claim 1, characterized in that it contains 0.1 to 20 parts by weight of a surfactant based on 100 parts by weight of the copolymer. An antifogging resin coating forming composition.