JPS59179647A - Anti-fogging composition having excellent adhesiveness - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which is excellent in sustained anti- fogging properties and surface hardness when wet, consisting of a specified modi fied PVA, an aq. emulsion of a high-molecular material and fine inorg. particles. CONSTITUTION:A copolymer of a vinyl ester (e.g. vinyl acetate) with 0.01- 10mol% of an olefinically unsaturated monomer contg. a silyl group of formula I or II (wherein R<2> is a 1-5C alkyl; R<2> is a 1-40C alkoxyl which may be substituted with an O-contg. substituent, acyloxyl; R<3> is H, methyl; R<4> is H, R<1>; R<5> is a 1-5C alkylene, a bivalent org. residue wherein two carbon chains are bonded to each other through an O or N atom; n is 0-4; m is 0-2) is saponified to obtain a modified PVA (a) contg. silyl groups in the molecule. 5-900pts.wt. (on a solid basis) aq. emulsion (b) of a high-molecular material (e.g. polyester emulsion) is blended with 100pts.wt. component (a). Alternatively, 0.5-95wt% component (a) is mixed with 99.5-5wt% inorg. particles having an average particle size of 200mu or below (e.g. colloidal silica), and the resulting mixture is then mixed with component (b).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an antifogging composition, and particularly to an antifogging composition that is excellent in adhesion, long-lasting heat protection, and surface-j hardness upon water absorption.

In general, transparent materials such as plastic materials and inorganic glasses are widely used as architectural, military, or aircraft window glasses, mirrors, eyeglass lenses, goggles, agricultural films, and food packaging films. However, these transparent materials have the disadvantage that moisture in the atmosphere condenses on the surface under conditions of high humidity or when the surface temperature is below the dew point, causing the surface to become cloudy. Furthermore, in the case of glass materials, there is a drawback that the surface is easily scratched, and transparency is easily reduced due to scratches.

Various attempts have been made to prevent this phenomenon and to impart antifogging properties and scratch resistance to the surface of transparent materials. For example, methods have been proposed in which surfactants, glycerin, polyalkylene glycols, cellulose derivatives, polyvinyl alcohol, polyhydroxyalkyl acrylates, polyethyleneimine, etc. are applied to improve the water wettability of the surface of transparent materials. However, although this method can temporarily impart antifogging properties, it has drawbacks such as the antifogging effect being degraded due to the outflow of the antifogging agent, and the scratch resistance being insufficient. had. Also, JP-A-53-19347, JP-A-55-999
87 or JP-A-57-73059 etc., the main ingredients are a hydrophilic polymer such as polyvinyl alcohol/V (hereinafter referred to as PVA) and silica, or a combination of these and a low-molecular organosilicon compound. A method for forming an antifogging film is disclosed. However, the anti-fog coatings produced by these methods have the disadvantage that their surface hardness is low when water is absorbed, and they are easily scratched by nails, etc., and their adhesion to transparent materials, especially plastics, is insufficient. , it was hardly of practical use.

The present inventors have overcame the above-mentioned drawbacks, and have made extensive studies to develop an antifogging agent that has sustained antifogging properties, has sufficient adhesion and surface hardness even when water is absorbed, and has excellent scratch resistance. As a result, an antifogging composition consisting of a supramolecular aqueous emulsion, a supramolecular aqueous emulsion, or a supramolecular aqueous emulsion of modified PVA having a silyl group in its molecule has the ability to maintain antifogging properties and has a surface hardness that decreases when water is absorbed. The present inventors have discovered that this antifogging agent has significantly higher scratch resistance than conventional antifogging agents, has excellent scratch resistance, and has high adhesion to transparent materials, and has completed the present invention.

The present invention will be explained in detail below.

The modified PVA having a silyl group in the molecule used in the present invention may be any one having a silyl group in the molecule, but the silyl group contained in the molecule may be an alkoxyl group or one of these. Particularly preferably used are those having a reactive substituent such as a silanol group or a salt thereof, which is a hydrolyzate.

Methods for producing such modified PVA include: 1. Introducing cycilyl groups into PVA or modified polyvinyl acetate containing carboxyl or hydroxyl groups by post-modification using a silica inhibitor, 2. A method for saponifying a copolymer with a group-containing olefinically unsaturated monomer,
)) A method of saponifying a vinyl ester polymer having a salt group. In the method of post-modifying PVA or modified polyvinyl acetate using a silylating agent, for example, the silylating agent is added to an organic solvent that does not react with the silylating agent, such as benzene, toluene, xylene, hexane, heptane, ether or acetone. The inhibitor is dissolved, and the powdered PVA or the above-mentioned modified polyvinyl acetate is stirred and dissolved in the solution at room temperature to the boiling point of the inhibitor. agent and PVA
Alternatively, a silyl group-containing modified PVA can be obtained by the above modification or by reacting with 35 1J vinyl acetate or by further saponifying the vinyl acetate unit of the modified polyvinyl acetate using an alkali catalyst or the like. The inhibitors used in post-denaturation include trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, vinyltrichlorosilane, diphenyldichlorosilane, and trichlorosilane. Organohalogen silanes such as fluorosilane, organosilicon esters such as trimethy/l/acetoxysilane, dimethyldiacetoxysilane, organoalkoxysilanes such as trimethylmethoxysilane, dimethylmethoxysilane, trimethylsilane, diethyl diacetoxysilane Examples include organosilano-)v such as O/v, aminoalkyl siphens such as N-aminoethylaminobrohyde/vl-rimethoxysifun, and organosilicon isocyanates such as trimethyl silicon isocyanate. The rate of introduction of the silylating agent, that is, the degree of modification, can be arbitrarily adjusted by adjusting the amount of the silylating agent used and the reaction time.

Also obtained is the IJ7 group-containing modification. The degree of polymerization and saponification of PVA can be adjusted as desired by the degree of polymerization and saponification of the PVA used, or the degree of polymerization and saponification of the above-mentioned modified polyvinyl acetate.

In addition, in a method of saponifying a copolymer of a vinyl ester and an olefinically unsaturated monomer containing a silyl group, for example, the vinyl ester and the olefinically unsaturated monomer containing a silyl group are combined with a radical initiator. A silyl group-containing modified PVA can be obtained by copolymerizing the copolymer and then saponifying the copolymer by adding an alkali or acid catalyst to an alcohol solution of the copolymer. Vinyl esters used in the above method include vinyl acetate, vinyl propionate, vinyl formate, etc., but vinyl acetate is preferred from an economical standpoint. Examples of the olefinically unsaturated monomer containing a silica group used in the above method include vinylsilanes represented by the following formula (1) and (meth)acrylamidoalkylsibane represented by (I[).

忰] CH 3=CH (CH 2) n S+
(JL 2)5-Hl (1)R4
Interchange CHs=OR5-ON-Bon5-Si-(R6-□
(II) [where n is 0 to 4, m is 0 to 2, R1 is an alkyl group having 1 to 5 carbon atoms (methyl, ethyl, etc.),
it2 is an alkoxyl group or an acyloxyl group having 1 to 40 carbon atoms (herein, the alkoxyl group or acyloxyl group may have an oxygen-containing substituent), R
3 is a hydrogen atom or a methyl group, IL' is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R5 is an alkylene group having 1 to 5 carbon atoms or a divalent group in which chain carbon atoms are bonded to each other by oxygen or nitrogen. Each organic residue is indicated. In addition, when two R1s exist in the same monomer, ll-l:R
1 may be the same or different. Furthermore, even when two or more of ``2'' exist in the same monomer, ``2'' may be the same or different.

Specific examples of the vinylsilane represented by formula (r) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-(β-methoxyethoxy)silane, vinyltriacetoxysilane, and allyltrimethoxysilane. Ran, Aril
Tri acetoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinylmethyljethoxysilane, vinyldimethylethoxysilane, vinylmethyldiacetoxysilane, vinyldimethylacetoxysilane, vinylisobutyldimethoxysilane, vinyltriisogloboxysilane, vinyl Triatoxysilane, vinyltrihexyloxysilane, vinylmethoxydihexyloxysilane, vinyldimethoxyoctyloxysilane, vinylmethoxydioleyloxysilane, vinyltrioctyloxysilane, vinylmethoxydifuryloxysilane, vinyldimethoxylacryloxysilane, vinyl Methoxydioleyloxysilane, vinyldimethoxyoleyloxysilane, and general formula % formula % (where R1 and m are the same as above, and X represents 1 to 20)
Examples include polyethylene glycolized vinylsilane represented by: Specific examples of the (meth)acrylamido-alkylsilane represented by formula (Il) include 6-(meth)acrylamidopropyltrimethoxysilane, 6-(meth)acrylamidopropyltriethoxysilane, 6-(meth)acrylamidopropyltriethoxysilane, (Meta) Arili Luami D-fu”ro Piru Tori (β-Tsume l-
xyethoxysilane, 2-(meth)acrylic silane
Do-2-methyl propyl trimethoxy silane, 2-(meth)acrylamide-2-
Methylethyltrimethoxysilane, N-(2-(meth)
Acrylamidoethyltrimethoxysilane, 3-(meth)acrylamide-prohyltriacetoxysilane, 2-(meth)acrylamide-
Ethyltrimethoxysilane, 1-('metalaacrylamidomethyltrimedoxysilane, 3-()Ari)acrylamidoglopylmethyldimethoxysilane, 3-(
meth)acrylamido-propyldimethylmethoxysilane, 5-(N-methyl-(meth)acrylamido)-propyltrimethoxysilane, 3-((meth)acrylamido-methoxy)-5-hydroxypropyltrimethoxysiland-methoxy)-propyl Trimethoxysilane, dimethyl/-3 (meth)acrylamide-propy/l/-3
Examples include -()rimethoxysily/L/)-propylammonium chloride, dimethy/L/T2-(meth)acrylamide-2-methyl bropylmethoxysily/l/)-propylammonium chloride, etc. It will be done.

In addition, when copolymerizing the K-attehabinyl ester and the silyl group-containing olefinic unsaturated monomer to produce modified PVA by this method, in addition to the above two components, it is also necessary to Saturated monomers such as styrene, alkyl vinyl ether, vinyl versatate,
(meth)acrylamide, ethylene, propylene, α-
Olefins such as hexeno and α-octene, (meth)acrylic acid, crotonic acid, (anhydrous) maleic acid, fumaric acid,
Unsaturated acids such as itaconic acid and their alkyl esters,
Alkali salts, sulfonic acid-containing monomers such as 2-acrylamido-2-methylpropanesulfonic acid and their alkali salts, trime 4-/I/-2-(1-(meth)acrylamido-1,1-dimethyl 3- (1-(meth)acrylamidopropylummonium chloride, 1-viny/l/-2
- It is also possible to have a cationic monomer such as methylimidazole and its quaternized product present in a small proportion.

In addition, in the method of saponifying a vinyl varnish 7/v polymer having a silyl group at the terminal obtained by polymerizing tehenyl ester) v in the presence of a mercaptan having a silyl group, for example, vinyl ester is converted into a vinyl ester using a radical initiator. During polymerization, a mercaptan having a silyl group is added to the polymerization system all at once, in portions, or continuously, so that the mercaptan having a silyl group is present in the polymerization system, and chain transfer to the mercaptan causes silyl at the terminal. Modified PVA having a silyl group can be obtained by producing a vinyl ester polymer having a group, and saponifying the polymer by adding an alkali or acid catalyst to an alcohol solution of the polymer.

The mercaptan having a silyl group used in this method is 5-(trimethoxysilyl)-propyl mercaptan, propyl mercaptane, and mercaptan.

When producing tetravalent PVA by this method, it is also possible to include a small proportion of an unsaturated monomer copolymerizable with the vinyl ester used in method (2).

In the above-mentioned three production methods of modified PVA having a silyl group in the molecule used in the present invention, a copolymer of a vinyl ester and an olefinically unsaturated monomer having a silyl group is used. A method of saponifying a vinyl ester polymer having a silyl group at the terminal obtained by polymerizing a vinyl ester in the presence of a mercaptan having a silyl group is easy for industrial production, and the resulting modification is easy. It is preferably used in terms of the homogeneity of PVA.

The content of silyl groups, degree of saponification or degree of polymerization in the modified PVA having silyl groups used in the present invention are appropriately selected depending on the purpose and are not particularly limited. The effect of silyl group is exhibited even at a relatively small content, and usually silyl group
) 0.01 to 10 mo/
L/%, preferably selected from the range of 0.1 to 2.5 mol%. The saponification degree is usually preferably in the range of 70 to 100 mol%. Further, the degree of polymerization is usually selected from the range of 10 to 3,000.

When dissolving the above-mentioned modified PVAI used in the present invention in water, the modified P'VAI is usually dissolved in water. A homogeneous aqueous solution can be obtained by dispersing A in water, adding alkali such as sodium hydroxide, potassium hydroxide, ammonia, etc. and heating with stirring.

Suitable examples of the aqueous polymer emulsion used in the present invention include emulsions of acrylic polymers, vinyl ester polymers, olefin polymers, diene polymers, and urethane polymers. Acrylic M combined emulsions include (meth)acrylic acid or its esters (methyl, ethyl,
Butyl or α-ethylhexy/
l/xy. 7) A homopolymer emulsion of v) (for example, a polyacrylic ester emulsion or a binary or tertiary or more copolymer emulsion with a monomer copolymerizable with these (for example, olefin such as ethylene, vinyl chloride)), etc. It's vignetting. Vinyl ester polymer emulsions include homopolymer emulsions of vinyl esters such as vinyl acetate (e.g., polyvinyl acetate emulsions) or polymers that can be copolymerized with vinyl esters (e.g., olefins such as ethylene, propylene, isobutyne, etc.). , higher fatty acid vinyl esters such as hinyl versatate, (meth)acrylic acid or its esters, maleic acid or its esters, vinyl chloride, olefinic monomers having a disilyl group in the molecule). Examples include copolymer emulsions (eg, ethylene-vinyl acetate copolymer emulsion, carboxyl-modified ethylene-vinyl acetate copolymer emulsion, vinyl acetate-vinyl versatate copolymer emulsion), and the like. Examples of the olefin polymer emulsion include homopolymer emulsions of olefins (for example, ethylene and dipropylene) and copolymer emulsions of 2 or 6 or more copolymers with monomers copolymerizable with the olefins. The diene polymer emulsion is a single IJiM polymer emulsion of diene (for example, butadiene, chloroprene, isobutylene) or a binary or ternary copolymer emulsion with a monomer copolymerizable with diene (for example, styrene, methyl methacrylate, isobutylene). Polymer emulsions (e.g. styrene-butadiene copolymer latex (SB)
R), carboxy/l/modified SBR.

acryloni) IJJ-butadiene copolymer latex,
Methyl methacrylate-butadiene copolymer latex, inbutylene-isofurene copolymer latex)
etc. This pond is polychlorinated! 77'n emulsion, ho! 7m vinyl/ray emulsion etc. can also be used. These aqueous polymer emulsions can be appropriately selected and used depending on the type of transparent material to be applied and the intended use.

A tackifier may also be added to the aqueous polymer emulsion. By using these polymer aqueous emulsions, the adhesion to transparent materials, particularly fibre-based transparent materials, can be further improved.

The blending ratio of the modified PVA having an IJ/shi group in the molecule used in the present invention and the polymer aqueous emulsion is preferably 5 to 1000 parts by weight in terms of solid content of the polymer aqueous emulsion per 100 parts by weight of the modified PVA. is 1
It is 0 to 900 parts by weight. Aqueous emulsion is jODD
If the amount is more than 5 parts, the water wettability may be poor and the antifogging property may be insufficient, and if the amount is less than 5 parts, the adhesion to transparent materials may be insufficient.

Inorganic substances that may be used in the present invention include:
Preferably, those containing elements such as aluminum, silicon, calcium, lacquer, etc. include clay, curcum, calcium carbonate, calcium silicate, silica, aluminum oxide, and water glass. ,
Water-soluble aluminum compounds (e.g. sodium aluminate,
Aqueous solutions of inorganic substances such as sulfate (sulfuric acid) and water-soluble zirconium compounds (eg zirconium carbonate) may also be used. However, when using an inorganic aqueous solution at a high temperature, C:
When mixed with PVA having a ShiIJ / Shi group in the molecule, the viscosity stability of the mixed aqueous solution is low and there is a possibility that Shige / V may occur in some cases, so it cannot be said to be the best choice. For the purpose of the present invention, inorganic fine particles are preferred, with an average particle size of 2
Inorganic fine particles with a particle diameter of 100 mμ or less, particularly colloidal silica or colloidal alumina, are preferable.
Inorganic particles of 0 mμ or less and colloidal silica are obtained immediately, which is the best in terms of the transparency of the coating film and the surface hardness upon water absorption. If the particle size exceeds 200 mμ, the resulting coating film tends to have poor transparency, which is not preferred.

In the composition of the present invention, there is no particular restriction on the blending ratio of modified PVA having a silyl group in the molecule and inorganic particles, particularly inorganic fine particles with an average particle diameter of 200 mμ or less, and any ratio may be used. Poison - Modified PVA with a group in the molecule and inorganic substances, especially those with an average particle diameter of 200
The weight mixing ratio of the inorganic fine particles of mμ or less is the former/latter 0-''/q 5), 5-9515, preferably 1/99-''/1o. If the latter ratio is less than 5, the surface hardness upon water absorption will be low, and if it exceeds 99.5, the resulting coating will have poor adhesion to transparent materials and poor scratch resistance when dry. .

As mentioned above, the antifogging composition of the present invention essentially consists of a modified PVA having a silicate group in the molecule, an aqueous polymer emulsion, or these and an inorganic substance, particularly inorganic fine particles having an average particle size of 200 mμ or less. However, in addition to these conditions, it is possible to include solvents, various additives, etc. depending on the purpose.

Water is preferably used as the solvent, but it can also be used in combination with solvents such as various alcohols, ketones, dimethylformamide, and dimethyl sulfoxide.

Additives include various antifoaming agents, nonionic or anionic surfactants, carboxymethyl cellulose,
Vas derivatives such as hydroxyethyl cellulose, poly(meth)acrylic acid, polyhydroxy(meth)acrylate or their co-mers, (meth)acrylic polymers such as polyacrylamide, polyvinylpyrrolidone or copolymers , carboxy group-containing modified PVA, sulfuric acid group-containing modified PVA, sulfonic acid group-containing modified PVA, IJ
Modified PVA containing an acid group, modified PVA containing a quaternary ammonium base, modified PVA containing an amine group, PVA derivatives such as general PVA, etc. can be added, and a silane coupling agent etc. can also be added as appropriate. .

The antifogging composition of the present invention can be dispersed in water or water containing the above-mentioned organic solvent and applied to various transparent materials as an aqueous dispersion, and the above-mentioned aqueous dispersion is usually applied to a transparent material. used by There are no special restrictions on the transparent materials to which the antifogging composition of the present invention can be applied;
Examples include inorganic glass, plastic, metal, etc.
In particular, the antifogging composition of the present invention exhibits excellent adhesion to plastics. Specifically, it is preferably used for window glasses of automobiles, trains, buildings, etc., lenses for glasses, mirrors for bathrooms, plastic films for agricultural greenhouses, plastic films for window glasses, etc.

Examples of methods for applying the antifogging composition of the present invention to transparent materials include brush coating, dip coating, spin coating, flow coating, spray coating, roll coating, air knife coating, and blade coating. Various methods known in the art can be used.

The antifogging composition of the present invention is applied to a transparent material by the above-mentioned method, but it is possible to further improve the sustained antifogging property and the surface upon water absorption by further acid treatment and heat treatment as appropriate. A coating film with high adhesion can be obtained on the surface of hard and transparent materials.

The coating film obtained by the antifogging composition of the present invention is sufficiently practical in itself, but in order to make the effect even more pronounced, various types of coatings are applied to the formed coating film. Post-treatments such as coating or impregnating with hydrophilic substances, surfactants, etc. are also effective.

In order to further improve the adhesion between the transparent material and the antifogging composition of the present invention, the surface of the transparent material may be coated with various types of brimer or adhesive, treated with an activated gas, or treated with an acid or Pretreatment such as chemical treatment with a base or the like is also effective.

The anti-fogging composition of the present invention has sustained anti-fogging properties, has high surface hardness upon absorption of water, has outstanding scratch resistance, and is characterized by high adhesion to transparent materials. be. Although the reason why the antifogging composition of the present invention has the above-mentioned remarkable performance is not fully elucidated, the modified PVA having a silyl group in the molecule used in the antifogging composition of the present invention Anti-fogging properties are exhibited due to the hydrophilicity of the hydroxyl group in the inside, and the silyl group to which an alkoxyl group or acyloxyl group is bonded, or the schiffnol group which is a hydrolyzate of these, or its salt is an inorganic or modified P.
Due to its high reactivity with the hydroxyl groups or silanol groups or their salts in VA, these react with each other to form a strong coating, which exhibits high surface hardness and scratch resistance even when water is absorbed. It is presumed that the adhesiveness of the synthetic resin emulsion provides high adhesion to transparent materials.

The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited by K. In addition, in the example, fil + elder sister word "饅" and [
Part J represents the weight standard.

Example 1 Contains 0.25 mol% of silyl group units obtained by saponifying a copolymer of vinyltrimethoxysilane and 5-vinyl acetate, with a degree of saponification of vinyl acetate units of 98 mol% and a degree of polymerization of 2.
A 10% aqueous solution was prepared by dissolving 000 modified PVA in water. Add maleic acid-modified ethylene to 100 parts of this aqueous solution.
Vinyl acetate emulsion (1% maleic unit x 75% unit, 24 vinyl acetate units, solid content 40
%) was added to obtain an aqueous dispersion of the invention. This aqueous dispersion was applied to a 125μ polyester/I/film so that the thickness after drying would be 5μ, dried at 105°C for 10 minutes, immersed in a 1/2N sulfuric acid bath, and further washed with water. , heat treatment was performed at 150°C for 1 minute. Adhesion to antifogging Wf and surface hardness were measured using the obtained test piece. The results are shown in Table 1.

From Table 1, it can be seen that the antifogging composition of the present invention is significantly superior in sustained antifogging properties, adhesion, and surface hardness upon water absorption.

Comparative Example 1 The aqueous dispersion of Example 1 (on the contrary, a commercially available low-molecular-weight surfactant-based antifogging agent was applied to a 125μ thick polyester film by a spray method, and the antifogging property was measured in the same manner as in Example 1) did. The results are shown in Table 1.

Comparative Example 2 Instead of the aqueous dispersion of Example 1, general partially saponified P'
VA (polymerization degree 600, saponification degree 88) 20 polyhydric solution 1
00 parts K, 100 parts of colloidal silica (Nissan Chemical Industries, Ltd., Snowtex-0, solid content 20%) and 4 parts of vinyl tris (β-methoxyethoxy) silane were mixed and heated at a temperature of 8.
The composition heated at 0°C for 1 hour was applied in the same manner as in Example 1, and the resulting coating film was heat-treated at 150°C for 6 minutes. Surface hardness was measured. The results are shown in Table 1.

Comparative Example 3 Instead of the aqueous dispersion of Example 1, a methanol solution of 2-hydroxyethyl methacrylate copolymer copolymerized with 5 mo/L/% glycidyl methacrylate was used and applied to a polyester film in the same manner as in Example 1. After heat-treating the resulting coating film at 120° C. for 30 minutes, antifogging properties, adhesion, and surface hardness were measured in the same manner as in Example 1. The results are shown in Table 1.

Table 1 1) Anti-fogging properties Place the test piece on a container that generates 40°C saturated steam in a room at -20°C for 10 seconds, apply saturated steam, then dry the test piece and place it on the container again. Do 10 times to put it on the chest, and the cloudy area will be 1i for 10 seconds.
-ij is expressed as the number of repetitions until it occurs in November.

Place it in a square 1r with a side length of 1mm' in a grid pattern.
: After making 100 pieces, immediately -1' (normal) or 2
After 12 hours of immersion in 0°C water or 1 hour of 80°C warm water, the test water was wiped off and a cellophane adhesive tape was applied to the surface, and when it was instantly removed, it did not come off. It is expressed as the number of squares remaining.

6) Surface hardness: The surface of the test piece was immersed in water at 20° C. for 12 hours as it was (normal state), and then scratched with pencil leads of various hardnesses, and the hardness was expressed as the highest pencil hardness without scratches.

Examples 2 to 5, Comparative Examples 4 to 5 The same procedure as in Example 1 was carried out except that the following aqueous emulsion or transparent material was used in place of the polymer aqueous emulsion or transparent material used in Example 1. The results are shown in Table 2.

Example 2: Ethylene-vinyl acetate copolymer emulsion (20 ethylene units,
4 parts of vinyl acetate units (80 fD, solid content 50%) were used, and a polyester film with a thickness of 50 μm was used as the transparent material.

Example 5: Vinyl acetate as a polymer aqueous emulsion
10 parts of a vinyl versatate copolymer emulsion (35% vinyl acetate units, 65 units vinyl versatate, solid content 40%) and a soft vinyl chloride film for agricultural greenhouses were used as a transparent material.

Example 4: 10 parts of a commercially available acrylic ester copolymer emulsion (solid content 40%) was used as a polymer aqueous emulsion, and a polymethacrylic ester plate was used as a transparent material.

Actual Mfx Example 5: A total of 5 parts of a commercially available urethane resin emulsion (solid content 40%) was used as a polymer emulsion, and a polyester film with a thickness of 12 μm was used as a transparent material.

Comparative Example 4: The same procedure as in Example 2 was carried out except that 0.8 parts of the polymer emulsion in Example 2 was used instead of 4 parts.

Comparative Example 5: The same procedure as in Example 2 was carried out except that 200 parts of the polymer emulsion in Example 2 was used instead of 4 parts.

Table 2 Example 6 Contains silyl groups obtained by saponifying a copolymer of vinyltrimethoxysilane and vinyl acetate as vinyl silane units at 0.5% v%, degree of saponification of vinyl acetate units 99
．． Modified PVA with a polymerization degree of 700 and 0 mol%
A 10% aqueous solution of modified PVA was prepared by dissolving it in water containing 1.5% of sodium hydroxide. To 100 parts of this aqueous solution, 5 parts of the vinyl acetate-vinyl versatate copolymer emulsion used in Example 3 and 50 parts of colloidal silica (Kaguchi Kagaku Kogyo ■, Snowtex-20, particle size 10-20 mμ, solid content 20%) were added. In addition, an aqueous dispersion of the antifogging composition of the present invention was obtained. This aqueous dispersion was coated on a glass plate with a bar coater to a thickness of 5 μm after drying, dried at 105 C for 10 minutes, immersed in a 1/2 N sulfuric acid bath, washed with water, and heated at 150° C. Heat treatment was performed at C for 1 minute. Using the obtained test piece, antifogging properties, adhesion to glass, and surface hardness were measured. The results are shown in Table 6.

Table 3 shows that the antifogging composition of the present invention is significantly superior in sustained antifogging properties, adhesion, and surface hardness upon water absorption.

Examples 7 to 13 The same procedure as in Example 6 was carried out except that the following modified PVA aqueous solution was used instead of the modified PVA aqueous solution used in Example 6.

The results are shown in Table 5.

Modified PVA aqueous solution used in Example 7: Contains 0.5 mol% of silyl groups obtained by saponifying a copolymer of vinyltriethoxysilane and vinyl acetate as vinyl silane units, and saponifies the vinyl acetate units. Modified PVA with a degree of polymerization of 98.5 mo/L/% and a degree of polymerization of 700 is added to
1 obtained by dissolving in an aqueous solution containing potassium hydroxide
0 water soluble g! .

Modified PVA aqueous solution used in Example 8 - 6-methacrylamide dropyltrimethoxysilane containing 0.15 mol% of methacrylamide silane units by saponifying the copolymer with vinyl acetate, A 10% aqueous solution obtained by dissolving modified PVA with a degree of saponification of vinyl acetate units of 88 mo)v% and a degree of polymerization of 2000 in water.

Modified PVA aqueous solution used in Example 9: 0.20 mo/L of silyl groups obtained by saponifying a copolymer of vinyltriacetoxysilane and vinyl acetate as vinylsilane units.
/%, and the degree of saponification of vinyl acetate units is 9B. 5mo)v
%, degree of polymerization 1750 (7) A 10% aqueous solution obtained by dissolving modified PVA in water.

Modified PVA aqueous solution used in Example 10: 0.25 silyl groups obtained by saponifying a copolymer of vinylμ triisopropoxycycne and vinyl acetate as vinylsilane units
m) Contains v%, and the degree of saponification of vinyl acetate units is 89.0.
A 10% aqueous solution obtained by dissolving modified PVA with a degree of polymerization of 1750 in water.

Modified PVA used in Example 11: 1 dimethyl-half-3
-Methacrylamide F-Propy/L/+- $ 5-)
Contains 0.2 mol% of silyl groups obtained by saponifying a copolymer of rimethoxysilylprobyl semi-ammonium crophyte and vinyl acetate, and the degree of saponification of vinyl acetate units is 98.
．． 10 aqueous solution obtained by dissolving 5 mol % modified PVA with a degree of polymerization of 1750 in water.

Modified PVA aqueous solution used in Example 12: When vinyl acetate is radically polymerized in methanol, 5-(trimethoxysilyl)-propynone mercaptan is continuously added to the polymerization system. Saponifying a modified polyvinyl acetate containing a silyl group to contain 1 mo) v% of a silyl group as a propyl mercaptan unit,
A 20% aqueous solution obtained by obtaining modified PVA with a degree of saponification of vinyl acetate units of 29.0 mo)v% and a degree of polymerization of 100, and dissolving this modified PVA in water.

Modified PVA aqueous solution used in Example 13: Contains 4 mo/I/% of silyl groups as propyl mercaptan units obtained by the same method as in Example 12, saponification degree of vinyl acetate units of 98.6 mol%, polymerization A 20% aqueous solution of modified PVA with a temperature of 25 degrees.

Table 6 Example 6 was carried out in the same manner as in Example 6, except that the following amounts were used in place of the 50 parts of colloidal silica in Example B. 4th result
Shown in the table.

Example 14 Varnish Notex-N (6san Kagaku Kogyo (Kawa,
Particle size 10-20rn/l, solid content 20%) 10 parts hN Example 1s Nisnortex-N-62 parts m Example 16: Snowtex-30 (Six San Kagaku Kogyo (Kan), particle size 10-2Qmμ , solid content 60%) Example 17: 150 parts of Snowtex-60 Table 4

Claims (1)

[Scope of Claims] (1) An antifogging composition with excellent adhesive properties, comprising a modified polyvinyl alcohol having a silyl group in the molecule, an aqueous polymer emulsion, or these and an inorganic substance. (2) A patent claim characterized in that the modified polyvinyl alcohol having a silyl group in the molecule is a saponified product of a copolymer of a vinyl ester and an olefinically unsaturated monomer having a silyl group in the molecule. The antifogging composition according to scope 1. (5) The olefinically unsaturated monomer having a group IJ)v in the molecule has the following general formula (1)% formula% (1) [where n is 0 to 4, m is 0 to 2, and R1 is Carbon number 1-5
The alkyl group R2 represents an alkoxyl group or an acyloxyl group having 1 to 40 carbon atoms (herein, the acyloxyl group may have a substituent containing an element k). ] The antifogging composition according to claim 2, which is a vinyl sulfate represented by: (4) The olefinically unsaturated monomer having a silyl group in the molecule has the following general formula (It) R'R'm CH2= CR5-0N -R''-8i -(R2)3
-In(ll) [Here, m is 0 to 2, and 1 is the number of carbon atoms
~5 fulky) v group, R2 is an alkoxyl group having 1 to 40 carbon atoms -IU acyloxyl, fl (i alkoxylacyloxyl group may have an oxygen-containing substituent), R3 is a hydrogen atom or The methyl group, W represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and 几5 represents an alkylene group having 1 to 5 carbon atoms or a divalent organic residue in which chain carbon atoms are bonded to each other by oxygen or nitrogen. ] The antifogging composition according to claim 2, which is a monomer represented by the following. (5) A saponified product of a polyvinyl ester having a silyl group at the end obtained by polymerizing a modified polyvinyl alcohol having a silyl group in the molecule in the presence of a mercaptan having a silyl group. The antifogging composition according to claim 1. (6) The antifogging composition according to claim 1, wherein the modified polyvinyl alcohol contains 0.01 to 10 mo/V% of a monomer unit having a silyl group in the molecule. (7) The aqueous polymer emulsion is made of one or more aqueous polymers selected from the group consisting of acrylic polymers, vinyl ester polymers, olefin polymers, diene polymers, and urethane resins. The antifogging composition according to claim 1, which is an emulsion. (8) Antifogging property according to claim 1, in which 10 to 900 parts by weight of a polymer aqueous emulsion is used in terms of solid content per 100 parts by weight of modified polyvinyl alcohol having a silyl group in the molecule/L/ Composition. (9) The antifogging composition according to claim 1, wherein the inorganic substance is fine particles having an average particle diameter of 200 mμ or less. 0. The antifogging composition according to claim 1, wherein the inorganic substance is fine particles having an average particle diameter of 100 +n/ or less. θ1) The antifogging composition according to claim 1, wherein the inorganic substance is colloidal silica.