JPS60250018A - Antifogging resin - Google Patents

Abstract

PURPOSE:The title resin having a water absorptivity which is high at low temperature but which decreases with an increasing temperature, comprising a specified N-alkyl- or N-alkylene-substituted (meth)acrylamide polymer. CONSTITUTION:A (co)polymer is obtained by (co)polymerizing an N-alkyl- or N-alkylene-substituted (meth)acrylamide monomer of formula I or II [wherein R1 is H or methyl, R2 is H, methyl, or ethyl, R3 is methyl, ethyl, or propyl, A is -(CH2)n or -(CH2)2-O-(CH2)2-, and n is 4-6] with, optionally, other copolymerizable monomers (e.g., acrylamide) in the presence of a polymerization initiator (e.g., ammonium persulfate) in a solvent (e.g., methanol). This (co)polymer is applied to an object such as a windowglass and heated to 60-250 deg.C to water- insolubilize it.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an antifogging resin. More specifically, the present invention relates to an antifogging resin made of a polymer of a specific (ivy) acrylamide derivative.

Prior art and its problems: Inorganic glass, transparent ceramics, plastic materials, etc. are used to make window glass for houses, trains, etc. by utilizing their transparency.
It is used for a variety of purposes, such as window glass for trains and other passenger vehicles, mirror surfaces, eyeglass lenses, and goggle tubes.

However, one major drawback of these various products is that if they are used in locations with high temperatures or high humidity, or in locations with large temperature or humidity conditions, water vapor will condense on their surfaces, resulting in cloudy surfaces. Particularly when the surfaces of window glass, eyeglass lenses, mirror surfaces, etc. become cloudy, various problems arise.

Conventionally, various attempts have been made to solve this problem. Acrylate polymer, various silicone compounds such as dimethylsiloxane, etc.
Methods such as applying or spraying one species or a combination of two or more species are being considered. However, none of these methods is yet fully satisfactory (and various improvements have been attempted).The reason for this differs depending on the method used, and various factors can be considered.

Means for Solving the Problem 2 The inventors of the present invention focused on the fact that most of the fogging occurs when the surface of cold glass comes into contact with warm air. As a result of intensive efforts to develop a temperature-sensitive water-absorbing resin, it was discovered that it functions as an excellent antifogging resin, leading to the present invention.

That is, the present invention provides a general formula (R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom, a methyl group or an ethyl group, and R3 is a methyl group, an ethyl group, or a propyl group). General formula (in the above formula, R2 is a hydrogen atom or a methyl group, A is ÷Cl4
For 2 horses, n is 4-6 or +C82% O(-CR2+2
wRepresent. ) N-alkyl or N-alkylene substituted (
Meta) Copolymer antifogging resin with other copolymerizable monomers.

The specific N-alkyl- or N-alkylene-substituted (meth)acrylamide of the present invention includes, for example, N-n-'propylacrylamide (polymer low point 32°C), N-n-propylmethacrylamide Amide, N-isopropylacrylamide (polymer strength point 29°C), N
- inopropylmethacrylamide, N-ethylacrylamide, N,N-diethylacrylamide, N-ethylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-acryloylpyrrolidine (N low point 51 °C), N-methacryloylpyrrolidine, N-acryloylpiperidine, N
-methacryloylpiperidine, N-acryloylmorpholine and the like.

In addition, monomers that can be copolymerized with the above monomers include:
Examples include hydrophilic monomers, ionic monomers, lipophilic monomers, etc.3, and one or more of these monomers can be applied. Specifically, examples of hydrophilic monomers include acrylamide,
Methacrylamide, N-methylacrylamide, diacetone acrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl acrylate, hydroxyethyl acrylate, 11 methoxypolyethylene glycol methacrylates, various methoxypolyethylene glycol acrylates, N-
Examples include vinyl-2-pyrrolidone, and vinyl acetate, glycidyl methacrylate, etc. can be introduced by copolymerization and hydrolyzed to impart hydrophilicity. Examples of ionic monomers include acrylic acid, methacrylic acid, vinyl sulfonic acid, allyl sulfone, methallylsulfone, styrene sulfone, 2-acrylamide-2-phenypropanesulfonic acid, and 2-acrylamide. l such as 2-methyl-propanesulfonic acid and salts thereof, N.

Amines and their salts such as N-dimethylaminoethyl methacrylate, N,N-diethylamine ethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminepropylmethacrylamide, N,N-dimethylaminopropylacrylamide, etc. Can you give me that? It is also possible to introduce various acrylates, methacrylates, acrylamide, methacrylamide, acrylonitrile, etc. by copolymerization and hydrolyze them to impart ionicity. Examples of lipophilic monomers include N-n-butylacrylamide, N
-n-butyl methacrylamide, N-tcrt, -
Butylacrylamide, N-tert, -butylmethacrylamide, N-n-hexylacrylamide, N-
n-hexylmethacrylamide, N-n-octylacrylamide, N-n-octylmethacrylamide,
N-tert, -octylacrylamide, N -n-
N-alkyl (meth)acrylamide derivatives such as dodecyl acrylamide, N-n-dodecyl methacrylamide, N, N-diglycidyl acrylamide, N,
N-diglycidyl methacrylamide, N-(4-glycidoxybutyl)acrylamide, N-(4-glycidoxybutyl)methacrylamide, N-(5-glycidoxypentyl)acrylamide, N-(6-glycidylmethacrylamide) N-(w-glycidochinoalkyl)(meth)acrylamide derivatives such as sidoxyhexyl)acrylamide, ethyl acrylate, methyl methacrylate, butyl methacrylate, butyl acrylate, lauryl acrylate, 2-
(meth)acrylate derivatives such as ethylhexyl methacrylate and glycidyl methacrylate, acrylonitrile, methacrylate trile, vinyl acetate, vinyl chloride, olefins such as ethylene, propylene, butene, styrene, α-methylstyrene, butadiene, isoprene, etc. I can give it to you.

Next, the above-mentioned monomers are polymerized to produce an antifogging resin. 1-filter Specific method (]) Polymerize in an aqueous solution, or use the polymer aqueous solution as it is or dry to remove water and polymerize. (2) After polymerization by polymerization in a solvent, the polymer may be precipitated as a polymer solution or by distilling off the solvent or adding it to a poor solvent that does not dissolve the polymer to precipitate the polymer. (3) Obtaining the polymer as a polymer emulsion by emulsion polymerization; (4) Obtaining the polymer as polymer particles by suspension polymerization; (5) Diluting the monomer with a solvent. There are methods such as directly polymerizing the polymer to obtain a polymer block, among which methods (1), (2), and (3) are preferred. In the method (2), a wide variety of solvents can be used during polymerization because (meth)acrylamide and its N-substituted derivatives have very good compatibility with various solvents.

Specifically, alcohols such as methanol and ethanol, cyclic ethers such as tetrahydrofuran and 1,4-dioxane, ketones such as acetone, amides such as N,N-dimethylformamidecetamide, benzene, Aromatic hydrocarbons such as toluene, halogenated hydrocarbons such as chloroform and methylene chloride, dimethyl sulfoxide, N-
Examples include chain glycols such as methylpyrrolidone, diglyme, and tetraglyme, and basic solvents such as pyridine.

At this time, the polymerization can be initiated by heating alone, but better results are usually obtained by using a polymerization initiator. The polymerization initiator is not limited as long as it has the ability to initiate radical polymerization (for example, inorganic peroxides, organic peroxides, combinations of these peroxides and reducing agents), azo compounds, etc. Specifically, ammonium persulfate, potassium persulfate, hydrogen peroxide, t
There are ert-butyl peroxide, benzoyl peroxide, cumene hydroxyperoxide, tert'-butyl peroxy-2-ethylhexanoate, perbenzoate butyl, etc., and the reducing agent to be combined with them is sulfite: linsalt. , hydrogen sulfur salts, salts with low ionic valences such as iron, copper, and cobalt, organic amines such as aniline, and reductions of aldoses, ketones, etc.; Examples of anion compounds include azobisinobutyronitrile, 2
,2-Anobi-2-amidinopropane salt 1"!Salt,
2,2-azobis-2,4-dimethylhaleronitrile,
4.4-Azobis-4-/ano-leic acid and the like can be used.

It is also possible to use two or more of the polymerization initiators listed in 1- in combination. In this case, the amount of the polymerization initiator added is within the normally adopted odd range, and for example, 0 per monomer.
01-5 Chonggong? o, preferably O. The amount of Cl3-2 is in the range of %.

Among the polymers thus obtained, those obtained in solid form can be dissolved in any solvent to provide a solution, or pulverized to provide a powder. At this time, the solution may be an aqueous solution or a solution of an organic solvent as described above. As such, the resin of the present invention has good compatibility with various solvents (
, and has excellent adhesion to transparent substrates such as glass.

Furthermore, if the dressing is water-soluble, there will be a problem in the sustainability of its anti-fogging properties, so it can also be used after being made insoluble in water.

There are two ways to make these polymers insoluble in water: during polymerization and after polymerization. (
A method of copolymerizing with a (meth)acrylamide derivative, a method of copolymerizing with an N-alkoxymethyl (meth)acrylamide derivative, a method of copolymerizing with a (meth)acrylamide derivative by increasing the ratio of the above-mentioned lipophilic hexamer, and a method of copolymerizing with a (meth)acrylamide derivative in a bulk form. A method of polymerization, a method of heat treating a polymer, a method of reacting a hydroxyl group or an amine group with a polyfunctional compound such as epichlorohydrin to insolubilize the polymer, and Copolymerization with a monomer substituted with a substituent having an active hydrogen such as a carboxy group, sulfonic acid group, hydroxyl group, etc., or forming a complex with a polymer substituted with those substituents, A method of insolubilization, etc. can be adopted.

More specifically, in the first method, as a crosslinking monomer,
For example, N,N'-methylenebisacrylamide, N,
N-diallylacrylamide, triacryl formal, N, N-diacryloimide, N, N-dimethacryloimide, ethylene glycol acrylate, ethylene glycol dimethacrylate, various polyethylene glycol diacrylates, various polyethylene glycol dimethacrylates, propylene glycol diacrylate , propylene glycol dimethacrylate, various polypropylene glycol diacrylates, various polypropylene glycol dimethacrylates, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, glycerol dimethacrylate, neo Pentyl glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane tritacrylate, trimethylolethane trimethacrylate, trimethylolethane triacrylate, tetramethylolmethanetetramethacrylate, tetramethylolmethane triacrylate, divinylbenzene,
You can use diallyl phthalate etc.

In this case, the polymer is insoluble in the solvent, so the specific method is to bring the monomer into contact with the object to be antifogged and allow the polymerization to occur on the object. N- in the second method
Alkoxymethyl (meth)acrylamide derivatives also include N-hydroxymethyl (meth)acrylamide, such as N-methylol (meth)acrylamide, N
-Methoxymethyl (meth)acrylamide, N-ethquinmethyl (meth)acrylamide, N-n-butoxymethyl (meth)acrylamide, N-tert, -butoxymethyl (meth)acrylamide, etc. can be used.

In this case, the polymer may be polymerized on the object to be antifogged, or the polymer may be applied onto the object.

In this case, insolubilization can be achieved more effectively by heat treatment at a temperature of 60 to 250°C. The ratio of the lipophilic monomer to the (meth)acrylamide derivative in the fifth method varies depending on the combination of the (meth)acrylamide derivative and the lipophilic monomer, and although it cannot be determined generally, it is generally preferred to be 1% or more. is 6% or more and 75% or less.

In this case as well, the two methods described above can be employed, but coating with a polymer is simpler and preferable.

As for the method of bulk polymerization according to the fourth method, it is better to polymerize by holding the monomer on the surface of the substrate to be protected without diluting it with a solvent, and then heat-treating at a temperature of 60 to 250 ° C. It can be insolubilized more effectively.

In the fifth method, which is a method of heat-treating a polymer, the heating conditions vary depending on the polymer and are not uniform, but generally, the temperature is 60 to 250°C, preferably 80 to 200°C, and the temperature is 70°C. What is necessary is to heat the base material to be antifogged which is integrated with the polymer by polymerization of the polymer or coating of the polymer. At this time, in applying the polymer solution, drying or distilling off the solvent may be performed concurrently with heat treatment. In the sixth method, in which a polyfunctional compound such as epichlorohydrin is reacted to crosslink and insolubilize, it is necessary to introduce a hydrophilic group or an amine group into the polymer in advance. Amine groups and carboxy groups can be easily introduced by copolymerization; Then, there is a method of saponifying with a basic substance to introduce hydroxyl groups.Then, the above-mentioned polymer is integrated with the object to be antifogged, and a polyfunctional compound such as epichlorohydrin is added and reacted. The seventh method involves copolymerization with the above-mentioned monomers having active hydrogen, compounding with copolymers of these extenders, replacing active hydrogen in the polymer with ammonium ions, etc. This is a method in which the mixture is mixed and then an acid is added to activate the active hydrogen to form a complex and make it insolubilized.The complex may be formed on the object to be antifogged, or the formed complex may be Although it is insoluble in water, some of it is soluble in organic solvents, so you can apply the polymer solution to the object to be antifogged and integrate it. In the case of an aqueous solution, it may become cloudy at a certain temperature as it is heated.On the other hand, in the case of a water-retaining gel insoluble in water, the amount of water retained changes from temperature 6 as shown in the reference example. The lower the temperature, the greater the water retention capacity.

As mentioned above, the RQL fat of the present invention has a property of absorbing a large amount of water at low temperatures and releasing water as the temperature increases.
1-Runote is most suitable as an anti-fog resin. This is because fogging occurs on glass surfaces in most cases when it comes into contact with cold surfaces or warm air, and the problem is the water absorption ability at low temperatures. It can be said that it exactly meets such requirements. Even better, as the temperature rises, they release the water they are holding.
This means that the water absorption capacity at low temperatures does not become saturated, and it is always ready to absorb water at low temperatures.

In a specific embodiment, when the resin of the present invention is a solution of water or other solvent, or an emulsion solution, it is directly applied to the surface of a transparent substrate such as a glass surface using a piece of cloth, a piece of paper, a sponge, etc. However, it may also be aerosolized using a propellant such as liquefied petroleum gas, fluorohydrocarbon, isobutane, dimethyl ether, or the like, or sprayed using a container on the side of the spray device. Thereafter, if necessary, heat treatment can be performed to distill off the solvent and to perform a solubilization treatment.

In addition, when polymerizing a monomer on the surface of a substrate, it is possible to expose the monomer to the surface by immersing it in the monomer or by condensing the monomer vapor on the surface under vacuum. Alternatively, the polymer may be polymerized by irradiation with irradiation or heat treatment. At this time, a polymerization initiator may be dissolved in the monomer.

The thickness of the resin on the surface of the base material is from several microns to several millimeters, and the thickness can be controlled by the number of the coating liquid and its concentration.

Additionally, various additives such as surfactants, fragrances, rust preventives, colorants, deodorants, preservatives, abrasives, and virgoos can be used with the resin of the present invention.

Function: As mentioned above, the antifogging resin of the present invention (1) has a high water absorption capacity at low temperatures and releases water when heated, so its water absorption capacity does not always saturate at low temperatures, and it can absorb water at any time at low temperatures. is in a state of (2)・1 Soybean fat is dissolved in various solvents,
In addition, a wide variety of insolubilization methods can be used, so various methods can be used for anti-fog treatment. (3) The resin has effects such as excellent adhesion to transparent substrates such as glass.

The present invention will be further explained below with reference to Examples.

Example 1 N-Acryloylpyrroline 757 was dissolved in 6552 distilled water, cooled to 10°C, transferred to a 1 ton stainless steel Ziwer bottle, and dissolved using a ball filter at a flow rate of 0.54/cm. Nitrogen gas was bubbled for 45 minutes. Then, 0.42 ml of ammonium persulfate was added to the aqueous solution in 1 ml of distilled water.
02 and a solution of sodium bisulfite 0171 dissolved in distilled water 107 are simultaneously added, and the aqueous solution is adiabatically polymerized to form 10
% polymer aqueous solution was obtained. After immersing a glass plate whose surface has been cleaned (degreased and cleaned) in the polymer aqueous solution, it is pulled up, 6
After vacuum drying at 0°C, it was heat-treated at 125°C overnight. The surface of the glass plate after the heat treatment remained transparent, and when brought into contact with water vapor, the surface of the glass plate did not become cloudy, became uniformly wet, and remained transparent. The phenomenon is
There was no change even after repeating the wet state and dry state five times.

Comparative Example 1 When a glass plate whose surface had been thoroughly degreased and cleaned was brought into contact with water vapor, fine water droplets adhered to the surface of the glass plate, resulting in fogging on the surface of the glass plate.

Examples 2 to 21 A 10% aqueous polymer solution having the copolymer composition shown in Table 1 was obtained in the same manner as in Example 1. A glass plate heat-treated with the polymer was obtained using a core polymer aqueous solution in the same manner as in Example 1, and the transparency of the glass plate and the antifogging property of the surface when the glass plate was brought into contact with water vapor were evaluated. The transparency was evaluated and the results shown in Table 1 were obtained.

Example 22 6me of a 1% polymer aqueous solution of acrylic ammonium was added to 1% polymer water/47 night 14me of N-7 chloroylpyrodine to make a homogeneous aqueous solution, and 2me of IN hydrochloric acid aqueous solution was added. . At the same time as the addition, the formation of a complex was confirmed at the interface with the salt 1 aqueous solution, and the complex was separated as a white film. The composite was washed with distilled water, dried and ground to obtain 'C powder. 10% N of the powder,
A glass plate treated with the composite was obtained in the same manner as in Example 1 using an N-dimethylformamide solution.

The surface of the glass plate was transparent, and when brought into contact with water vapor, the surface of the glass plate became uniformly wet, did not become cloudy, and remained transparent.

Example 26 Table-1 Translucency: O-transparent, Δ-slightly cloudy, ×-white cloudy Antifogging property: O-Surface is uniformly wet and does not become cloudy. △ - Adheres in the form of large water droplets.

×=Fine, adheres in the form of water droplets.

1) N-EtAAM; N-ethylacrylamide,
N-AcPy: N-acryloylpyrrolidine.

N-PrAAM; N-n-propylacrylamide, N
-BuAAM; N-n-7 tylacrylamide, N-A
A composite was obtained in the same manner as in Example 22 using cPi; 1% aqueous solution of N-acryloyl piperidine/N--n-propylacrylamide lVj. A glass plate treated with the composite was laminated in the same manner as in Example 22 using the composite.

The surface of the glass plate was transparent, and when it was brought into contact with water vapor, the surface of the glass plate became uniformly wet, did not produce any cracks, and remained transparent.

Example 24 N,N-dimethylformamide M 100 mlTc
N-acryloylpyrrolidine 92 and acrylonitrile 1
2, and azobisisobutylnitrile 0.1641i'
was added and dissolved, and after purging the inside of the reactor with nitrogen gas, polymerization was carried out at 50°C. After polymerization, the polymer was poured into ethyl ether to precipitate the polymer, which was then dried with P and N-
90 between acryloylpyrrolidine and acrylonitrile:
A copolymer with a composition ratio of 10 was obtained.

A glass plate treated with the copolymer was obtained in the same manner as in Example 1 using a 10% aqueous solution of the copolymer.

The surface of the glass plate was transparent, and when it came into contact with water vapor, the surface of the glass plate became uniformly wet, did not produce any odor, and remained transparent.

Patent Applicant Mitsui Toatsu Chemical Co., Ltd. Procedure Amendment Book 1985≠Month? Q Manabu Shiga, Commissioner of the Japan Patent Office 1 Display of the case Patent Application No. 106468 filed in 1982 2 Name of the invention Anti-fogging resin 3 Relationship to the case of the person making the amendment Patent applicant address 3-chome Kasumigaseki, Chiyoda-ku, Tokyo No. 2 No. 5 Name (
3] 2) Mitsui Toatsu Chemical Co., Ltd. Specification, Detailed Description of the Invention, Column 6, M jE f) n g.

The following example is included at the end of page 26 of the specification.

[Example 25] 1 of N-11-propylacrylamide was prepared in exactly the same manner as in Example 1 except that N-n-propylacrylamide was used instead of N-acryloylpyrrolidine.
A 0% polymer aqueous solution was obtained.

A glass plate heat-treated with the polymer was obtained in the same manner as in Example 1 using the polymer aqueous solution.

The surface of the glass plate after heat treatment remained transparent, and when brought into contact with water vapor, the surface of the glass plate uniformly leaked without fogging and remained transparent.

Example 26 10 of N-isopropylacrylamide was prepared in exactly the same manner as in Example 1 except that N-isopropylacrylamide was used instead of N-acryloylpyrrolidine.
% polymer aqueous solution was obtained.

A glass plate heat-treated with the polymer was obtained in the same manner as in Example 1 using the polymer aqueous solution.

The surface of the glass plate after heat treatment remained transparent, and when brought into contact with water vapor, the surface of the glass plate uniformly leaked without fogging and remained transparent.

Example 27 10% N,N- of N,N-diethylacrylamide
The dimethylformamide solution was transferred to a dewar bottle, the liquid was subjected to oxygen substitution, and then 15% azobisinobutyronitrile was added at 60°C to polymerize adiabatically.

A 10% polymer solution of N-diethylacrylamide was obtained. A glass plate was heat-treated with the polymer in the same manner as in Example 1 using the polymer solution. The surface of the glass plate after heat treatment remained transparent, and when brought into contact with water vapor, the surface of the glass plate uniformly leaked without fogging and remained transparent.

Example 28 A 10% aqueous polymer solution of N-acryloylmorpholine was obtained in exactly the same manner as in Example 1, except that N-acryloylmorpholine was used instead of N-acryloylpyrrolidine. Example 1 using the polymer aqueous solution
A glass plate heat-treated with the polymer was obtained in the same manner as above. The surface of the glass plate after heat treatment remained transparent, and when brought into contact with water vapor, the surface of the glass plate uniformly leaked without fogging and remained transparent. ” Patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. General formula represented by general formula (1) or general formula (II) (in the above formula, R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom, a methyl group or an ethyl group, and R3 is a methyl group) group, ethyl group or propyl group.) General formula (In the above formula, R1 is a hydrogen atom or a methyl group, A is +Cl-
I2 +n and n is 4 to 6 or +CR2+-, O+ C
)I! +2 represents 1-0) An antifogging resin comprising a single or copolymer of N-alkyl or N-alkylene-substituted (meth)acrylamide, or a copolymer with other copolymerizable monomers.