JPS62186488A - Blur-free molded unit - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an anti-fogging molded article having excellent anti-fogging properties, abrasion resistance and durability.

[Prior art] Plastics and glass have traditionally been widely used in applications such as window glass, windows of trains and automobiles, shop windows, eyeglasses, mirrors, and front panels of televisions, taking advantage of their properties as transparent substrates. It's being used.

However, the disadvantage of products using plastic and non-glass substrates is that when they are used in places with high temperature and humidity, or at interfaces with large temperature or humidity differences, condensation occurs on the surface of the product. It is to become cloudy. In particular, it is a serious safety problem that the surface of products such as window glass, windows and mirrors used in automobiles, and eyeglass lenses becomes cloudy or cloudy.

Therefore, requests for these improvements have been made from various quarters, and various attempts to impart antifogging properties have been proposed. For example, a method of coating a substrate with an antifogging composition, a method of antifogging by heating the substrate by placing an electric heating wire inside the substrate, and a method of increasing the temperature of the substrate by placing an electric heater on the back side of the substrate. There is also an anti-fog method in which a transparent conductive film layer is formed on a base material and the temperature of the surface of the base material is raised by applying electricity.

[Problems to be Solved by the Invention] However, these methods are unsatisfactory in terms of practical performance. The method of coating a substrate with an antifogging composition cannot withstand long-term use in a high temperature and high humidity environment. The method of arranging heating wires within the substrate has the disadvantage that it significantly obstructs the field of view in the case of transparent substrates. Furthermore, anti-fogging methods using electric heaters have the disadvantage that it is difficult to raise the temperature depending on the substrate, and electricity consumption is large. The method of forming a transparent conductive film layer provides good visibility even on a transparent base material, and the temperature of the base material surface can be raised with a small electric current, but the antifogging property is completely lost if no current is applied. Generally speaking, there is a drawback that it takes some time to complete the temperature rise after the start of energization, and fogging occurs before the temperature rises.

[Means for solving the problem] As a result of intensive research into improving the problem, the present inventors found that
The present invention was completed based on the discovery that the anti-fogging molded article of the present invention, which will be described in detail below, is extremely useful for solving the problem.

That is, the present invention provides an anti-fogging molded article having excellent anti-fogging properties and good abrasion resistance and chemical resistance.

The present invention consists of the following configuration. That is, the present invention relates to an anti-fog molded article characterized in that an anti-fog coating is provided on the outermost layer of a base material having an electrically heated structure.

The base material having an electrical heating mechanism as used in the present invention is not particularly limited as long as the base material can be heated by passing an electric current through it. There is no problem in heating the base material whether the entire base material or only the surface thereof is heated. Furthermore, even if only the portions requiring antifogging properties can be heated, the purpose can be sufficiently achieved. In addition, electrical heating refers to heating by Joule heat generated by passing an electric current, but it is possible to achieve the purpose without damaging the properties of the base material as much as possible. Preferably, a method is applied in which a conductive film is provided on the conductive film and the conductive film is energized. The voltage used for energization is determined experimentally depending on the resistance value of the conductive film, the substrate to be heated, necessary heating conditions, environmental conditions, etc. It is particularly preferable to use a transparent conductive film layer as a conductive coating for applications requiring transparency, such as windows, front, night, or rear windows of automobiles. Here, the transparent conductive film layer refers to various materials that have been known under that name, such as gold, silver,
Metal thin films such as palladium, conductive inorganic oxide thin films, and even organic transparent conductive films obtained by electrolytic polymerization of pyrrole can be used, but tin oxide-containing thin films are particularly suitable for durability, conductivity, etc. It is useful in this respect.

In forming such a thin film, vacuum evaporation method, sputtering method, physical vapor phase method thereof, chemical vapor phase method of metal halide or organic derivative, or thin film forming method from liquid phase may be used as appropriate. used. In forming such a thin film, various chemical and physical surfaces of the base material can be used and the surface of the base material can be modified as necessary.

The antifogging coating provided on the outermost layer of the base material of the present invention is not limited in any way as long as it has antifogging properties.

For example, methods of improving the wettability of the surface of the article by coating or mixing a hydrophilic substance such as a surfactant into a coating, methods of coating a hydrophilic polymer, or adhering an anti-fog film. It is possible to form an anti-fog coating.

A preferable example of an anti-fog film having excellent anti-fog properties, abrasion resistance, and durability is a cured film obtained from the following components The elemental content of carbon and silicon is carbon/silicon (C/S i
) The gravity ratio is approximately 0.7/1°0 to 2.0/1.0,
In addition, in the surface layer, the above-mentioned ratio is larger than the C/S i ratio of the entire cured film, and is 1.7/
It is a coating having a coefficient of 1.0 or more.

B. Polyvinyl alcohol 100' 1 part, fine particulate silica with an average particle diameter of about 5 to 200 mμ
60-300 weight most part c, general formula RI R2aS i (
OR3) The right side represented by 3-a is a silicon compound and/or
or its hydrolyzate 0.5 to 30 polyesters (here, R1 is a zero base having 1 to 10 carbon atoms, R2 is a hydrocarbon group having 1 to 6 carbon atoms, R3 is an alkyl group having 1 to 8 carbon atoms) group, alkoxyalkyl group or acyl group, a is O or 1).

Here, the polyvinyl alcohol used as component (A) refers to one obtained by partial or complete hydrolysis of polyvinyl ester such as polyacetate-coated vinyl, and has an average degree of polymerization of 250 to 3000 and a degree of saponification of 70. Polyvinyl alcohol with a mole % or more is preferably used in the present invention. If the average degree of polymerization of polyvinyl alcohol is less than 250, durability, especially water resistance, tends to be poor, and if it is greater than 3000, the viscosity increases when used as a paint, making it difficult to obtain a smooth coating. I have a work problem.

Roughly speaking, if the degree of saponification is lower than 70 mol%, there is a tendency that sufficient performance in terms of anti-fogging properties cannot be expected.

Furthermore, an effective example of the particulate silica having an average particle diameter of 5 to 200 mμ, which is a daily component, is silica sol. Silica sols are colloidal dispersions of high molecular weight silicic anhydride in organic solvents such as water and/or alcohols. For purposes of the present invention, an average particle size of about 5 to 2
00 mμ is preferably used, but about 7 to 50 m
The diameter after μ is particularly preferable. If the average particle size is less than about 5μ, the stability of the dispersion state is poor and it is difficult to obtain products of consistent quality.If the average particle size is more than 200μ, the resulting coating film will have poor transparency and large turbidity. There is a tendency to only get things.

The silicon compound represented by the general formula %, which is the component C, is a necessary component for improving water resistance and adhesion to the base material, and specific examples include β-glycidoxy Ethyl 1-rimethoxysilane,
γ-Glycidoxypropyl 1-helimethoxysilane, γ-
Glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyljethoxysilane, γ-glycidoxypropylmethyldimethoxysilane ~xysilane, γ-glycidoxypropylmethyljethoxysilane, β-glycidoxyethyldimethoxysilane, γ~glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyljethoxysilane, β-glycidoxy Propylethyljethoxysilane, β-glycidoxyethylprobyldimethoxysilane, β-(3,4 epoxycyclohexyl)
Ethyl 1-rimethoxysilane, β-(3,4 epoxycyclohexyl)ethyltriethoxysilane, methyl 1-
Rimethoxysilane, methyl 1-liethoxysilane, vinyl 1-rimethoxysilane, vinyltriethoxysilane,
Vinyl triatoxysilane, vinyl trimethoxyer 1
~xysilane, γ-chloropropyl 1-rimethoxysilane, γ-chloropropyl 1-ethoxysilane, γ-chloropropyl tripropoxysilane, γ-chloropropyl 1-rib 1-xysilane, phenyltrimethoxysilane, phenyl Trimethoxysilane, γ-trifluoropropyl! Herimethoxysilane, γ-methacryloxypropyl 1-rimethoxysilane, dimethyldimethoxysilane,
Examples include γ-chloropropylmethyldimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane. Moreover, these compounds can be used not only alone but also in combination of two or more.

When using the above-mentioned organosilicon compound as component (iii), it can be added as a component as it is, or it can be hydrolyzed in advance and then the silane hydrolyzate is added thereto.

Further, for hydrolysis, a conventional method can be used, for example, a method of hydrolysis using an inorganic acid such as hydrochloric acid, an organic acid such as acetic acid, an alkali such as caustic soda, or using only water.

If the antifogging film has the above-mentioned components (A), (3), and (C) as essential components, it will have excellent antifogging properties and durability, and will be the most practical.

Further, this antifogging film is essentially a cured film having a surface layer portion in which the component A is relatively larger than that in the entire film.

The surface layer refers to the outermost layer that comes into contact with the outside air and can be distinguished from the layer below by its composition.

The base material with electrical heating is treated with activated gas, physical treatment such as Nando Plus 1, chemical treatment with acids, bases, and hydrating agents in order to improve the adhesion with the antifogging coating. It is also possible to use a grain treated with a silane coupling agent or a primer.

On the other hand, in the above-mentioned anti-fog coating, if the content of the surface layer component is less than the above-mentioned value, the water resistance tends to decrease, and if it exceeds this value, the anti-fog property tends to decrease.

The thickness of the surface layer is preferably in the range of 0.001 μm to 5 μm, and if it is too thin, the antifogging properties tend to decrease, while if it becomes thick, the water resistance tends to decrease.

The thickness of the entire coating is preferably 0.1 μm or more; if it is less than this, the antifogging properties will be insufficient and the hardness will also decrease. There is no particular limit to the thickness, but a thickness of about 30 μm or less is preferably used in consideration of painting workability, heating effect due to energization, etc.

In addition to the above-mentioned essential components, the antifogging film of the present invention may also contain additives, various modifiers, and the like.

In addition, when forming an antifogging film by coating in the form of a paint, examples of solvents used include water, various alcohols, alcohols, esters, ethers, cyclic ethers, dimethylformamide, dimethyl sulfoxide, etc. It can be used as appropriate.

As additives, various surfactants can be used for the purpose of improving surface smoothness, and examples include silicone compounds, fluorine surfactants, and organic surfactants. Furthermore, examples of the modifier include organic polymers having good compatibility with the composition of the present invention, such as hydroxyethyl cellulose, polyhydroxyethyl methacrylate, or copolymers thereof, alcohol-soluble nylon, polyacrylamide, polyvinylpyrrolidone, or copolymers thereof. It will be done. It is also possible to add tetrafunctional silane compounds such as ethylsilicone, 1-bn-butylsilicate, i-butylsilicate-1., and t-butylsilicate. Examples of modifiers that can be added include various epoxy resins, melamine resins, and amide resins.

In addition, various catalysts known as catalysts for the condensation of silanol and/or the reaction between silanol and hydroxyl groups are used for the purpose of accelerating curing if necessary.
An aluminum chelate compound represented by -Y3-o can be preferably used.

(Here, X is a lower alkoxy group, Y is MIC○CHpC
Ligands (Ml, M2.M
3 and M4 are lower alkyl bases), n is 0, 1 or 2
).

Various types of aluminum chelate compounds can be used, but examples of preferred compounds from the viewpoints of catalytic activity, solubility in the composition, and stability include aluminum acetyl acetate. +～nato, aluminum ethyl acetoacetate bisacetylacetonate, aluminum bisa t
? 1 to acetate acetylacetonate, aluminum di-n-71 to oxide monoethyl acetoaretate-1 to aluminum di-propoxide monomethyl acetoaretate, and mixtures of these compounds can also be used.

Additive components other than these essential components may vary depending on the application of the present invention, such as heat resistance, weather resistance, water resistance, adhesiveness, or chemical resistance, to the antifogging coating film of the present invention. The practical properties of urethane are improved.

It is also possible to color the antifogging film by adding dyes and pigments within a range that does not impair transparency.

On the other hand, in order to specifically produce an antifogging film in which the surface layer has a relatively larger amount of component A than the total component A, as described in claim (6) of the present invention, the lower layer must be After formation, coating is performed twice by roughly forming the surface layer portion thereon.

In this case, the lower layer forming composition is applied, and after curing, the surface layer forming composition is applied.Alternatively, the lower layer forming composition is applied, and after a slight setting, the surface layer forming composition is applied in a so-called wet manner. It is also possible to use on-wet coating to avoid curing of films with different compositions on the surface layer at once.The formation of a cured film is usually carried out at a temperature of 50 to 250°C.At low temperatures, curing is insufficient, and at high temperatures, the film is hardened. This may cause discoloration or deterioration.

In addition, the coating composition is applied in one coat, and the surface layer and/or component C is reduced by a cured film or a wet treatment after curing, so that the surface layer has a relatively larger amount of component A than the total component A. can be manufactured.

Here, the wet treatment refers to immersing the film in water or an organic solvent, or leaving it in a high humidity atmosphere. At this time, it is heated if necessary.

Furthermore, instead of the above-mentioned wetting treatment, the surface of the coating can be treated with flexible articles such as gauze, non-woven fabric, etc., or paper, or articles made more flexible by moistening with water. A similar coating can also be produced by wiping and friction treatment.

There are no particular restrictions on the anti-fogging molded article of the present invention as long as it requires the characteristics of the present invention, but examples of the anti-fogging molded article of the present invention that have significant practical value and are generally recognized as having the characteristics of the present invention include windows for bathrooms, etc. It is preferably used for windows of automobiles or trains, architectural windows, etc.

The antifogging film formed as the outermost layer in the present invention is generally coated with a composition capable of exhibiting antifogging properties, dried,
and/or formed by curing,
Application methods include spacing, dip coating, spin coating, flow coating, spray coating, roll coating,
Various methods commonly known in the art can be used, such as curtain flow painting.

Although it is possible to form an antifogging film directly on a base material equipped with an electric heating machine, in order to improve wear resistance and adhesion, it is possible to form an antifogging film directly on a base material that has an electric heating device. It is also possible to form an antifogging film after providing the above on the base material in advance.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

In addition, parts and percentages in the examples are based on weight.

Example 1 (1) Preparation of antifogging coating composition■ Preparation of γ-glycidoxypropyltrimethoxysilane hydrolyzate 236q of γ-glycidoxypropyltrimethoxysilane was charged into a reactor equipped with a rotor. , "Liquid temperature 10'C
o, o.
i Gradually drop 54 Cl of normal hydrochloric acid aqueous solution. After the dropwise addition was completed, cooling was stopped to obtain a hydrolyzate of γ-glycitoxypropyltrimethoxysilane.

◎ Preparation of paint Polyvinyl alcohol (Nippon Gosei Kagaku Kogyo Co., Ltd. product,
AL-06, degree of saponification 91.0-94.0 mol%) 1
After weighing 5 Iffi% water) 8 liquid 250 C] into a beaker, 289 g of water, 10.4 g of the above γ-glycidoxypropyl 1-rimethoxysilane hydrolyzate, and
: Methanol-dispersed colloidal silica (30% solids,
Add 105 g of average particle size 13±1 mμ, respectively. To this mixed dispersion were added 1,4 dioxane 105Q, 0.24 q of fluorosurfactant, and 1.5 g of aluminum arethyl aretoner 1'' and mixed thoroughly with stirring to prepare paint A. Among the film-forming components of this paint: The content of carbon M and silicon was approximately 1.6 in terms of C/Si weight.

(2) Preparation of coating composition for primer■ γ-
Preparation of glycidoxypropyltrimethoxysilane hydrolyzate 95.3 g of γ-glycidoxypropyltrimethoxysilane was charged into a reactor equipped with a rotor, and 10 g of γ-glycidoxypropyltrimethoxysilane was charged.
'C while stirring with a magnetic stirrer.
．． 21.8 g of 01N hydrochloric acid aqueous solution was gradually added dropwise. After the dropwise addition was completed, cooling was stopped to obtain a hydrolyzate of γ-glycidoxypropyltrimethoxysilane.

◎ Preparation of paint Add 216 q of methanol, 216 g of dimedylformamide, and 0.5 g of fluorine surfactant to the silane hydrolyzate.
, bisphenol A type epoxy resin (manufactured by Shell Chemical Co., Ltd.,
Add and mix 67.5 g of Epikote 827 (trade name), and add and mix roughly colloidal pentadispersed antimony sol (trade name, Nissan Chemical Co., Ltd., antimony sol A-2550, average particle size 60 m).
μ>27OC+, 5q of aluminum acetylacenate 1 to 13° was added, and after thorough stirring, a coating composition for a primer was prepared.

(3) Preparation of anti-fog molded inorganic glass (70 x 80 x 1
mm) with the coating composition prepared in (2) at a pulling speed of 10 cm/min, pre-curing at 80'C/10 min, and further
℃ for 2 hours, then the surface of the cured film was treated with pixel gas plasma treatment, and the A paint prepared in (1) was dip coated at a pulling rate of 10 cm/min.
After heating at 100'C for 110 minutes, then at 130'C for 2 hours, immersion treatment was performed in hot water at 90'C for 1 hour.

After exposing the terminals by partially scraping off each coating film of the transparent conductive film layer portion of the glass molded body having the anti-resistance coating, electrodes are applied to the terminals made of the transparent conductive film layer using conductive layer ink. has been established. Lead wires were attached to the electrodes, and anti-fog moldings were used to attach them.

(4) Evaluation There was no clouding at all, either because exhalation was blown before applying the current. Next, after aging at an ambient temperature of 23°C and humidity of 50% R1-1, measurements were taken for 2 hours after it started to become cloudy after being placed in a box with a temperature of 40'C and a humidity of 100% R1-1.
Clouding occurred after 25 seconds.

When I tested everything in the same way except for applying a voltage of 1.5 volts and energizing, no fogging occurred in any of the tests 1 to 1 above. I tried to measure the time it took to start, but no fogging occurred even after 30 seconds, and no fogging occurred even after 10 minutes.

Comparative Example Electrodes and lead wires were provided on an inorganic glass having a transparent conductive film layer in the same manner as in the example.

When exhaled air was blown onto it without electricity, the entire surface turned white and cloudy. Furthermore, in the same manner as in the example, 40°C, 100%
When we applied 15 volts of electricity at the same time we placed it in the RH box and measured the time it took for it to start fogging, we found that the surface became foggy instantly and it took 30 seconds for the fog to disappear, indicating that there was a problem with the initial resistance. there were.

[Effects of the Invention] The anti-oxidation molded article obtained by the present invention has sufficient anti-oxidation properties even under severe conditions, and further has excellent wear resistance and durability, and has extremely high commercial value.

In general, when the anti-fogging molded article of the present invention is used in an electric heater or an article on which a transparent conductive film layer is formed, it can prevent the occurrence of fogging from the start of energization to the completion of heating.

For example, when this is applied to a car window, it is possible to prevent the windshield from moving to the right immediately after getting into the vehicle, even in winter or in humid seasons.

Claims (6)

[Claims] (1) An anti-fog molded article characterized in that an anti-fog coating is provided on the outermost layer of a base material having an electric heating mechanism. (2) Claim (1) characterized in that the base material having an electrical heating mechanism is a base material that can be heated by applying electricity to a conductive coating present on the whole or at least a part of the base material. Anti-fogging molded article as described. (3) The anti-fogging molded article according to claim (2), wherein the conductive film is a transparent conductive film layer. (4) The anti-fogging molded article according to claim (3), wherein the transparent conductive film layer is a tin oxide-containing thin film. (5) The anti-fogging molded article according to claim (1), wherein the anti-fogging coating is abrasion resistant. (6) The antifogging film is a cured film obtained from the following components A, B, and C, and the elemental content of carbon and silicon in the cured film is approximately 10% by weight in terms of carbon/silicon (C/Si). 0.7/1.0 to 2.0/1.0, and the above weight ratio in the surface layer is larger than the C/Si weight ratio of the entire cured film, and 1.7/1. Claim No. (1) characterized in that the coating is 0 or more.
Anti-fogging molded article as described in . A. Polyvinyl alcohol 100 parts by weight B. Fine particulate silica with an average particle diameter of about 5 to 200 mμ
60 to 300 parts by weight c, general formula R^1R^2_aSi(OR^3)_3_-
Organosilicon compound and/or hydrolyzate thereof represented by _a 0.5 to 30 parts by weight (where R^1 is an organic group having 1 to 10 carbon atoms, R^2 is a hydrocarbon having 1 to 6 carbon atoms) group, R^3 is an alkyl group, alkoxyalkyl group, or acyl group having 1 to 8 carbon atoms, and a is 0 or 1).