JPH0543820A - Actinic radiation curing antifogging composition - Google Patents

Abstract

PURPOSE:To provide the title composition by the addition of a polyvinyl alcohol or the like and a specific fluorinated surfactant to an actinic radiation curing compound and subsequent application of the mixture on a polymer surface followed by curing with an actinic radiation. CONSTITUTION:A mixture containing at least one actinic radiation curing compound (e.g. alkyl acrylate) is mixed with a solution of polyvinyl alcohol or polyvinyl alkyl ether in an organic solvent and then with at least one fluorinated surfactant having perfluoroalkyl or perfluoroalkenyl groups. Then, a polymerization initiator or promoter, such as benzophenone or benzoin isopropyl ether, and a silicone leveling agent are added to the mixture. The resulting mixture is dissolved by heating and applied on the surface of a polymeric material (e.g. rigid polyvinyl chloride plate). The subsequent drying and curing with an actinic radiation (e.g. ultraviolet light) gives the title composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to preparation of an antifogging composition for imparting antifogging property to the surface of a polymeric substance such as a plastic mirror or plastic glasses in a bathroom.

[0002]

2. Description of the Related Art Conventionally, a method which has been carried out for exhibiting the antifogging property of a polymer substance is to knead a polymer substance with a nonionic surfactant, or a nonionic surfactant, an anion or a cation. They even spray the surface with surfactants. Further, there is a method in which a mixed solution containing a water-soluble polymerizable monomer, a copolymerizable vinyl monomer, and a thermal polymerization initiator is impregnated with a plastic molded article and then heat-polymerized to perform antifogging treatment.

[0003]

[Problems to be Solved by the Invention] Kneading a surfactant into a polymer material requires a high processing temperature, which leads to decomposition and deterioration of the surfactant, causing discoloration and affecting processing sustainability. Not been done. It has been implemented with soft vinyl chloride agricultural sheets and polyethylene agricultural sheets. The method of spray depositing a surfactant solution is not durable as the coating is washed with water. Further, a method of impregnating a polymer material into a mixed solution of a water-soluble polymerizable monomer and a copolymerized vinyl monomer and then performing thermal polymerization is not suitable for mass production because the polymerization time is long.

[0004]

A method for producing an active energy ray-curable anti-fogging composition is provided as a method of performing anti-fogging property on the surface of a polymer material without impairing transparency and in a single hour work. It According to the present invention, the antifogging composition is thinly applied to the surface of the polymer material and the composition is cured by irradiating the active energy ray for several seconds, so that the adhesion to the surface of the polymer material is good and the antifogging property is maintained for a very long time. It The present invention is characterized in that an active energy ray-curable compound is mixed with polyvinyl alcohol or polyvinyl alkyl ether in the production of the antifogging composition. Further, the present invention is characterized in that a fluorine-based surfactant containing a perfluoroalkyl group or a perfluoroalkenyl group is simultaneously mixed and mixed.

[0005]

According to the present invention, a composition having good transparency and good antifogging performance can be prepared by mixing and using an active energy ray-curable compound and polyvinyl alcohol or polyvinyl alkyl ether. By adding a small amount of a fluorinated surfactant containing an alkenyl group, it is possible to obtain a composition having excellent antifogging performance. When this substance is thinly applied on the surface of a polymer substance and irradiated with an active energy ray, it is instantly cured and a film having a completely satisfactory antifogging property can be produced. The polymer substance which is the object of the present invention includes a hard vinyl chloride plate, a corrugated plate, a soft vinyl chloride sheet, the same film, a polymethacrylic plate, a polyester plate, a polycarbonate plate, a corrugated plate, a polypropylene plate, and other commercially available moldings. Almost all plastic products are applicable. The polyvinyl alcohol used in the present invention preferably has a degree of saponification of polyvinyl acetate of about 35% and a degree of polymerization of 100 to 700. This is dissolved in methanol or ethanol and mixed with an active energy ray-curable compound. If the degree of saponification is too large, it is difficult to dissolve in alcohol and does not sufficiently mix and dissolve with the active energy ray-curable compound. The same thing can be said when the degree of polymerization is too large, but it is preferably about 200 to 400. This polyvinyl alcohol is dissolved in methanol or ethanol to give a 50-60% solution. Examples of polyvinyl alkyl ether include methyl ether and ethyl ether,
Make a 50 to 70% solution with a solvent such as methanol, ethanol, toluene, or mineral spirits. These polyvinyl alcohols or polyvinyl alkyl ethers may be mixed in a proportion of 20 to 60 parts by weight based on the total amount of the active energy ray-curable compound, preferably 30 to 50 parts. If it is too small, the antifogging effect is poor, and if it is too large, the surface is soft and the strength is lowered. Further, by adding a small amount of a fluorine-containing surfactant containing a perfluoroalkyl group or a perfluoroalkenyl group, it is possible to obtain a completely good antifogging performance. The fluorosurfactant used here is a perfluoroalkyl group or a perfluoroalkenyl group in which a part or all of the hydrogen bonded to the carbon atom of a normal surfactant is replaced by fluorine. Is a surfactant containing. Typical examples are shown below. (1) Anionic fluorinated surfactant

[Chemical 1] (Fluoroalkyl groups in which some or all substituted by fluorine atoms of the hydrogen atoms of Rf and R'f are each an alkyl group in the above formula, D represents ^{-CO -, - SO 2 -,} - (CH 2) m
-, Y is an alkylene group of C ₁ ~C _6, M is a hydrogen atom, N
H ₄ , an alkali metal, an alkaline earth metal, R ₁ represents a hydrogen atom or a lower alkyl group, and m represents an integer of 1-10. ) (2) Cationic fluorinated surfactant

[Chemical 2] (In the above formula, Rf, D, R, and Y have the same meanings as described above, R ₂ is the same as R ₁ , HX is an acid, and X is a halogen or an acid radical.) (3) Amphoteric fluorinated surfactant

[Chemical 3] (Wherein Rf, D, R ₁ and Y have the same meanings as described above,
Y'represents an alkylene group of C ₂ -C _6. ) (4) Nonionic fluorinated surfactant

[Chemical 4] (Wherein Rf, D, R ₁ and Y have the same meanings as described above,
R ₃ represents a C _{2 to} C ₃ alkylene group, R ₄ represents a C _{1 to} C ₂₂ alkyl group, n represents an integer of 1 to 30, and a, b, and c each represent an integer of 1 to 100. ) Among the above-mentioned fluorine-based surfactants, nonionic surfactants are preferable and examples thereof include the following.

[Chemical 5] Such fluorine-based surfactants may be used alone or in combination of two or more. These fluorine-based surfactants are used in an amount of 0.5 to 7 parts by weight, preferably 2 to 100 parts by weight based on the total amount of the active energy ray-curable compound.
5 parts by weight is suitable. If it is too small, the anti-fog effect will be poor,
It is uneconomical because too much is expensive. On the other hand, examples of the active energy ray-curable compound include alkyl (meth) acrylate (methyl, ethyl, propyl, ..., Lauryl, stearyl), hydroxyethyl alkyl (meth) acrylate (methyl, ethyl, propyl, ..., lauryl, stearyl), tetrahydrofurfuryl (meth) acrylate, alkoxy (meth) acrylate,
Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, n-ethylene glycol di (meth) acrylate (n: 1 to 16), n-propylene glycol di (meth) acrylate (n: 1 to 16) ), Alkylenediol di (meth) acrylate (C _{2 to} C ₁₆ ), neopentyl glycol di (meth) acrylate, bisphenol A (EO) _0-10 di (meth) acrylate, trimethylolpropane tri (meth) acrylate , trimethylolpropane (E · O) ₆ tri (meth) acrylate, glycerin mono (di) (meth) acrylate, pentaerythritol tri (tetra) acrylate, ditrimethylolpropane tetraacrylate, tetramethylolmethane tetraacrylate, Pentaerythritol hexaacrylate monofunctional, polyfunctional compounds are many,
These are often used in combination of two or more kinds depending on the purpose, rather than used alone. Therefore, the amount of these used is not limited. Polymerizable oligomers used in the antifogging composition of the present invention include acrylic oligomer type, oligoester acrylate type, epoxy acrylate type, urethane acrylate type, and many are commercially available until the chemical structure is not clarified. .. There is no general limit to the amount used, and 5 to 70% of the total amount of the curable antifogging composition may be used, or two or more types may be mixed or may not be used at all. Electron beams, radiation, and ultraviolet rays can be considered as active energy rays, but ultraviolet rays are commonly used for electron beams and radiation due to the large size of the device and high price. In that case, a polymerization initiator or an accelerator is required, and the following substances can be mentioned. Benzophenone, anthraquinone, naphthoquinone, benzoin, benzoin alkyl (phenyl) ether, benzoin alkyl ketal, dibenzyl, diacetyl, benzyl diphenyl disulfide, piparoin alkyl ether, benzyl ketal, dichloroacetophenone, 2-methylthioxanthone, Michler's ketone, phenylglyoxylate, There are many such as benzophenone amine type. 1 to 10 parts by weight of the total amount of the curable compound may be used alone or in combination of two or more kinds. The curable compounds as described above are mixed to form a liquid paint, but the viscosity must be adjusted depending on the coating method. Roll coat, spray coat, spin coat,
The method is determined by the shape of the base material such as the dipping method and the curtain wall method and the purpose, and the viscosity is determined accordingly.
Roll coating and spin coating can be applied with a relatively high viscosity, but the spray method must have an extremely low viscosity. The above-mentioned polymerizable oligomer generally has a high viscosity, and a low-viscosity reactive diluent such as an alkyl acrylate is mixed to reduce the viscosity, and in some cases, benzene,
Dilute with a solvent such as toluene, hexane, or alcohol cellosolves.

[0006]

EXAMPLES Next, the present invention will be described with reference to examples, but the present invention is not limited to the examples and can be applied to a wider range of applications. Examples Examples-1 to 7 and Comparative Examples-1 to 3 are collectively shown in Table-I. The oligomer of each example, a reactive monomer, a polyvinyl alcohol 50% methanol solution or a polyvinyl methyl ether 70% ethanol solution, and a fluorosurfactant were dissolved according to the quantitative ratio of each example in Table 1, and benzophenone and benzoinisopropyl were dissolved. Ether and silicone leveling agents are added according to the exemplified quantitative ratios and dissolved by heating with stirring. This solution is applied to a test piece using a bar coater, dried in a dryer at 40 ° C. for 8 to 10 minutes, and then irradiated with ultraviolet rays to be cured. The curing conditions are as follows. Bar coater: RD Specialties wire bar coater ROD No.9 UV lamp: Sen Special Light Source Co., Ltd. ozone-less high pressure mercury lamp 80 W / cm 1 lamp

[0007]

[Table 1] Distance between light source and test piece: 10 cm Conveyor speed: 20 m / min. Irradiation number: 8 times each Application example of coated plastic test piece Examples -1, -2: Soft vinyl chloride sheet 1.5 x 100 x 150 mm Example -3 ~ -7: Polycarbonate plate 0.5 x 100 x 150 mm Comparative Examples-1 and -2: Same as above Examples of oligomers used Examples-1 and -2: Daicel-UCB Co., Ltd. EB-769 Example-5: Kyoeisha Yushi Kogyo ( 200PA manufactured by Daicel Co., Ltd. Example-7: EB-265 manufactured by Daicel-UCB Co., Ltd. Comparative Examples-1, -2, -3: Same as above Example of monomer used Example-1: LA, 1.6 manufactured by Kyoeisha Fat & Oil Co., Ltd. HX-A Example-2: Same as above LA, 9EGA Example-3, -5: Same as above EC-A, 4EGA Example-4, -6: Same as above BP-4EA, Daicel UCB Co., Ltd. 1BOA Example -7: Same as above TMPA Same as above 1BOA Comparative example-1: Same as above NP10EA, 9EGA Comparative example-2, -3: Same as above EC-A, BP-4E A Example of Using Polyvinyl Alcohol or Polyvinyl Alkyl Ether Examples-1 to -5: manufactured by BSF Japan Co., Ltd. Lutonal M40 (70% ethanol solution) Examples -6, -7: manufactured by Nippon Synthetic Science Co., Ltd. Go Cefimer L-5407 (50% methanol solution) Fluorosurfactant use examples Examples -1, -2: Asahi Glass Co., Ltd. Surflon S-141 Examples -3, -4, -5: Same as above Surflon S- 145-7, Comparative Example-3: Same as above Surflon S-145 Silicone-based leveling agent usage example Each example: Shin-Etsu Chemical Co., Ltd. KP-340 Next, evaluation of each test piece coated with an antifogging composition and cured. The test methods are described and the test results are listed in Table 2. 1) Appearance: Visually check the transparency and color tone. 2) Adhesion ···················································································· With a cutter to make 100 pieces of stitches And observe the adhesion state of the coating film with a magnifying glass. 3) Anti-fog initial performance: Pour boiling water into a small beaker, cover each test piece coated with the anti-fog composition and harden it, and visually observe the state of adhesion of fine water droplets. 4) Anti-fogging sustainability ...
After soaking in the water for 100 hours, the same test as the initial performance test is performed.

[0008]

[Table 2]

[0009]

EFFECTS OF THE INVENTION According to the present invention, antifogging property is imparted to the surface of various kinds of polymer substances, and it is expected to be used in various fields such as plastic mirrors in bathrooms, plastic glasses, and other fields such as agriculture.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 29/04 LGW 6904-4J 29/10 LGZ 6904-4J C09D 5/00 PNN 6904-4J C09K 3 / 18 8318-4H

Claims (2)

[Claims] 1. An active energy ray-curable compound is mixed with polyvinyl alcohol or polyvinyl alkyl ether when an antifogging composition for imparting antifogging property to a surface of a polymer substance is prepared. . 2. A fluorosurfactant containing a perfluoroalkyl group or a perfluoroalkenyl group is used in combination with the polyvinyl alcohol or polyvinyl alkyl ether.