JPH07207049A - Method for modifying the surface of fluoroplastic moldings - Google Patents

Abstract

PURPOSE:To impart high adhesiveness, high wettability, etc., to the surface of a fluororesin by irradiating the surface of the molding with ultraviolet laser beams in the presence of an ultraviolet-abosrbong compound and a fluorine- containing surfactant. CONSTITUTION:The surface of a fluororesin molding is coated with an aqueous solution containpng 0.05-2wt.% ultraviolet absorbing compound and 0.05-10wt.% fluorine-containing surfactant and dried by heating to 60-150 deg.C. This surface is then irradiated with ultraviolet laser beams under conditions including a fluence of 50mJ/cm<2>/pulse or above, an incident energy of 0.2-2.0-mJ/cm<2> and a shot number of 1-20.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for modifying the surface of a fluororesin molding to impart particularly high adhesion and wettability to the surface of the fluororesin molding.

[0002]

2. Description of the Related Art Fluorine resin is superior to other resins in that it is superior in water / oil repellency, slidability, antifouling property, heat resistance, chemical resistance, and electrical characteristics. However, due to its inactive surface, it has a drawback in that it is difficult to apply an adhesive or paint, and it is difficult to form a composite with other materials.

Various methods have been proposed as solutions to such problems. For example, (i) a method of treating with a complex compound solution prepared from a solution of sodium metal and naphthalene in tetrahydrofuran [ER Nelson]
Ind. Eng. Chem., 50, 329 (195).
8 years)], (ii) Method of using glow discharge [Kakuda et al.
Industrial Materials, Volume 29 (No. 2), Page 105 (1981)
], (Iii) Method of processing by high-frequency sputter etching under low pressure (see Japanese Patent Publication No. 53-22108), (iv) Special gas atmosphere such as B (CH ₃ ) ₃ or Al (CH ₃ ) ₃ In the inside, a method of irradiating laser light (JP-A-2-
(See Japanese Patent Publication No. 197634), (v) Method of directly irradiating excimer laser light (see Japanese Patent Publication No. 3-57143), (v)
i) Method of processing by low temperature plasma sputter etching (Japanese Patent Publication No. 58-21928 / JP-A-2-12744)
No. 2 and Japanese Patent Publication No. 3-58375) and
(vii) A method in which a light-absorbing substance is kneaded in advance and then irradiated with an ultraviolet laser beam (see Japanese Patent Laid-Open No. 5-125208) and the like can be mentioned.

However, these reforming methods have the following problems. In the case of method (i), there is a risk of ignition during processing and the processing solution is unstable, which not only poses a problem in terms of work hygiene, but also exposes the modified surface to sunlight and high temperatures. There is a drawback that the adhesiveness and the like are significantly reduced. The method (ii) has a drawback that the effect of surface modification is significantly lower than that of a fluorine-free polymer such as polyethylene. In the case of the method (iii), the processing speed is slow, the etched resin component is expensive and not only adheres to the inside of a large-sized vacuum processing apparatus, but also the easily abradable irregularities formed on the resin surface have a low flow rate. There is a problem that it does not provide sufficient adhesiveness, paintability, etc., to a hydrophilic adhesive or paint. In the case of the method (iv), there is a problem that the processing speed is slow, a highly toxic gas and an expensive and large vacuum processing apparatus are required. Method
In the case of (v), there is a drawback that the adhesiveness and wettability of the fluororesin surface cannot be sufficiently improved. Furthermore, method (vi)
In the case of, since the chemical composition of the treated surface does not change, it is difficult to obtain high adhesive strength, and in order to obtain adhesiveness equivalent to that of method (i) in which relatively high adhesive strength is obtained, a narrow range is required. The treatment must be carried out for a long time under the treatment conditions of No. 1, which is not sufficient as an industrial treatment technique. Furthermore, the method (vii) has a drawback that it cannot be applied to the surface modification of a fluororesin molding containing no light absorbing substance.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a method for solving various problems of the above-mentioned conventional method for modifying the surface of a fluororesin and for imparting high adhesiveness and wettability to the surface of the fluororesin for general use. It was made to provide.

[0006]

That is, the present invention is characterized in that the surface of a fluororesin molding is irradiated with ultraviolet laser light in the presence of an ultraviolet absorbing compound and a fluorosurfactant. The present invention relates to a method for modifying a body surface.

The fluororesin molding to which the present invention is applied is a molding produced from a fluorine-containing organic polymer compound. As the base resin of the molded article, polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer
(FEP), tetrafluoroethylene-hexafluoropropylene-perfluoroalkoxyethylene terpolymer (EPE), tetrafluoroethylene-ethylene copolymer (ETFE), polychlorotrifluoroethylene (PC
TFE), trifluorochloroethylene-ethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF),
Examples include polyvinyl fluoride (PVF) and a resin mixture of any two or more of these. The specific form of the fluororesin molded product treated according to the present invention is not particularly limited, but examples thereof include a molded product having a sheet, a film, a pipe, a porous membrane and any other shape.

As the ultraviolet absorbing compound, those known per se may be appropriately used and are not particularly limited, but aromatic ultraviolet absorbing compounds such as aromatic hydrocarbons, aromatic carboxylic acids and the like. Salts, aromatic aldehydes, aromatic alcohols, aromatic amines and salts thereof, aromatic sulfonic acids and salts thereof, and phenols are preferable. Examples of aromatic UV absorbing compounds of this type include the following: naphthalene, phenanthrene, anthracene, naphthacene, biphenyl, sodium benzoate, phthalic acid, benzaldehyde, benzyl alcohol, phenylethanol, benzenesulfonic acid, 2 -Naphthalenesulfonic acid, anthraquinone-2
-Sodium sulfonate, phenol, cresol,
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
n-octoxybenzophenone, 4-dodecyloxy-
2-hydroxybenzophenone, 2-hydroxy-4-
Octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,
4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2'-hydroxy-4-chlorobenzophenone,
2 (2'-hydroxy-5-methoxyphenyl) benzotriazole, 2 (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2 (2'-hydroxy-3'-t- (Butyl-5′-methylphenyl) benzotriazole, phenyl salicylate, p-octylphenyl salicylate, p-t-butylphenyl salicylate, carboxyphenyl salicylate, strontium salicylate,
Methyl salicylate, dodecyl salicylate, resorcinol monobenzoate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl-2-cyano-3,3-diphenyl acrylate, Ni-bisoctylphenyl sulfide, [2,2 ' -Thiobis (4-t-octylphenolato)]-n-butylamine-Ni.

As the fluorine-containing surfactant used together with the above-mentioned ultraviolet absorbing compound, a surfactant known per se having a fluorocarbon chain as a hydrophobic group may be appropriately used. Examples of this type of fluorine-based surfactant include the following surfactants. (1) Anionic fluorinated surfactant RfCOOM RfSO ₂ N (R) ₂ CH ₂ COOM RfCONRYOSO ₃ M RfSO ₂ NRYOSO ₃ M RfSO ₃ M RfCH ₂ O (CH ₂ ) ₂ SO ₃ M

[Chemical 1]

[Chemical 2]

[Chemical 3] In the above formula, Rf and Rf ′ represent a fluoroalkyl group, R represents a hydrogen atom or a lower alkyl group,
Y represents a lower alkylene group, M is a hydrogen atom, -N
H _3, an alkali metal atom or alkaline earth metal atom.

[0010] (2) RfCONHYN fluorinated cationic surfactant (R) (R ') · HX RfSO 2 NHYN (R) (R') · HX

[Chemical 4]

[Chemical 5] In the above formula, Rf, R and Y are as defined above, R'represents a hydrogen atom or a lower alkyl group, and HX
Represents an acid, and X represents a halogen atom or an acid radical.

(3) Amphoteric fluorinated surfactant

[Chemical 6]

[Chemical 7] In the above formula, Rf, R and Y are as defined above.

(4) Nonionic Fluorine Surfactant RfOH

[Chemical 8]

[Chemical 9] In the above formula, Rf and R are as defined above, and n
Indicates a number from 1 to 30. In addition, two or more kinds of the above-mentioned fluorine-containing surfactants may be appropriately used in combination as desired.

Further, as a suitable commercially available fluorochemical surfactant, "Surflon S-111" manufactured by Asahi Glass Co., Ltd.
(Perfluoroalkylcarboxylate), "Surflon S
-112 "(perfluoroalkyl phosphate)," Surflon S-113 "(perfluoroalkylcarboxylate)," Surflon S-121 "(perfluoroalkyltrimethylammonium salt)," Surflon S-131 "(Perfluoroalkyl Sulfate) Fluoroalkyl betaine), "Surflon S-13
2 "(perfluoroalkyl betaine)" Surflon S-1
41 "(perfluoroalkylamine oxide)," Surflon S-145 "(perfluoroalkylethylene oxide adduct) and the like are exemplified.

The form in which the above-mentioned ultraviolet absorbing compound and the fluorine-containing surfactant are present on the surface of the fluororesin molding is not particularly limited. The liquid and / or fine powdery ultraviolet absorbing compound and the fluorosurfactant may be allowed to be present directly on the surface of the fluororesin molding, but from the viewpoint of modification efficiency and workability of the surface, It is preferable to attach a solution, dispersion or suspension of an ultraviolet absorbing compound and a fluorosurfactant using water or a water-soluble organic solvent as a solvent to the surface. As the solvent for the solution or the like, a mixture of water and a water-soluble organic solvent such as a lower alcohol (eg, methanol, ethanol, isopropanol, butanol, etc.) may be used. When used as an aqueous solution, in order to enhance the solubility of the ultraviolet absorbing compound and the fluorine-based surfactant, a water-soluble organic solvent, for example,
You may mix | blend lower alcohols, such as isopropanol, suitably.

The concentration of the solution or the like of the ultraviolet absorbing compound using water and / or a water-soluble organic solvent as a solvent depends on the kind of the compound, the solubility in water and the like, the kind of the fluororesin to be treated,
It depends on the type and concentration of the coexisting fluorosurfactant and is not particularly limited, but is generally 0.
It is from 05 to 10% by weight, preferably from 0.1 to 5% by weight.

The concentration of the above-mentioned fluorosurfactant in an aqueous solution or the like may be any concentration as long as it allows the above-mentioned ultraviolet absorbing compound to be uniformly present on the surface of the fluororesin molded product in a sufficient concentration, and is not particularly limited. , In general, 0.05-
It is 2% by weight, preferably 0.1 to 1% by weight.

The method of allowing the above-mentioned aqueous solution of the ultraviolet absorbing compound and the fluorosurfactant to be present on the surface of the fluororesin molding may be any of coating method, spraying method, dipping method and the like. Further, after the aqueous solution or the like is allowed to exist on the surface of the fluororesin molding, a drying treatment may be performed before the irradiation with the ultraviolet laser light. Natural drying is sufficient for the drying treatment, but if desired, it may be forcedly performed at, for example, 60 to 150 ° C. Due to the action of the fluorosurfactant, the ultraviolet absorbing compound is uniformly present on the surface of the fluororesin molded article in a sufficient concentration.

In the present invention, the surface of the molded article is irradiated with an ultraviolet laser beam under the condition that the ultraviolet absorbing compound and the fluorosurfactant are present on the surface of the molded fluororesin. The wavelength of UV laser light is 40
0 nm or less is preferable, and an argon laser beam, a krypton ion laser beam, an Nd: YAG laser beam, N
₂ laser light, dye laser light, excimer laser light and the like are exemplified, but excimer laser light of 193 to 308 nm is particularly preferable. Particularly, KrF excimer laser light (wavelength: 248 nm) and ArF excimer laser light (wavelength: 193n) that can stably obtain high output over a long period of time.
m) and XeCl excimer laser light (308 nm) are preferred. Irradiation of excimer laser light is usually performed at room temperature in the air, but may be performed in an oxygen atmosphere. Also,
The irradiation conditions of the excimer laser light depend on the type of fluororesin and the desired degree of surface modification, but the general irradiation conditions are as follows. Fluence: About 50 mJ / cm ² / pulse or more Incident energy: About 0.1 J / cm ² or more Shot number: About 100 or less

Particularly preferred KrF excimer laser light, Ar
The commonly used irradiation conditions of F excimer laser light and XeCl excimer laser light are as follows. KrF fluence: 100 to 500 mJ / cm ² / pulse Incident energy: 0.2 to 2.0 J / cm ² Shot number: 1 to 20 ArF fluence: 50 to 150 mJ / cm ² / pulse Incident energy: 0.1 to 1. 0 J / cm ² shot number: 1-20 XeCl fluence: 100-600 mJ / cm ² / pulse incident energy: 0.1-2.0 J / cm ² shot number: 1-20

[0020]

EXAMPLES The present invention will be described below with reference to examples. Example 1 "Surflon S-11 was added to a 1% aqueous solution of sodium benzoate.
3 "[made by Asahi Glass Co., Ltd. perfluoroalkylcarboxylate solution (solid content: 30% by weight, medium: water / isopropanol], 0.05% by weight, 0.5% by weight or 1.0% by weight) Using the applicator (Yoshimitsu Seiki Co., Ltd. YA type applicator),
PFA, FEP or ETFE film (10
(0 μm) on the surface (coating thickness: 50 μm) and naturally dried for about 60 minutes, and then irradiated with ArF excimer laser light (150 mJ / cm ² / pulse, 2 shots). The 180 ° peel strength of the obtained surface modified film was measured by the following test method, and the results are shown in Table 1. 180 degree peel strength test test film (30 mm × 150 mm × 100 μm) and stainless steel plate SUS304 (25 mm × 150 mm × 300 μ)
m) is attached using an epoxy resin type room temperature curing adhesive (“Bond E set cleaner” manufactured by Konishi Co., Ltd.)
After leaving it for 20 hours at room temperature with a pressure of 0 g / cm ² applied, pull the test film at a speed of 100 mm / min using a tensile tester (“Autograph P-100” manufactured by Shimadzu Corporation) 180 degree peel strength is measured by.

[0021]

[Table 1]

Comparative Example 1 The 180 ° peel strength of the test film whose surface was modified was measured in the same manner as in Example 1 except that the treatment using the aqueous pretreatment liquid was not performed, and the results are shown in Table 1. The 180-degree peel strength of the test films that were neither treated with the aqueous pretreatment liquid nor subjected to the excimer laser light irradiation treatment was below the measurement limit value (0.01 Kg / cm) in all the films.

Example 2 The blending amount of "Surflon S-113" was set to 1.0% by weight,
The 180 degree peel strength of the test film surface-modified in the same manner as in Example 1 was measured except that the excimer laser light irradiation was performed under the conditions shown in Table 2 below, and the results are shown in Table 2.

[0024]

[Table 2]

Example 3 Instead of sodium benzoate, 2-naphthalenesulfonic acid, benzenesulfonic acid or sodium anthraquinone-2-sulfonate was used, and KrF excimer laser irradiation treatment was performed at 300 mJ / cm ² / pulse for 2 shots. The 180 degree peel strength of the test film whose surface was modified was measured in the same manner as in Example 2 except that the test was carried out under the conditions described in 1. and the results are shown in Table 3 below.

[0026]

[Table 3]

Example 4 An aqueous pretreatment liquid prepared by blending 1% by weight of "Surflon S-113" into a 1%, 5% or 10% aqueous solution of sodium benzoate was used to prepare a PTFE film (300 μm) using an applicator. ) Coated on the surface (coating thickness: 25 μm),
After natural drying, it was irradiated with KrF excimer laser light (26
0 mJ / cm ² / pulse, 4 shots). The 180 ° peel strength of the obtained surface-modified film was measured in the same manner as in Example 1, and the results are shown in Table 4 below.

[0028]

[Table 4]

Example 5 80 parts by weight of "Teflon G-190" (PTFE resin powder manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) and "PFA-"
A test film (500 μm) was produced by molding and firing a compound weight in which 20 parts by weight of “001” (glass fiber manufactured by Nitto Boseki Co., Ltd.) was powder-mixed. "Surflon S-121" in a 1% aqueous solution of sodium benzoate
[Asahi Glass Co., Ltd. perfluoroalkylammonium salt solution (solid content concentration: 30% by weight, medium: water / isopropanol)] or "Surflon S-132" [Asahi Glass Co., Ltd. perfluoroalkylbetaine solution (solid content concentration: 3
0% by weight, solvent: water / isopropanol)] 0.5% by weight
An aqueous pretreatment liquid prepared by blending was applied to the above-mentioned test film using an applicator (application thickness: 25 μm),
After air-drying, it was irradiated with KrF excimer laser light (30
0 mJ / cm ² / pulse, 4 shots). The 180 ° peel strength of the obtained surface modified film was measured in the same manner as in Example 1, and the results are shown in Table 5 below.

[0030]

[Table 5]

Example 6 A PFA film (100 μm) was immersed for 1 minute in an aqueous pretreatment liquid prepared by blending 1% by weight of “Surflon S-113” into a 1% aqueous solution of sodium anthraquinone-2-sulfonate. After pulling up and air-drying, XeCl (308n
m) Excimer laser light irradiation treatment (500 mJ / c
m ² / pulse, 2 shots). The 180 ° peel strength of the surface-modified PFA film was measured in the same manner as in Example 1 and found to be 1.3 kg / cm.

Example 7 "Surflon S-1 was added to a 1% aqueous solution of sodium benzoate.
13 "in an amount of 1% by weight to prepare an aqueous pretreatment liquid for PF
After applying to A film (100 μm) (application thickness: 50
Immediately, the pretreated surface of the film was irradiated with KrF excimer laser light (fluence: 200 mJ /
cm ² / pulse, number of shots: 3 or 4). The 180 ° peel strength of the surface-modified PFA film was measured in the same manner as in Example 1, and was 0.4 kg / cm (shot number: 3) or 0.6 kg / cm (shot number: 4). .

Comparative Example 2 A PFA film not treated with the aqueous pretreatment liquid was subjected to K
The 180-degree peel strength of the film was measured in the same manner as in Example 7 except that the film was irradiated with rF excimer laser light, and found to be 0.01 kg / cm or less.

Example 8 An alcoholic pretreatment liquid prepared by adding 1% by weight of "Florard FC-430" (commercially available product of Sumitomo 3M: fluorinated alkyl ester) to a 1% ethyl alcohol solution of carbazole was made of PFA. After coating on film (100 μm)
(Coating thickness: 50 μm) Immediately, the pretreated surface of the film was irradiated with KrF excimer laser light (fluence: 3
00 mJ / cm ² / pulse, shot number: 2). The 180 ° peel strength of the surface-modified PFA film was measured in the same manner as in Example 1 and found to be 0.9 kg / cm.

Example 9 An alcoholic pretreatment liquid prepared by blending 0.1% by weight of "Florard FC-430" into a 1% isopropyl alcohol solution of phenanthrene was used as a PFA film (100).
(Coating thickness: 50 μm), immediately after applying Kr
The pre-treated surface of the film was irradiated with F excimer laser light (fluence: 300 mJ / cm ² / pulse, shot number: 2). The 180 ° peel strength of the surface-modified PFA film was measured in the same manner as in Example 1.
It was 3 kg / cm.

Example 10 The 180 ° peel strength of a PFA film treated in the same manner as in Example 9 except that ethyl p-hydroxybenzoate was used instead of phenanthrene was 0.7.
It was kg / cm.

Example 11 1.0% of sodium anthraquinone-2-sulfonate
An aqueous pretreatment solution prepared by adding 0.75% by weight of "Surflon S-113" to an aqueous solution was applied to a PFA film (100 µm) (coating thickness: 25 µm) and immediately irradiated with KrF excimer laser light. (Fluence: 100 mJ / cm ² / pulse, shot number: 9). The wettability of the surface-modified film was measured with a standard solution of wetness index defined in JIS K6768. That is, a series of mixed liquids whose surface tensions change in sequence were sequentially dropped onto the film, and the highest surface tension of the mixed liquid determined to wet the film was evaluated as a wetting index.
It was 5 dyn / cm.

Comparative Example 3 K was added to a PFA film which was not treated with the aqueous pretreatment liquid.
The wetting index was measured in the same manner as in Example 11 except that the irradiation with rF excimer laser light was performed, and was found to be 31 dyn / c.
It was m or less.

Example 12 A PFA film (100 μm) was brushed with an alcoholic pretreatment prepared by blending 0.1% by weight of “Florard FC-430” in a 0.5% isopropyl alcohol solution of phenanthrene. After natural drying, K
The pretreated surface of the film was irradiated with rF excimer laser light (fluence; 100 mJ / cm ² / pulse, shot number: 4). When the wetting index of the surface-modified film was measured in the same manner as in Example 11, it was 54 dyn / cm.
That was all.

According to the present invention, since the ultraviolet absorbing compound is uniformly present on the surface of the fluororesin molded article in a sufficient concentration due to the action of the fluorosurfactant, fluorine which is chemically and physically inactive. The surface of the resin can be effectively modified by irradiation with an ultraviolet laser beam, whereby the wettability, adhesiveness, printability and paintability of the fluororesin are greatly improved. In this case, the excellent heat resistance, chemical resistance and electrical characteristics of the fluororesin are not impaired. Therefore, the surface-modified fluororesin molded product or the like according to the present invention can be subjected to secondary processing such as various printing and coating treatments and composite treatments with other resins and inorganic materials. The added value of is dramatically increased.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B05D 7/02 7717-4D // C08L 27:12 (72) Inventor Yuichi Shimizu Mitsui, Neyagawa, Osaka No. 25-1 Minamimachi, Japan Hara Institute for Power Research Takasaki Research Center Osaka Branch (72) Inventor Shunichi Kasai 25-1, Mitsui Minamimachi, Neyagawa City, Osaka Prefecture Within Japan Hara Power Research Institute Takasaki Research Center Osaka Branch (72) Invention Shunichi Sugimoto 25-1 Mitsuiminami-cho, Neyagawa-shi, Osaka Japan Hara Institute for Nuclear Power Takasaki Research Institute Osaka Branch Foundation, Foundation for the Promotion of Radiation Irradiation (72) Masao Endo 14-5 Shimokita-machi, Neyagawa, Osaka No. Kurashiki Spinning Co., Ltd. Technical Research Laboratory (72) Inventor Tomohiro Nagase 14-5 Shimokitada-cho, Neyagawa-shi, Osaka Kurashiki Spinning Co., Ltd. Technical Research Center

Claims (7)

[Claims] 1. A method for modifying the surface of a fluororesin molded article, which comprises irradiating the surface of the fluororesin molded article with an ultraviolet laser beam in the presence of an ultraviolet absorbing compound and a fluorosurfactant. 2. The method according to claim 1, wherein the ultraviolet absorbing compound is an aromatic ultraviolet absorbing compound. 3. The aromatic ultraviolet absorbing compound is an aromatic hydrocarbon, an aromatic carboxylic acid or a salt thereof, an aromatic aldehyde, an aromatic alcohol, an aromatic amine or a salt thereof, or an aromatic sulfonic acid. The method according to claim 2, which is one or more compounds selected from the group consisting of: and salts thereof and phenols. 4. The fluorosurfactant is a perfluoroalkyl phosphate, a perfluoroalkyl carboxylate,
The method according to claim 1, which is one or more surfactants selected from the group consisting of perfluoroalkyltrimethylammonium salts, perfluoroalkylbetaines, perfluoroalkylamine oxides and perfluoroalkylethylene oxide adducts. 5. The method according to claim 1, wherein the ultraviolet laser light is ArF excimer laser light, KrF excimer laser light or XeCl excimer laser light. 6. The method according to claim 1, wherein the surface of the fluororesin molding is coated with an aqueous solution of an ultraviolet absorbing compound and a fluorosurfactant. 7. The method according to claim 1, wherein the surface of the fluororesin molded article is coated with a lower alcohol solution of an ultraviolet absorbing compound and a fluorosurfactant.