JP2733487B2 - Gas phase fluorine-containing functionalization of polymer surface - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing functionalizing method for bonding a fluorine compound to a polymer surface.

2. Description of the Related Art Fluorine compounds, especially fluorine-containing polymers having a perfluoro group in which hydrogen of hydrocarbons such as aliphatic, alicyclic, and aromatic hydrocarbons are all replaced with fluorine are water-repellent, oil-repellent, and antifouling. , Non-adhesion, high lubrication (low friction and wear resistance), water and chemical resistance, low electrical insulation,
It has many unique properties such as low dielectric constant, low dielectric breakdown, and low refractive index (hereinafter referred to as “fluorine-containing function”).

Utilizing its properties, fluorine-containing polymers having a fluorine-containing function are used in many products such as highly lubricated (slidable) molded articles, water- and oil-repellent paints, electrical insulating coatings, and optical fiber materials.

On the other hand, fluoropolymers are extremely expensive, do not have excellent mechanical properties such as strength, rigidity and hardness, and have poor moldability. Therefore, there is a limit in product development.

Therefore, in a molded article such as a fiber, a film, and a plastic molded product, a resin containing a fluoropolymer having a perfluoro group on its surface is used instead of the fluoropolymer as described above, using a normal polymer material. To form a product having the above function.

However, since such a product is a coated product, performance degradation such as peeling, abrasion, and deterioration of the resin during long-term use is likely to occur. Further, in the case of a fiber film product, practical properties such as feeling, feel, drapability and the like tend to decrease.

Problems to be Solved by the Invention The present invention is to adsorb or chemically bond a fluorinated compound having a fluorinated function on the surface of a polymer material serving as a base of a product, so that it can be used for a long time as described above. It is an object of the present invention to provide a novel surface treatment method which does not cause a decrease in function and hardly causes a decrease in performance due to surface processing even in a fiber or film product. In particular, those chemically bonded are preferable since they hardly deteriorate over time.

Means for Solving the Problems The present invention provides a polymer at least on its surface, in the gas phase with a fluorinated functional agent containing a perfluoro group and a group showing adsorption or reactivity to the polymer, The present invention relates to a method for functionalizing a polymer surface with fluorine, comprising binding the fluorine-containing functional agent to the polymer surface.

The polymer targeted by the present invention is not limited, but preferably has a group that reacts with an external reactive reagent, or has the property of adsorbing other components by heating, for example, polyester. Such products may be used, but particularly effective are protein products such as wool, silk, leather, and fur; cotton, hemp, rayon, acetate, paper,
Cellulose products such as pulp and wood; and synthetic resins such as polyvinyl alcohol, polyvinyl butyral, phenolic resins, epoxy resins, phenoxy resins, melamine resins, alkyd resins, modified acrylic resins, modified methacrylic resins, and modified polyurethane resins. Also, a copolymer modified polymer in which an active group (reactive group) is introduced into a normal polymer by a method such as copolymerization, a graft polymer having a reactive graft bonded to the surface, corona discharge, ozonation, plasma treatment, An active group-derived polymer in which an active group is derived by a physical or chemical method such as a chemical reaction can also be used as a target of the present method.

As the fluorinated functional agent, those containing a group having reactivity with the above polymer are particularly useful, but a perfluoroalkyl group Rf I, a perfluoroalkenyl group Rf II represented by the following structural formula, or Pafluoroallyl Rf
Any of perfluoro group Rf of III, carboxylic acid halide (-COX: X = halogen atom such as F, Cl, Br, I, etc.), carboxylic anhydride Sulfonic acid halide (-SO ₂ -X), dihalide phosphonate (-POX _2), phosphorous streaks halides (-PX _2), aldehyde (-COH), methylol (-CH ₂ -OH), thiol (-SH) , amino (-NH _2), nitrile (-C≡
N), isocyanate (-N = C = O), isothiocyanate (-N = C = S), epoxide Halosilane (Si _(R) 3 -mXm, wherein R = -H, -CH ₃ or -C ₂ H _5, m = 1,2 or 3), alkoxysilane (-Si
(R) ₃ -m (OR ′), wherein R is as defined above, R ′ = −
CH ₃ or -C ₂ H ₅ ), isocyanate silane (-Si (R)
₃ ) _3- m (N = C = O) m where R and m are as defined above)
And a fluorine-containing functional agent having a highly active reactive group Y such as Furthermore, in the present invention, the fluorinated functional material is at 85 ° C.
The amount of evaporation in the space of 500 cm ² is 0.1 mg / cm ² or more at,
Those having a vaporization property of 100 mg / g or less can be effectively used.

When the amount of evaporation is less than the above value, the binding is too small to exhibit effective properties, and when the amount of diffusion and loss exceeds the above value, the fluorinated functional agent harmful to the human body leaks to the outside world. Adversely affecting labor health.

 The measurement of both vaporization characteristics is performed by the following method.

(I) Evaporation amount: A weighing bottle having an inner diameter of 5.4 mm is placed in a three-neck separable flask having an inner diameter of 120 mm and an inner volume of 500 cm ³ . A drying tube filled with silica gel is attached to the upper end of the cooling tube.

In measuring the amount of evaporation, about 1 to 2 g of the sample fluorine-containing functional agent is put into a weighing bottle, the weighing bottle is weighed, and the weighing bottle is put into a separable flask preheated to about 80 ° C. The separable flask is immersed in a hot water bath whose temperature has been adjusted to 85 ° C., and the lid of the weighing bottle is lifted upward and left to stand for 30 minutes. The lid is then removed, the weighing bin is closed and taken out of the flask and reweighed. In the present invention, the difference between the twice weighed values is defined as the amount of evaporation.

(Ii) diffusion geologic volume: bottom inner diameter 5 cm, Erlenmeyer flask having an inner volume of 50 cm ^3, add weighing bottle was weighed sample fluorinated functional agent put about 1 to 2 g. 5mm inside diameter, 20c length in Erlenmeyer flask
Attach a drying tube with silica gel at the upper end of the cooling tube. The flask is immersed in a thermostat controlled at 85 ° C. and allowed to stand for 12 hours. The Erlenmeyer flask is taken out of the system, the weighing bottle is covered, and the weighing bottle is weighed. In the present invention, the difference between the two weighed values is defined as the diffusion loss amount.

Among the fluorine-containing functional agents satisfying the above-mentioned requirements, the compounds represented by the following general formulas (I), (II), (III) and (IV) are comprehensively evaluated in terms of function development, cost, productivity and the like. It is particularly effective in practical use.

_{(Rf I-E-A l} Y (I) [ wherein Rf I and Y are as defined above; E is _{- (CH 2) n -,} - O- (CH 2) n -, or - (OC
H ₂ CH _{2) n} - represents an (n is 0, 1 or 2); (N represents 1, 2 or 3); l represents an integer of 1 or 2].

In the general formula (I), Y is, for example, a group of an acid anhydride. In the case of, 1 represents _2, and becomes (Rf I-E-A ₂ Y).

[Wherein Rf I, Y, E and 1 are as defined above; Rj is -H or _{-CpiF 2 pi + 1 (pi =} 0,1 or 2) (j represents 1, 2, 3, or 4, The compound represented by the formula: [Wherein, Rf II, A, Y, 1, R _{1 to} R ₄ are as defined above]
Compound represented by; (Rf III-E-A l Y (IV) [ wherein, Rf III, E, A, l, Y, is the same as defined compound represented by.

To perform the gas-phase fluorine-containing functionalization treatment using a fluorine-containing functional agent, the fluorine-containing functional agent is heated to a temperature equal to or higher than the melting point, and 50
A steam of ~ 150 ° C is created, and the polymer material to be treated falls in this atmosphere.

The vapor of the fluorinated functional agent may be saturated vapor or sublimation vapor in the above temperature range, or may be a mixed gas diluted to 60% with an inert gas such as nitrogen or helium.

If the heating temperature of the fluorinated functional agent is less than 50 ° C., adsorption and reactivity are poor, and if it is more than 150 ° C., the object to be treated is undesirably deteriorated such as coloring and deterioration of mechanical performance.

The treatment time varies depending on the polymer to be treated, the type of the fluorinated functional agent, and the degree of fluorinated functionalization, but is from several minutes to about 30 minutes.

After the end of the vapor phase treatment of the polymer material with the fluorine-containing functional agent, the object to be treated is air, purging with an inert gas,
The unbound fluorine-containing functional agent is removed from the polymer surface by a method such as volatilization under reduced pressure or washing with a solvent.

 Hereinafter, the present invention will be described with reference to examples.

Example 1 Inner diameter 120 m equipped with thermometer (5) and cooling pipe (6)
m, the following structural formula as a fluorinated functional agent on the bottom of a separable flask having an internal volume of 500 cm ³ (FIG. 1); 15.7500 g of perfluoroalkenyloxybenzoic acid chloride (abbreviated as “PFBC”) (evaporation 3.6 mg / cm ² , volatilization loss 0.7 mg / g) represented by the formula: Silica filter paper (Toyo Advantech) (1) 0.7892 g Is spread, and a 4 mm high corrosion-resistant aluminum spacer (2) / perforated plate (3) set is placed on top of it. The perforated plate (3)
As a sample to be treated, 0.9335 g of a quantitative filter paper (natural paper: Toyo Advantech 5A) (4) was placed.

The flask prepared as described above was set in a thermostat adjusted to 85 ° C. and allowed to stand for 5 minutes.

Thereafter, the sample to be treated was taken out of the system, quickly washed with acetone in several portions, and air-dried. Thereafter, the sample to be treated was dried in a dryer at a temperature of 50 ° C.

No increase in weight of the obtained sample before and after treatment could be detected.

Further, the contact angle of the dropped water droplet was measured on the obtained sample using a goniometer type contact angle measuring device (manufactured by Elma; G-1 type for normal temperature). The results are shown in Table 1.

Example 2 The following structural formula as a fluorine-containing functional agent: Perfluorooctanoic acid chloride (abbreviated as “PFOC”) (vapor amount 7.4 mg / cm ² , volatile amount 1.6 mg /
g) A filter paper for quantitative determination (natural paper: natural paper:
Toyo Advantech 5A) The gas phase fluorinated functionalization treatment was performed under the same conditions as in Example 1 except that 0.9545 g was used.
Evaluation was performed similarly.

Also in this example, no increase in the weight of the object before and after the treatment could be detected.

 The results are shown in Table 1.

Example 3 A polymer sample to be treated was prepared by using the same apparatus as shown in FIG. 1 (FIG. 2) except that a stirring apparatus (7) was provided;
Polyvinyl alcohol film (non-crosslinked product, thickness 10μ)
m) was placed on a perforated rod (8) standing on a perforated plate (3), and the same perfluoroalkoxybenzoic acid chloride as in Example 1 and the same perfluorooctanoic acid chloride as in Example 2 were used as the fluorinated functional agent. The fluorinated functionalization treatment was performed under the same conditions as in Examples 1 and 2, and the evaluation was performed in the same manner.

Also in this example, no increase in weight was detected before and after the treatment.

 The results are shown in Table 1.

Comparative Example Table 1 also shows the evaluation results in Examples 1 to 3 without performing the gas phase treatment of the fluorine-containing functional agent.

EFFECTS OF THE INVENTION The treated product treated according to the present invention can have a remarkable fluorinated function in a very small amount of treated layer that cannot be detected by weight measurement.

The present invention, without affecting the practical properties such as hand,
In addition, the effect of the fluorine-containing function can be enjoyed for a long time.

[Brief description of the drawings]

1 and 2 show an example of a gas phase contact device for carrying out the present invention.

Claims (5)

(57) [Claims] 1. The polymer surface has a vaporization characteristic of an evaporation amount of 0.1 mg / cm ² or more and a diffusion loss amount of 100 mg / g or less in a space of 500 cm ³ at 85 ° C., and has the following structural formula: A perfluoroalkyl group (Rf I), a perfluoro group (Rf) selected from the group consisting of a perfluoroalkenyl group (Rf II) and a perfluoroallyl (Rf III) and a carboxylic acid halide, a carboxylic anhydride, A highly active reactive group (Y) selected from the group consisting of sulfonic acid halides, phosphonic dihalides, phosphorous dihalides, aldehydes, ) Is contacted with a fluorine-containing functional agent having a temperature of 50 ° C to 150 ° C in a steam atmosphere. Gas phase fluorine-containing functionality Act of that polymer surface: 2. A fluorine-containing functional agent following general formula; (Rf I-E-A l Y [Rf I and Y in the formula according to claim 1 and as defined; E is - (CH _{2)
n -, - O- (CH 2} ) n -, or _{- (OCH 2 CH 2) n} -
(N represents 0, 1 or 2); A represents-, Wherein n represents 1, 2 or 3; l represents an integer of 1 or 2.]. 3. The fluorinated functional agent has the following general formula: [Wherein Rf I and Y are as defined in claim 1; E and l are as defined in claim 2; R _j is -H or -C _pi F _{2pi + 1} (p _i = 0, 1, or 2) (j represents 1, 2, 3, or 4; The method according to claim 1, wherein the compound is any of the compounds represented by the following formulas: 4. A fluorine-containing functional agent represented by the following general formula: [Wherein Rf II and Y are as defined in claim 1; A and l are as defined in claim 2; Rj is as defined in claim 3. The method according to claim 1, wherein the compound is any of the compounds represented by the following formulas: 5. A fluorine-containing functional agent represented by the following general formula: (Rf III-E-A ₁ Y wherein Rf III and Y are as defined in claim 1; E, A and 1 are as defined in claim 2. The method according to claim 1, which is any of the compounds represented by the following formulas: