JPS63120789A - Surface modifier for resin and surface modification method - Google Patents

Abstract

PURPOSE:To prepare a resin which is excellent in water and oil repellency and stain resistance and has a small coefficient of friction, by heat treating a resin containing a particular compd. added thereto. CONSTITUTION:A resin (e.g., PP) is mixed with 0.5-10wt% surface modifier of formula I or II (wherein Rf is a 1-10C perfluoroalkyl; X<1> is H, Cl, F, or methyl; X<2> is H, Cl, F, methyl, phenyl, carboxyl, methoxycarbonyl, acetyloxy, cyano when X<1> is H, Cl when X<1> is Cl, F when X<1> is F, and methoxycarbonyl when X<1> is methyl; Y is H, a halogen, or carboxyl; and n s 1-20), followed by heating at 50-200 deg.C for 0.5-2hr.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a resin surface modifier and a resin surface modification method. More specifically, the resin has water and oil repellency,
Stain resistance, Fi! The present invention provides a surface modifier and a surface modification method capable of imparting surface properties such as a low coefficient of friction.

[Conventional technology]

Polytetrafluoroethylene (hereinafter referred to as PTFE)
However, it is well known that PTFE has excellent surface properties such as being oily, stain resistant, and having a low coefficient of friction. However, PTFE has limited molding methods, is expensive, etc. There were some drawbacks, and the scope of its use was limited.

Therefore, methods of imparting the surface characteristics of PTFH to general-purpose resins have been studied. One method is to coat the resin surface with a polymer having a perfluoroalkyl group.

However, this method has problems such as deterioration of surface properties over time. On the other hand, a method has been reported in which a compound containing a perfluoroalkyl group is kneaded into a resin to reduce the friction coefficient of the resin surface (Japanese Patent Laid-Open No. 55-7
(See Publication No. 820).

[Problems to be Solved by the Invention] However, since the compound used in the above method has a structure having a perfluoroalkyl group in the side chain, the surface migration of the perfluoroalkyl group is poor, and the perfluoroalkyl group is attached to the resin. This method was not sufficient as a method for imparting the characteristics of a fluoroalkyl group.

The object of the present invention is to provide a high degree of ta water on the resin surface by adding and mixing a small amount to the resin, which has excellent surface migration properties.
Resin surface modifiers that can impart surface properties such as oiliness, antifouling properties, and low coefficient of friction, and can be used to achieve more advanced surface modification effects. The object of the present invention is to provide a method for surface modification of resin.

[Means to solve the problem]

The gist of the present invention is the general formula % formula % () [wherein R2 is a perfluoroalkyl group having 1 to 10 carbon atoms, Xl is a hydrogen atom, chlorine atom, fluorine atom or methyl group, and X2 is a hydrogen atom When xl is a hydrogen atom, chlorine atom, fluorine atom, methyl group, phenyl group, carboxyl group, methoxycarbonyl group, acetyloxy group or cyano group, when xl is a chlorine atom, a chlorine atom,
When is a fluorine atom, it is a fluorine atom, when Xl is a methyl group, it is a methoxycarbonyl group, Y is a hydrogen atom, a halogen atom or a carboxyl group, and n is an integer from 1 to 2o. ] A method for modifying the surface of a resin, which comprises adding and mixing the surface modifying agent for a resin made of a compound represented by the following formula to the resin, and then heat-treating the resin.

The present inventors have discovered that a telomer (low polymer) compound having a structure represented by the above general formula has moderate compatibility with various resins, has excellent surface migration properties, and has t8 water on the resin surface. The present invention was completed based on the discovery that surface properties such as oiliness, antifouling properties, and low coefficient of friction can be imparted. Conventionally, perfluoroalkyl groups are hydrophobic and oleophobic, but are known to be incompatible with resins other than fluororesins. Therefore, as a result of repeated research on telomer compounds having perfluoroalkyl groups and structural units that are compatible with resins, the present inventors added and mixed telomer compounds represented by the above general formula to resins. It was found that by doing so, the water-repellent T8 oil function, etc. possessed by the perfluoroalkyl group can be imparted to the resin, and the effect is permanent.

Furthermore, the present inventors added and mixed the surface modifier of the present invention to the resin and then heat-treated it at a temperature of 50 to 200°C for 0.5 to 2 hours (hereinafter referred to as annealing treatment), thereby reducing the amount of addition. It has been found that a sufficient amount of TA water, IB oil, etc. can be obtained. This is thought to be because heat treatment improves the surface migration of perfluoroalkyl groups.

Among the above-mentioned compounds (1), those having an iodine atom at the terminal can be synthesized by a normal telomerization reaction.

RrI〇H1工CX'X"11→Rr(CHzCX'X") can be obtained by substituting . The above-mentioned telomerization reaction can be smoothly carried out in an appropriate solvent by the action of a polymerization initiator. The polymerization temperature is not particularly limited as long as it is within the temperature range where the polymerization initiator effectively acts, but it is usually about 20 to 100°C, preferably 40 to 70°C.
A temperature of approximately ℃ is adopted. Usable solvents include, for example, trichlorotrifluoroethane, ethyl ether, tetrahydrofuran, acetone, dioxane, benzene, toluene, etc. Polymerization initiators include well-known agents for initiating polymerization of ethylenically unsaturated compounds. <, 2.2"-azobisisobutyronitrile, 2.2'-azobisisobutyramidine dihydrochloride, 2,2'-azobis(2,4-dimethyl-4-methoxy (valeronitrile), sodium peroxide, hydrogen peroxide, or ammonium persulfate.

The telomer compounds obtained by the above-mentioned telomerization reaction can be fractionated according to the degree of polymerization by solvent extraction.

Moreover, the above-mentioned compound (II) is a compound (1) obtained by the above-mentioned manufacturing method, and has the general formula % (% formula %) (wherein, R2, X"=X" and n have the same meanings as above). Obtained by reacting the iodide compound shown with concentrated nitric acid.

When the above-mentioned telomer compound is used for surface modification of a resin in the present invention, a small amount is sufficient for adding the telomer compound to the resin, but it is usually about 0.5 to 10% by weight, preferably about 0.5 to 10% by weight based on the resin. is about 1 to 10% by weight. Further, if annealing treatment is to be performed, addition of about 0.5 to 5% by weight is sufficient. Of course, it is possible to add and mix more than the amount shown here, but it is usually not preferred because it impairs economic efficiency.

The method of adding and mixing the telomer compound to the resin is not particularly limited, and various methods can be adopted depending on the type of resin. For example, a dry method of mixing the telomer compound of the present invention and resin powder with a mixer etc. Examples include a blending method and a wet blending method in which the telomer compound and resin powder are dissolved in a solvent, and then the solvent is evaporated and dried.

In the present invention, the resin to be treated is not particularly limited, and may include a wide range of conventionally known resins, such as polyethylene, polystyrene, polypropylene, vinyl chloride resin, vinylidene chloride resin, methacrylic resin, Examples include vinyl acetate resin, fluororesin, ABS resin, EVA resin, epoxy resin, phenol resin, and urea resin.

〔Example〕

Next, the present invention will be explained in more detail with reference to Reference Examples and Examples.

Reference Example 1 A stirred stainless steel autoclave with an internal volume of 500 m1 contained 47.5 g of perfluorooctyl iodide at 120 mA! of dichlorotrifluoroethane solution and 1 g of diisopropyl peroxydicarbonate were heated to 50°C, then diluted with vinylidene fluoride gas
As soon as the pressure was increased to 3 kg/cm"G, the pressure started to drop, and after 1 hour, the pressure decreased to 19.5 kg/cm"G. Thereafter, the reaction was continued at the same temperature while keeping the pressure inside the autoclave at 20 kf/am''G with vinylidene fluoride gas, and after 3 hours, the reaction was stopped by releasing the pressure and cooling, and 220 g of slurry containing white solids was obtained. This was filtered through a glass filter and dried to obtain 118 g of a white powdery product.

50 g of this white powder product was subjected to solvent fractionation. First, 100 m j of trichlorotrifluoroethane! Extract with
The solvent was distilled off from this extract and CsF +t (CHzC
15 g of a telomer compound Fz)nl was obtained. In addition, n
=4 means that the average degree of polymerization of the telomer compound is 4, which is the result measured by F-NMR.

The meaning and measurement method of the number n are the same below. Next, extract the residue with trichlorotrifluoroethane and add 100mj of methanol! CsF+t(CH
12 g of the telomer compound zCFt)if was obtained. After extraction with methanol, the residue was extracted with 100 mj of acetone.
! CsF+t(CHxCFz)*
10 g of the telomer compound I was obtained. Next, the residue after extraction with acetone was heated to 50°C and extracted with acetone.
1, and in the same way, CsF + fu (CHgCFz) +
8 g of a telomer compound +T was obtained.

Reference Example 2 Except for replacing perfluorooctyl iodide in Reference Example 1 with perfluoroethyl iodide,
Telomer was produced in the same manner as in Reference Example 1, and C* F 5 (CHzCFz),
A telomer compound Log of 1 was obtained.

Reference Example 3 To 8 g of the telomer compound CaF+t(CHzCFt)++1 obtained in Reference Example 1, 10 ml of fuming nitric acid (98%) was added and reacted at 100°C for 5 hours. After cooling the reaction product, ether was added. Extracted three times. After drying this ether extract with sodium nitrate, the ether was distilled off to obtain 5 g of a telomer compound CsF+y(CHgCFz)+oCHzCO○H.

Reference Example 4 35.1 g of perfluorooctyl iodide, 35.1 g of methyl acrylate, and 0.35 g of azobisisobutyronitrile were placed in an eggplant-shaped flask with an internal volume of 200 mA, and the mixture was cooled with dry ice. After that, the inside of the system was replaced with nitrogen gas.Next, the system was reacted at about 80°C for 20 minutes while stirring in a water bath.After the reaction was completed, Ce F + t (CHtCHCOOCH
z) 30 g of a telomer compound x*I was obtained.

Example 1 CsF+t(CHiCFg) obtained in Reference Example 1, I(
A telomer compound in which n is 4.6.9 or 11) was added to polyvinyl chloride at a ratio of 1% by weight, dissolved in tetrahydrofuran, and then deposited on a glass plate to prepare a film. The water resistance of 1a was evaluated by measuring the contact angle with water on the surface of the obtained film. The I8 oiliness was also evaluated by measuring the contact angle with n-hexadecane on the film surface. The measurement results are shown in Table 1. Note that the larger the contact angle, the more ta
This indicates that the water-based or T8 oil-based content is large.

From the results shown in Table 1, it can be seen that by adding the telomer compound to the resin, a high degree of water repellency and T8 oil property are imparted to the resin.

Example 2 CsF 17 (CHzCF z)h obtained in Reference Example 1
Example 1 A telomer compound r was mixed with polyvinyl chloride, polyethylene, polypropylene, and polystyrene in various proportions, and a film was formed by the following method to obtain water repellency and oil resistance.
Each was evaluated in the same manner. The IBJ method involves mixing the telomer compound with polyethylene and polypropylene powder, and then press-molding the mixture at a temperature of 170 to 180°C. In the case of polyvinyl chloride, tetrahydrofuran is used as the solvent, and in the case of polystyrene, the solvent is chlorobenzene and methyl ethyl ketone at a volume ratio of 5:1.
After the resin and telomer compound were dissolved in these solvents, a film was formed on a glass plate.

The measurement results for t8 water-based are shown in Table 2, and the measurement results for 18 oil-based are shown in Table 3.

(The following is a blank space) It can be seen from Tables 2 and 3 that by adding the telomer compound to the resin, 18 aqueous property and 10 oil property are imparted to the resin.

Example 3 The telomer compound CzFs (CHzCFz)* obtained in Reference Example 3 was added in various proportions to a co-13 combination of vinylidene fluoride and ethylene trifluoride (vinylidene fluoride 54 mol%), The TA water resistance and oil repellency were evaluated in the same manner as in Example 1 except that methyl ethyl ketone was used as the solvent.

Further, the obtained film was annealed at 100° C. for 2 hours, then cooled to room temperature, and the Iθ aqueous property and tθ oil property were evaluated in the same manner.

Table 4 shows the measurement results for 1a aqueous, and Table 5 shows the measurement results for ta oil.

(Margins below) From the results in Tables 4 and 5, it is clear that annealing improves water and oil repellency, and even with a smaller amount added than without annealing. altitude tn
It can be seen that it exhibits water-based and oil-repellent properties.

Example 4 C*F+t(CHtCFt)+ obtained in Reference Example 3. C
A telomer compound called HICOOH, polyvinyl chloride,
It was added to polymethyl methacrylate and polystyrene in various proportions, and the TA aqueous property and TA oil property were evaluated in the same manner as in Example 2. Note that as a solvent for forming the polymethyl methacrylate film, a mixture of methyl isobutyl ketone and methyl ethyl ketone at a volume ratio of 5:1 was used.

The measurement results for t8 aqueous properties are shown in Table 6, and the measurement results for oil repellency are shown in Table 7.

(The following is a blank space) From the results in Tables 6 and 7, it can be seen that by adding the telomer compound to various resins, 18 aqueous properties and +a oil properties are imparted to the surfaces of each resin.

Example 5 CeF+y(CHzCFi)+oC obtained in Reference Example 3
A telomer compound called HzCOOI-1 was added to polyvinyl chloride and polymethyl methacrylate powders in various proportions and formed into a sheet with a thickness of 2 mm, and the static friction coefficient and dynamic friction coefficient were measured. A Boden-Lehen type friction force measuring machine was used for the measurement, and the load at the time of measurement was 200 g.

The measurement results are shown in Table 8.

(Left space below) From the results in Table 8, it can be seen that by adding the telomer to the resin, both the static friction coefficient and the kinetic friction coefficient are reduced, and it is possible to reduce the friction coefficient of each resin surface.

Example 6 C*F + t (CH*C
HCO0CHt)z. The telomer compound (2) was added to polystyrene in various proportions, and the same procedure as in Example 2 was carried out.
tr3 oiliness was evaluated. The results are shown in Table 9.

From the results shown in Table 9, it can be seen that a high degree of oil repellency can be imparted to polystyrene with low ta oiliness.

〔Effect of the invention〕

According to the present invention, resin can be easily applied to water repellency, 1B oiliness and PJL! ! It is possible to impart the characteristics of a perfluoroalkyl group, such as a small coefficient.

that's all

Claims (1)

[Claims] 1. General formula R_f(CH_2CX^1X^2)_nY or R_f(CH_2CX^1X^2)_nCH_2COO
H [In the formula, R_f is a perfluoroalkyl group having 1 to 10 carbon atoms, X^1 is a hydrogen atom, chlorine atom, fluorine atom, or methyl group, and X^2 is hydrogen when X^1 is a hydrogen atom. When X^1 is a chlorine atom, it is a chlorine atom; when X^1 is a fluorine atom, is a fluorine atom,
When X^1 is a methyl group, a methoxycarbonyl group,
Y represents a hydrogen atom, a halogen atom, or a carboxyl group, and n represents an integer of 1 to 20, respectively. ] A surface modifier for resins consisting of the compound shown below. 2. General formula R_f(CH_2CX^1X^2)_nY or R_f(CH_2CX^1X^2)_nCH_2COO
H [In the formula, R_f is a perfluoroalkyl group having 1 to 10 carbon atoms, X^1 is a hydrogen atom, chlorine atom, fluorine atom, or methyl group, and X^2 is hydrogen when X^1 is a hydrogen atom. When X^1 is a chlorine atom, it is a chlorine atom; when X^1 is a fluorine atom, is a fluorine atom,
When X^1 is a methyl group, a methoxycarbonyl group,
Y represents a hydrogen atom, a halogen atom, or a carboxyl group, and n represents an integer of 1 to 20, respectively. ] A method for surface modification of a resin, which comprises adding and mixing the compound shown in the formula to the resin, and then heat-treating the resin. 3. The method for surface modification of a resin according to claim 2, wherein the temperature of the heat treatment is 50°C to 200°C.