JPH04252235A - High molecular composition and production thereof - Google Patents

Abstract

PURPOSE:To provide a surface-modified high molecular composition having excellent durability against repeated washing, and high water-repellent, oil- repellent and stain-repeated characteristics or high hydrophilicity and to provide a process for producing the same. CONSTITUTION:A chemically absorbed film 3 is provided on the surface of a high molecular composition through siloxane bonds 2, whereby the chemically adsorbed film 3 is not peeled from the surface of the composition and whereby the functions such as good water repellency, oil repellency and stain resistance imparted to the chemically adsorbing film 3 can be preserved.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD The present invention relates to a surface-modified polymer composition and a method for producing the same.

0002

[Prior Art] As a method for modifying the surface of polymers,
For example, coating with a fluorine-containing silane coupling agent to impart water and oil repellency, coating with wax to impart lubricity, and coating with polyvinyl alcohol to impart hydrophilicity. Coating methods are generally well known, such as a method of coating a fluorocarbon polymer suspension to impart antifouling properties.

0003

[Problems to be Solved by the Invention] However, the coating film obtained by the conventional method has a weak bonding force with the substrate containing polymers, and if the surface is repeatedly wiped with a cloth or washed with water, the coating film will deteriorate. There was a problem that the surface treatment effect would be lost due to peeling off from the substrate. In addition, because the molecules of conventional coating films are oriented in random directions, there are many pinholes in the coating film, resulting in insufficient properties. Furthermore, for example, there is a problem that a coating film of a fluorocarbon polymer cannot be used for transparent plastic optical materials, etc., which are strongly required to have transparency, because of a lack of transparency.

The present invention was made in view of the conventional drawbacks, and includes, for example, a water-repellent, oil-repellent, and stain-resistant polymer composition, or a superhydrophilic polymer composition, which has excellent durability against repeated washing and has high properties. The first objective is to provide highly functional polymer compositions such as products. A second object of the present invention is to provide a simple method for producing such a highly functional polymer composition.

[0005]

Means for Solving the Problems In order to achieve the first object, the present invention provides a polymer composition in which a chemically adsorbed film having siloxane bonds is formed on the surface of a substrate containing a polymer. In addition, in order to achieve the second objective, after oxidizing the surface of the substrate containing the polymer, this substrate is immersed in a non-aqueous organic solvent to chemically adsorb the chlorosilane surfactant on the surface, and the siloxane A chemically adsorbed film having bonds is formed to produce a polymer composition.

[0006]

[Operation] In the polymer composition of the present invention, a chemically adsorbed film is formed on the surface of a substrate containing a polymer by chemical bonding via siloxane bonds. Therefore, even if the surface is repeatedly washed, for example, the chemical adsorption film will not peel off from the substrate surface containing polymers, and the chemical adsorption film will not peel off from the substrate surface containing polymers. Functionality is preserved.

In the method for producing a polymer composition of the present invention, the surface of a substrate containing a polymer is oxidized to form a hydrophilic group such as a hydroxyl group, and then a chlorosilane surfactant is chemically adsorbed onto the surface of the substrate. As a chemically adsorbed film having siloxane bonds is formed, even if the polymer does not have a hydrophilic active hydrogen such as a hydroxyl group as a repeating unit,
A chemisorption film can be easily formed. Moreover, a chemically adsorbed film with close packing can be automatically formed by simply immersing a substrate containing a polymer in a nonaqueous solvent containing a chlorosilane surfactant. As a result, the chemically adsorbed film formed exhibits, for example, high water repellency, oil repellency, antifouling properties, or superhydrophilic properties depending on the function of the chlorosilane surfactant.

[0008]

[Embodiment] As shown in FIG. 1, an embodiment of the polymer composition of the present invention is one in which a chemically adsorbed film 3 is formed on the surface of a substrate 1 containing a polymer via siloxane bonds 2.

[0009] Examples of the polymeric material of the substrate used in the present invention include polycarbonate resin, acrylic resin, vinyl chloride resin, polystyrene resin, polyethylene resin, polypropylene resin, polyamide resin, and acrylic butadiene styrene copolymer (ABS) resin. , acetal resin,
Thermoplastic resins such as methylpentene resins, such as epoxy resins, urea resins, melamine resins, phenolic resins, alkyd resins, urethane resins, unsaturated polyester cured resins, thermosetting resins such as ebonite, or thermosetting resins such as butadiene-styrene rubber, butyl rubber , nitrile rubber, chloroprene rubber, urethane rubber, silicone rubber, etc., and any general-purpose plastic material may be used. In addition, the above-mentioned polymeric materials may be mixed with so-called fillers such as silicon dioxide, calcium carbonate, and titanium oxide, and may also be mixed with so-called plasticizers such as dibutyl phthalate. Alternatively, it may be dyed with a pigment and is applied to a substrate containing a polymeric material.

[0010] When imparting water and oil repellency, stain resistance or slipperiness to the polymer composition of the present invention, a chlorosilane surfactant having a fluorinated alkyl group is used as the material constituting the chemisorption film. It will be done. In addition, when imparting superhydrophilicity to the polymer composition of the present invention, a chlorosilane surfactant having an alkyl group with a terminal vinyl group is used to form a chemically adsorbed film, and then, for example, an electron beam is applied to the polymer composition in an oxygen atmosphere. ,X
The terminals are changed into hydroxyl groups by irradiation with radiation such as rays, gamma rays, and ultraviolet rays, or after a chemically adsorbed film is formed using tetrachlorosilane, the chlorosilyl bonds are converted into silanol bonds by reacting with water.

Examples of the chlorosilane surfactant having a fluorinated alkyl group include CF3(CF2)7(CH
2) 2SiCl3, CF3CH2O(CH2)15Si
Cl3, CF3(CH2)2Si(CH3)2(CH2
)15SiCl3,F(CF2)4(CH2)2Si(
CH3)2(CH2)9SiCl3,F(CF2)8(
CH2)2Si(CH3)2(CH2)9SiCl3,
CF3COO(CH2)15SiCl3,CF3(CF
2) Trichlorosilane surfactants such as 5(CH2)2SiCl3, etc., as well as CF3(CF2)7(
CH2)2SiCln(CH3)3-n,CF3(CF
2) 7(CH2)2SiCln(C2H5)3-n,C
F3CH2O(CH2)15SiCln(CH3)3-
n, CF3CH2O(CH2)15SiCln(C2H
5) 3-n, CF3(CH2)2Si(CH3)2(C
H2) 15SiCln(CH3)3-n,F(CF2)
4(CH2)2Si(CH3)2(CH2)9SiCl
n(C2H5)3-n, F(CF2)8(CH2)2S
i(CH3)2(CH2)9SiCln(CH3)3-
n, CF3COO(CH2)15SiCln(CH3)
3-n, CF3(CF2)5(CH2)2SiCln(
Examples include lower alkyl group-substituted monochlorosilane or dichlorosilane surfactants such as CH3)3-n (where n in the formula is either 1 or 2). Among these, chlorosilyl bonds other than those bonded to the hydrophilic group of the trichlorosilane surfactant are particularly
Since intermolecular bonds are formed between adjacent chlorosilane groups and siloxane bonds, it becomes a stronger chemically adsorbed film, which is preferable. In addition, CF3(CF2)nCH2CH2SiCl3 (where n in the formula is an integer, and 3 to 25 is easiest to handle) has properties such as solvent solubility, chemisorption, water repellency, oil repellency, and stain resistance. This is preferable because it is well balanced. Furthermore, C=C in the alkyl chain or fluorinated alkyl chain portion
If C≡C groups are incorporated, it is possible to further improve the hardness of the chemisorption film itself since it can be crosslinked by electron beam irradiation of about 5 megarads after formation of the chemisorption film.

As the chlorosilane surfactant having an alkyl group, for example, CH3(CH2)18SiCl
3,CH3(CH2)15SiCl3,CH3(CH2
)10SiCl3, CH3(CH2)25SiCl3, etc., as well as trichlorosilane surfactants such as CH3(CH2)18SiCln(CH3)3-n,C
H3(CH2)18SiCln(C2H5)3-n,C
H3(CH2)15SiCln(CH3)3-n,CH
3(CH2)10SiCln(CH3)3-n,CH3
Examples include lower alkyl group-substituted monochlorosilane or dichlorosilane surfactants such as (CH2)25SiCln(C2H5)3-n. Among these, C
H3(CH2)nSiCl3 (where n in the formula is an integer, and about 3 to 25 is easiest to handle) is preferred from the viewpoint of solvent solubility. Also, for example, CH2=CH(CH2)n
The alkyl group of the chlorosilane surfactant may have a vinyl group at the end, such as SiCl3 (where n in the formula is an integer, and is easiest to handle from about 3 to 25). As mentioned above, the terminals of chlorosilane surfactants containing hydrocarbon groups can be changed into hydroxyl groups by irradiation with electron beams, X-rays, γ-rays, ultraviolet rays, etc. in an oxygen atmosphere, and Molecular compositions can be rendered hydrophilic. The chlorosilane surfactant used in the present invention is not only linear as exemplified above, but also has a branched form with a fluorinated alkyl group or a hydrocarbon group, or a fluorinated alkyl group or a hydrocarbon group on the terminal silicon. A form in which a hydrocarbon group is substituted (i.e., a form with the general formula R2SiCl2, R
3SiCl, R1R2SiCl2 or R1R2R3
SiCl, etc.) may be used, but in order to increase the adsorption density, a straight chain is generally preferred. Furthermore, for example, Si
Cl4, SiHCl3, SiH2Cl2, Cl-(Si
Cl2O) n-SiCl3 (where n is a natural number in the formula), S
iClm(CH3)4-m, SiClm(C2H5)4
-m (where m is an integer from 1 to 3), HSiCll (C
When a substance containing multiple chlorosilyl bonds such as H3)3-l, HSiCl(C2H5)3-l (where l is 1 or 2 in the formula) is chemically adsorbed and then reacted with water, the chlorosilyl bonds on the surface are Converts into a hydrophilic silanol bond,
The polymer composition becomes hydrophilic. Among the substances containing multiple chlorosilyl groups, tetrachlorosilane (S
iCl4) is preferable because it has high reactivity and a small molecular weight, so it can provide silanol bonds with higher density. By making the substrate hydrophilic in this way, the hydrophilicity can be made higher than by oxidation treatment of a substrate containing a polymer. Although the polymer composition made superhydrophilic in this way can be used as it is, for example, a chlorosilane surfactant containing a fluorinated alkyl group can be chemically adsorbed onto it, and the chemically adsorbed film obtained in this way can be Since the density is higher, functions such as water repellency, oil repellency, and stain resistance are further enhanced.

The method for producing a polymer composition of the present invention includes the steps of oxidizing the surface of a substrate containing a polymer to make it hydrophilic;
The method includes a step of immersing the oxidized surface in a non-aqueous organic solvent to chemically adsorb a chlorosilane surfactant onto the surface to form a chemically adsorbed film having siloxane bonds.

[0014] As a method for oxidizing a substrate containing a polymer, conventional methods such as oxygen plasma treatment, corona treatment, or immersion in a mixed solution of concentrated sulfuric acid and potassium dichromate (chromium mixed acid solution treatment) are available. Applicable.

[0015] The non-aqueous solvent used in the method for producing the polymer composition of the present invention does not dissolve the polymer contained in the substrate forming the chemisorption film and has active hydrogen that reacts with the chlorosilane surfactant. Any organic solvent may be used. Examples include 1,1-dichloro,1-fluoroethane,
1,1-dichloro,2,2,2-trifluoroethane,
1,1-dichloro,2,2,3,3,3-pentafluoropropane, 1,3-dichloro,1,1,2,2,3-
Fluorine solvents such as heptafluoropropane; hydrocarbon solvents such as hexane, octane, hexadecane, and cyclohexane; ether solvents such as dibutyl ether and dibenzyl ether; methyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, etc. Any of the ester solvents is preferred.

Further, the chemically adsorbed film formed on the surface of the polymer composition of the present invention can sufficiently exhibit its function even with only one layer of monomolecular chemically adsorbed film. To form only one layer of monomolecular chemisorption film, all that is required is to chemically adsorb a chlorosilane surfactant or a substance containing multiple chlorosilyl groups and then wash it with a non-aqueous solvent without contacting it with water. It can be easily performed without requiring any steps. Furthermore, it goes without saying that the chemically adsorbed film may be an accumulation of monomolecular films. In this way, when the chemically adsorbed film forms a monomolecular film, the groups exhibiting the imparted functionality are oriented, and the density is also improved, so that higher functionality can be exhibited.

Next, the present invention will be explained using specific examples. Example 1 A substrate containing a polymer, 5 cm in length and width and 0.3 cm in thickness.
Using a polycarbonate substrate of Heptadecafluorodecyltrichlorosilane was used as the chlorosilane surfactant, and the concentration was 10-2 mol/
1 of cyclohexane solution for 60 minutes at room temperature under a nitrogen atmosphere, and subsequently, unreacted heptadecafluorodecyltrichlorosilane was washed with cyclohexane, and then washed with pure water to remove the siloxane bond containing the fluorinated alkyl group. A chemically adsorbed monolayer was formed on the surface of a polycarbonate substrate.

Example 2 The polycarbonate substrate of Example 1 was replaced with an acrylic resin substrate, heptadecafluorodecyltrichlorosilane was replaced with tridecafluorooctyltrichlorosilane, and cyclohexane was replaced with 1,1-dichloro,2,2,3,3,3. - An experiment was carried out in the same manner as in Example 1 except that pentafluoropropane was used.

Example 3 An experiment similar to Example 1 was conducted except that the polycarbonate substrate in Example 1 was replaced with a polypropylene substrate, and heptadecafluorooctyltrichlorosilane was replaced with perfluorododecyltrichlorosilane.

Example 4 The same experiment as in Example 1 was conducted except that the polycarbonate substrate in Example 1 was replaced with an ABS resin substrate.

Example 5 An experiment similar to Example 1 was conducted except that the polycarbonate substrate in Example 1 was replaced with an epoxy resin substrate and cyclohexane was replaced with dibutyl ether.

Example 6 Example 1 was prepared by changing the polycarbonate substrate of Example 1 to a polyurethane resin substrate and replacing cyclohexane with ethyl acetate.
conducted a similar experiment.

Example 7 The polycarbonate substrate of Example 1 was replaced with a butadiene-styrene rubber substrate, and cyclohexane was replaced with 1,1-dichloro,2
,2,3,3,3-pentafluoropropane,
An experiment was conducted in the same manner as in Example 1.

Example 8 The polycarbonate substrate of Example 1 was replaced with a butyl rubber substrate.
Cyclohexane is 1,1-dichloro, 2,2,3,3,
An experiment was carried out in the same manner as in Example 1 except that 3-pentafluoropropane was used.

Example 9 The polycarbonate substrate of Example 1 was replaced with a nitrile rubber substrate, and cyclohexane was replaced with 1,1-dichloro,2,2,3,3
, 3-pentafluoropropane was used, and an experiment was carried out in the same manner as in Example 1.

Example 10 The heptadecafluorooctyltrichlorosilane of Example 1 was changed to 18-nonadecenyltrichlorosilane, and after forming a chemically adsorbed monomolecular film, it was heated at 300 keV and 0 in an oxygen atmosphere.
．． 02 Mrads-1 electron beam was irradiated for 1 minute.

Example 11 An experiment was conducted in the same manner as in Example 1 except that heptadecafluorooctyltrichlorosilane in Example 1 was replaced with tetrachlorosilane.

Example 12 An experiment was carried out in the same manner as in Example 1, except that the oxidation treatment method was changed to a method of immersion in concentrated sulfuric acid containing 10 wt % potassium dichromate for 5 minutes.

Comparative Example 1 A silane coupling agent (
2w of heptadecafluorodecyltrimethoxysilane)
After spin-coating a t% methanol solution, it was dried at 120° C. for 1 hour.

Comparative Example 2 A chemically adsorbed monomolecular film of heptadecafluorodecyltrichlorosilane was formed on the polycarbonate substrate of Example 1 without oxidation treatment.

Comparative Example 3 A suspension of polytetrafluoroethylene was spray-coated on the surface of the polycarbonate substrate of Example 1, and then heated at 120°C.
It was heated and dried for 1 hour.

The contact angles of the samples of Examples 1 to 12 and Comparative Examples 1 to 2 with respect to ultrapure water and oil (Nissin Salad Oil) were investigated. The contact angle was measured immediately after forming the chemisorbed film or coating film, and once on the surface with a cloth moistened with water.
The test was performed after 0,000 times of rubbing. The results are shown in Table 1.

[0033]

[Table 1]

[0034] As is clear from Table 1, the polymer composition of the present invention retained its water- and oil-repellency or hydrophilicity even after the surface was washed by repeatedly rubbing it with a water-containing cloth. However, in Comparative Example 1, water and oil repellency were lost. Furthermore, in the sample of Comparative Example 2 in which the surface of the polymer composition was not subjected to oxidation treatment, a chemisorption film having siloxane bonds could not be formed.

The polymer composition of the present invention in which a chemically adsorbed monomolecular film containing a fluorinated alkyl group was formed on the surface had excellent antifouling properties. After the friction test, the sample of Example 1 was dipped in salad oil and wiped with tissue paper, and the oil was wiped off cleanly, but in the sample of Comparative Example 1, even after wiping it with tissue paper several times, an oil film remained on the surface. It was sticky.

The polymer composition of the present invention can also be used as an optical material. The visible light transmittance of the polycarbonate substrate of Example 1 was 92%, which was unchanged from before forming the chemically adsorbed monomolecular film, but in the sample coated with polytetrafluoroethylene of Comparative Example 3, the transmittance was 92%.
The transparency decreased to 0% or less, and the transparency became poor like that of frosted glass.

Note that the chemically adsorbed films described in the above examples are cases where only a single layer of monomolecular film is used, but even if the polymer composition has an accumulation of chemically adsorbed monomolecular films, unreacted chlorosilane surfactant Even when the chemically adsorbed film was formed without washing, there was no change in its functionality. Furthermore, in each of the above examples, an example was shown in which a single polymer substrate was used as a substrate containing a polymer, but even if the polymer contains a filler, a plasticizer, a coloring agent, etc., the polymer composition There was no change in the function given to the object.

[0038]

[Effects of the Invention] As described above, the polymer composition of the present invention has
Since a chemisorption film with siloxane bonds is provided on the surface, it has superior durability against repeated cleaning compared to conventional products, and when the chemisorption film contains fluorinated alkyl groups, it has high water repellency and Shows oil and dirt repellency.

Further, in the method for producing a polymer composition of the present invention, the surface of the polymer composition is oxidized in advance to easily chemically adsorb the chlorosilane surfactant onto the surface of the polymer composition. A chemisorption film having siloxane bonds can be formed. As described above, the present invention has great industrial value.

[Brief explanation of the drawing]

FIG. 1: Cross-sectional view of an example of the polymer composition of the present invention.

[Explanation of symbols]

1 Substrate containing polymer 2 Siloxane bond 3. Chemical adsorption membrane

Claims (7)

[Claims] 1. A polymer composition characterized in that a chemisorption film having a siloxane bond is provided on the surface of a substrate containing a polymer. [Claim 2] Claim 1, wherein the chemisorption film contains a fluorinated alkyl group or an alkyl group.
The polymeric composition described. 3. The polymer composition according to claim 1, wherein the chemically adsorbed film is a monomolecular film. 4. The polymer composition according to claim 1, wherein the polymer is a thermoplastic resin, a thermosetting resin, or a rubber. 5. An oxidation step of oxidizing the surface of a base material containing a polymer, and immersing the polymer composition in a non-aqueous organic solvent to chemically adsorb a chlorosilane surfactant onto the surface of the polymer composition. and forming a chemically adsorbed film having siloxane bonds. [Claim 6] The non-aqueous organic solvent is a fluorine-containing solvent,
7. The method for producing a polymer composition according to claim 6, wherein the solvent is a hydrocarbon solvent, an ether solvent, or an ester solvent. 7. The method for producing a polymer composition according to claim 6, wherein the chemisorption film is formed from tetrachlorosilane.