JPH04270734A - Office supply - Google Patents

Abstract

PURPOSE:To obtain inexpensive office supplies having excellent water-repellent property and stainproof property and made of a plastic by providing a chemical absorption film containing an alkyl fluoride group through siloxane bond on the surface of office supplies made of the plastic. CONSTITUTION:(A) Oxidation treatment (e.g. oxygen plasma treatment) is, as necessary, applied to the surface of an office supply (e.g. ball point pen made of acrylic resin), and then (B) the office supply is dipped in a solution of a chlorosilane-based surfactant having an alkyl fluoride group, preferably a cyclohaxane solution of a trichlorosilane-based surfactant (e.g. heptadecafluorodecyltrichlorosilane) having the alkyl fluoride group at ambient temperature under nitrogen atmosphere and successively (C) the unreacted surfactant on the office supply is removed with a solvent (e.g. cyclohexane). Then the office supply is washed with pure water to provide the objective office supply on which a chemical absorption film (preferably monomolecular film) 3 containing the alkyl fluoride group is formed on the surface of a plastic 1 through siloxane bond 2.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to surface modification of plastic molded articles used for office supplies. Especially water repellency
Regarding plastic office supplies with excellent stain resistance.

0002

BACKGROUND OF THE INVENTION Conventionally, many plastic molded products have been used for office supplies. For example, it is used in various fields, including fountain pens, ballpoint pens, mechanical pencils, pencil cases, binders, desks, and chairs. This is because plastic is durable, lightweight, and has a good appearance. For example, cellulose resin, acrylic resin, polyethylene, polypropylene, hard vinyl chloride resin, polyester, polystyrene resin, ABS resin, nylon resin, etc. are used.

0003

[Problems to be Solved by the Invention] However, the above-mentioned plastic molded products have a problem in that they have inferior stain resistance compared to, for example, fluororesins such as polytetrafluoroethylene. In addition, although fluororesin has excellent stain resistance,
There are problems in that the mechanical properties are not very high and it is expensive.

[0004] The present invention was made in view of the conventional drawbacks, and an object of the present invention is to provide office supplies using an inexpensive plastic material that has excellent water repellency and stain resistance.

[0005]

[Means for Solving the Problems] In order to achieve the above object, the office supplies of the present invention are office supplies made of plastic, which contain a fluorinated alkyl group on the surface of a base material of a plastic molded article via a siloxane bond. It is characterized by using a plastic molded product provided with a chemical adsorption film.

[0006] In the above structure, it is preferable that the chemisorption film is a monomolecular film.

[0007]

[Function] According to the structure of the present invention, since the chemically adsorbed film containing fluorinated alkyl groups is provided on the surface of the base material of the plastic molded product through siloxane bonds, water repellency and
Office supplies can be made of inexpensive plastic molded products that have excellent stain resistance and can take advantage of the mechanical strength and other properties of the plastic base material. That is, since the fluorinated alkyl group is present in the surface layer of the chemisorption membrane, it has excellent water repellency and antifouling properties. In addition, since the base of the chemisorption film is formed by chemical bonding through siloxane bonds, the film can be made with excellent durability, and even if the surface is repeatedly washed, the chemisorption film will remain plastic. Does not peel off easily from the surface. Furthermore, since the chemisorption film of the present invention is an extremely thin film on the order of nanometers or angstroms, it does not impair properties such as mechanical strength of the plastic substrate.

[0008] Furthermore, according to the preferred configuration of the present invention in which the chemisorption film is a monomolecular film, it is possible to form a thin film with a uniform thickness, which has excellent transparency and does not impair the aesthetic appearance of the base material. There is no.

[0009]

[Embodiment] As shown in FIG. 1, the office supplies of the present invention use a plastic molded article in which a monomolecular film 3 containing a fluorinated alkyl group is formed on the surface of a plastic 1 via siloxane bonds 2.

Among office supplies, fountain pens and ballpoint pens are made of cellulose resin or acrylic resin, caps are made of polyethylene, underlays are made of hard vinyl chloride resin, and ink containers are made of hollow molded polyethylene. Styrene resin is used for pencil cases, styrene resin is used for pencil sharpeners, ABS resin, nylon resin, and phenolic resin are used for typewriter and copier cases, and push buttons and knobs are made of styrene resin.
Urea resin and cellulose resin are used.

The chemical adsorption film provided on the surface of the plastic molded product used in the office supplies of the present invention is preferably formed using a chlorosilane surfactant having a fluorinated alkyl group.

Examples of the chlorosilane surfactant having a fluorinated alkyl group include CF3 (CF2)7
(CF2)2SiCl3,CF3CH2O(
CH2)15SiCl3,CF3(CH2)2
Si(CH3)2(CH2)15SiCl3,
F(CF2)4(CH2)2Si(CH3)
2 (CH2)9 SiCl3,F(CF2)8
(CH2)2 Si(CH3)2 (CH2)
9 SiCl3, CF3 COO(CH2)15S
iCl3, CF3 (CF2)5 (CH2)2
Including trichlorosilane surfactants such as SiCl3, for example, CF3 (CF2)7 (CH
2)2SiCln(CH3)3-n,CF3
(CF2)7 (CH2)2 SiCln (C
2H5)3-n, CF3CH2O(CH2)
15SiCln (CH3)3-n, CF3CH
2O(CH2)15SiCln(C2H5)3
-n, CF3 (CH2)2 Si(CH3)2
(CH2)15SiCln (CH3)3-n
,F(CF2)4(CH2)2Si(CH3
)2 (CH2)9 SiCln (C2 H5)
3-n,F(CF2)8(CH2)2Si(
CH3 )2 (CH2 )9 SiCln (CH3
)3-n,CF3COO(CH2)15SiC
ln (CH3)3-n, CF3 (CF2)5
(CH2)2SiCln (CH3)3-n
Examples include lower alkyl group-substituted monochlorosilane or dichlorosilane surfactants such as (where n in the formula is either 1 or 2). Among these, in particular, chlorosilyl bonds other than the chlorosilyl bonds bonded to the hydrophilic group of the trichlorosilane surfactant form intermolecular bonds with adjacent chlorosilane groups and siloxane bonds.
This is preferable because it results in a stronger chemisorption film. Also,
CF3 (CF2)n CH2 CH2 SiCl3
(However, n in the formula is an integer, and 3 to 25 is easiest to handle) is preferable because it has a good balance between solvent solubility, chemical adsorption, and functionality such as water repellency and stain resistance. . Furthermore, if an ethylene group or acetylene group is incorporated into the fluorinated alkyl chain portion, the hardness of the chemisorption film itself can be further improved since it can be crosslinked by electron beam irradiation of about 5 megarads after formation of the chemisorption film. be.

The chlorosilane surfactant that can be 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 has a fluorinated alkyl group on the terminal silicon. or a hydrocarbon group (i.e., R, R1, R2, R3 are fluorinated alkyl groups or hydrocarbon groups, and the general formula R2 SiC
12 , R3 SiCl, R1 R2 SiCl2 or R1 R2 R3 SiCl, etc.), but in order to increase the adsorption density, a linear shape is generally preferred. Furthermore, for example, SiCl4, SiHCl3,
SiH2Cl2, Cl-(SiCl2O)n-
SiCl3 (where n is a natural number in the formula), SiClm (
CH3)4-m, SiClm(C2H5)4
-m (where m is an integer from 1 to 3), HSiCll
(CH3)3-l, HSiCl(C2H5
) 3-l (where l is 1 or 2 in the formula), etc. When a substance containing multiple chlorosilyl bonds is chemically adsorbed and then reacted with water, the chlorosilyl bonds on the surface change to hydrophilic silanol bonds, The surface of the plastic molded product becomes hydrophilic.

[0014] Among these substances containing a plurality of chlorosilyl groups, tetrachlorosilane (SiCl4) is preferable because it has high reactivity and a small molecular weight, so that silanol bonds can be provided at a higher density. By making the substrate hydrophilic in this manner, the hydrophilicity can be made higher than when the substrate containing a polymer is oxidized. For example, a chlorosilane surfactant containing a fluorinated alkyl group can be chemically adsorbed onto this, and the chemically adsorbed film obtained in this way has a higher density, so it has higher functions such as water repellency and stain resistance. It will be done.

The method for forming a chemically adsorbed film containing a fluorinated alkyl group via a siloxane bond on the surface of a plastic molded product used in the office supplies of the present invention involves oxidizing the surface of the plastic molded product to make it hydrophilic. The oxidized surface is brought into contact with a non-aqueous organic solvent by immersion, etc., and the chlorosilane surfactant is chemically adsorbed onto the surface of the base material, resulting in chemical adsorption containing fluorinated alkyl groups via siloxane bonds. Preferably, the method includes a step of forming a film.

[0016] As means for oxidizing the surface of the plastic molded product, 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) can be used. Applicable.

The non-aqueous solvent used in the method of forming a chemically adsorbed film containing a fluorinated alkyl group via a siloxane bond on the surface of a plastic molded product used in the office supplies of the present invention is used to form a chemically adsorbed film on the surface of a plastic molded product. Any organic solvent may be used as long as it does not dissolve the product and does not have active hydrogen that reacts with the chlorosilane surfactant. Examples include 1,1-dichloro,1-fluoroethane, 1,1-
dichloro, 2,2,2-trifluoroethane, 1,1-
Fluorine solvents such as dichloro, 2,2,3,3,3-pentafluoropropane, 1,3-dichloro, 1,1,2,2,3-heptafluoropropane, such as hexane, octane, hexadecane, cyclohexane, etc. Hydrocarbon solvents such as ether solvents such as dibutyl ether and dibenzyl ether, and ester solvents such as methyl acetate, ethyl acetate, isopropyl acetate and amyl acetate are preferred.

Further, the chemically adsorbed film formed on the surface of the plastic molded product used in the office supplies of the present invention can sufficiently function even with just 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 An acrylic resin molded for a ballpoint pen was treated with oxygen plasma for 10 minutes in a UV dry stripper (oxygen flow rate: 1 l/min) to oxidize the surface, and then treated with heptadecafluorodecyltrichlorosilane. 10-2mol
/l 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 form a siloxane bond containing a fluorinated alkyl group. A chemically adsorbed monomolecular film was formed on the surface of the acrylic resin. A monomolecular film with a thickness of about 15 angstroms was formed.

Example 2 The same experiment as in Example 1 was conducted except that the acrylic resin molded for the ballpoint pen in Example 1 was replaced with a hard vinyl chloride resin for the underlay, and cyclohexane was replaced with 1,1-dichloro,1-fluoroethane. .

Example 3 The acrylic resin molded for a ballpoint pen in Example 1 was replaced with the styrene resin molded for a pencil sharpener, and after oxygen plasma treatment, a 1 wt % tetrachlorosilane solution (
Solvent: 1,1-dichloro, 1-fluoroethane) under nitrogen atmosphere at room temperature for 60 minutes, unreacted tetrachlorosilane was washed with 1,1-dichloro, 1-fluoroethane, and then purified. Using a sample washed with water and dried, an experiment similar to Example 1 was carried out except that cyclohexane was replaced with 1,1-dichloro,1-fluoroethane.

The office supplies of Examples 1 to 3 were used continuously for 1000 hours under normal usage conditions.

As a comparative example, a product without a chemically adsorbed film was used. After 1000 hours, the antifouling properties of both were compared.

[0025] In the comparative example, the surface of the plastic was extremely dirty and the dirt could not be removed even by wiping with a cloth, but in the example of the present invention, there was almost no dirt. Also,
Even if there was dirt on it, it could be easily removed by wiping it with a cloth. Furthermore, the examples had excellent water repellency.

As is clear from the above results, the office supplies of the comparative example showed no stain resistance after 1000 hours of use, but the office supplies of the present invention showed remarkable stain resistance. Ta.

As described above, the office supplies of this example are superior to conventional ones by using a plastic molded article with a chemisorption film containing a fluorinated alkyl group provided on the surface via a siloxane bond. In comparison, it has significantly better antifouling properties.

Furthermore, since the office supplies of the present invention use a general-purpose resin, they can be made cheaper than using a fluororesin. Furthermore, since it is possible to coat a single layer of molecules, it can also be used where transparency is required. As described above, the present invention has great industrial value.

[0029]

As explained above, according to the present invention, a chemically adsorbed film containing a fluorinated alkyl group is provided on the surface of a base material of a plastic molded product through a siloxane bond, resulting in water repellency and stain resistance. It is possible to make office supplies using plastic molded products that have excellent properties, can take advantage of the properties such as mechanical strength of the plastic base material, and are inexpensive.

[0030] Furthermore, according to the preferred configuration of the present invention in which the chemisorption film is a monomolecular film, it is possible to form a thin film with a uniform thickness, which has excellent transparency and does not impair the aesthetic appearance of the base material. There is no.

[Brief explanation of the drawing]

FIG. 1 is a conceptual cross-sectional view enlarged to the molecular level of a plastic molded product used in the office supplies of the present invention.

[Explanation of symbols]

1...Plastic molded product 2...Siloxane bond 3...Chemisorption film

Claims (2)

[Claims] [Claim 1] An office article made of plastic, characterized in that a plastic molded article is provided with a chemically adsorbed film containing a fluorinated alkyl group via a siloxane bond on the surface of the base material of the plastic molded article. Office supplies. [Claim 2]Claim 1, wherein the chemisorption film is a monomolecular film.
Office supplies listed in .