JPH11265058A - Object having surface with coexistence of hydrophilic part and super-water repellent part, its manufacture and printing device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an object which is used for a printing device using water-color ink and where a super-water repellent surface and a part other than it co-exist by forming a part where a contact angle with water is within a specified range on the surface and, then, permitting substance having the surface where the contact angle with water is <= a specified value to be connected or stuck to the part. SOLUTION: Relating to the object having the surface where the contact angle with water is >=150 deg., a part where the contact angle with water is 80-130 deg. is partially formed on the surface and, then, substance having the surface where the contact angle with water is <=70 deg. is connected or stuck to the part. That is, the coating film of substance where the contact angle with ater is <=70 deg. is selectively stuck to the surface with super-water repellent property. Therefore, the surface indicating super-water repellent property is formed on the prescribed surface of the object, a compound where hydrophilic property is increased by receiving light irradiation is coated on the surface after that and a part where super-water repellent property is desired to be reduced is irradiated with light so as to lose super-water repellent property. Then, substance where hydrophilic property is provided and the contact angle with water is <=70 deg. is stuck to the light irradiation part.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an article having a surface in which a hydrophilic portion and a super-water-repellent portion coexist, a method of manufacturing the same, a printing apparatus using the article, and unevenness such as formation of a fine pattern using the article. It relates to the forming method. Although there is no clear definition of super water repellency, the contact angle with water is generally 150 °.
The above surface is called a super water repellent surface.

[0002]

2. Description of the Related Art Letterpress used for printing includes intaglio printing, letterpress printing, lithographic printing (offset printing), photo printing and the like.
Of these, offset printing accounts for about 67% of the total printing value
This is an important printing method that occupies (FY 1994). For example, the mainstream of letterpress currently used for printing newspapers, newspaper advertisements, posters, magazines, and the like is offset printing.

An example of the offset printing method (operations (a) to (d)) is shown below. (a): Exposure Light is applied to the part of the letterpress to which the ink is to be attached. The part irradiated with light is cured (light-cured). Unirradiated parts do not cure. (b): The surface of the unirradiated part of the fixing light (light uncured part) is removed. In this way, a version is completed. (c): dampening with water Water is adhered to the places where the uncured portions have been removed by the operation of (b). This is commonly called dampening. Thereafter, the ink is applied, but the ink used at this time is hydrophobic.
Therefore, ink does not adhere to the portion where water adheres. (d): The printing plate ink is adhered and transferred to paper or the like. Of the above operations (a) to (d), the dampening operation of (c) requires considerable skill, so waterless offset printing that does not require this operation is actually performed, and its improvement A method has also been proposed (for example, Japanese Patent Application Laid-Open No. 4-251256). Furthermore, in order to eliminate the defects of the offset printing method, several printing techniques using water-based ink have been proposed. For example,
Forming a liquid-adhesive area selectively or selectively and reversibly on a surface of a member having a strong repulsion force to a liquid, supplying the liquid ink to this area, and transferring the liquid ink to plain paper or the like. A recording medium effective for obtaining a clearer image (Japanese Patent Application Laid-Open No. 5-31875); a lithographic printing plate in which a portion where a powder is fixed in an image-like manner is formed on the surface of a polymer layer; 20 ° contact angle with water on the area where
A printing plate wherein the contact angle of water on the surface of the polymer layer to which the powder is not fixed is 70 ° or more (JP-A-4-136
No. 940);

[0004]

However, in waterless offset printing, it is quite difficult to control the temperature of the letterpress at the time of printing, and moreover, since the ink is hydrophobic, dust and the like adhere to the printed portion electrostatically. There was trouble to do. In order to make it difficult for dust and the like to adhere, it is conceivable to make the ink water-based.

[0005] It is an object of the present invention to provide a new printing apparatus using an aqueous ink different from conventional waterless offset printing, and an article having a surface having both a super-water-repellent surface and a part which is not used in the apparatus. That is. Another object of the present invention is to provide a method for manufacturing said article. Another object of the present invention is to provide a new method for forming unevenness, since an article having a surface having a super-water-repellent surface and a portion having no super-water-repellent surface can be formed by light irradiation. At that time, the contact angle with water of the part that does not show super water repellency
It is considered that a finer processing can be achieved by lowering the angle to 70 ° or less.

[0006]

The dampening of the above (c) is not required if the unexposed portion has sufficient ink repellency, and therefore unnecessary if the contact angle of the unexposed portion with ink is sufficiently large. It is thought that there is a possibility that the use of an aqueous ink can considerably prevent electrostatic adhesion of dust. As a result, the present inventors have found that the following means are effective in overcoming the above problems, and have reached the present invention. 1. In an article having a surface having a contact angle with water of 150 ° or more, a portion having a contact angle with water of 80 to 130 ° is partially formed on the surface, and then the portion is contacted with water. An article characterized in that a substance having a surface having an angle of 70 ° or less is bonded or adhered. 2. The article according to 1 above, wherein the substance having a contact angle with water of 70 ° or less contains 50% by weight or more of a resin component. 3. The article according to 2 above, wherein the substance having a contact angle with water of 70 ° or less contains particles having an average particle size of 0.01 to 3 μm in an amount of 10 to 100% by weight of the resin component. 4. An article according to the above item 3, wherein the constituent material of the particles having an average particle size of 0.01 to 3 μm is selected from silicon oxide, aluminum oxide and titanium oxide. 5. The article according to the above item 2, wherein the resin has a salt structure. 6. The article according to 5 above, wherein the salt structure of the resin comprises a carboxyl group and an amino group. 7. The article according to 6 above, wherein the resin having a salt structure comprising a carboxyl group and an amino group comprises polyacrylic acid and polyallylamine. 8. In the above item 1, the substance whose contact angle with water is 70 ° or less is R
-Si (OR ') ₃ or Si (OR') ₄ (where R is a linear or branched alkyl group or vinyl group having 1 to 18 carbon atoms, an aminoalkyl group having 1 to 3 carbon atoms in the alkyl group, A tolyl group or a phenyl group, OR ′ is a methoxy group or an ethoxy group), or R-Si (OR ′) ₃ or Si (OR ′) ₄ (where R and OR ′ are as defined above) ) And water or a reaction product of water and a surface having a contact angle of 150 ° or more with water. In 9. above 1-8, in member having a contact angle with water of forming a surface of more than 150 ° formula: Rf- (R) z [wherein, Rf is the following structure: F (CF (CF _{3) -CF 2 -O-) m-CF (} CF 3) CONH-; F (CF 2 -CF 2 -CF 2 -O-) m'-CF 2 -CF 2 -CONH-; or -HNOC - [(- _{CF 2 -CF 2 -O-) n- (} CF 2 -O-) n '] - it is selected from CF ₂ -CONH-, wherein, m and m' is an average 9 to 54, n is an average 8 And n 'is an average of 10 to 40, R is the following structure:

[0007]

Embedded image Wherein z is 1 or 2.]. 10. In a method for producing an article having a portion having a contact angle with water of 70 ° or less on a surface having a contact angle with water of 150 ° or more, the contact angle with water is partially irradiated by irradiating the surface with light. Is 80-130 °
The method according to claim 1, further comprising the step of forming a portion of the above, and then bonding or attaching a substance having a surface having a contact angle with water of 70 ° or less to the portion. 11. The method according to 10 above, wherein the light irradiation is performed by a laser, a xenon lamp, or a mercury lamp. 12. The method according to 10 or 11, wherein the operation of attaching a substance having a surface having a contact angle with water of 70 ° or less is performed by attaching an aqueous solution or aqueous suspension of a substance having hydrophilicity. how to. 13. In 10 or 11 above, the operation of bonding a substance having a surface having a contact angle with water of 70 ° or less is performed by contacting the substance with a vapor forming a substance having hydrophilicity. Method. 14. In a printing apparatus using a letterpress formed using light, the contact angle of water of the letterpress used in the apparatus is 150 ° or more in an unexposed portion, and the contact angle with water on the exposed portion is 70 °.
° A printing device characterized by the fact that a substance of less than or equal to ° is attached or bound. 15. The printing apparatus according to the above 14, wherein the substance having a contact angle with water of 70 ° or less contains a resin component of 50% by weight or more. 16. The printing apparatus according to the above 15, wherein the substance having a contact angle with water of 70 ° or less contains particles having an average particle diameter of 0.01 to 3 μm in an amount of 10 to 100% by weight of the resin component. 17. The printing apparatus according to 16 above, wherein the constituent material of the particles having an average particle diameter of 0.01 to 3 μm is selected from silicon oxide, aluminum oxide, and titanium oxide. 18. The printing apparatus according to the above 15, wherein the resin has a salt structure. 19. The article according to 18 above, wherein the salt structure of the resin comprises a carboxyl group and an amino group. 20. The printing apparatus according to 19 above, wherein the resin having a salt structure comprising a carboxyl group and an amino group comprises polyacrylic acid and polyallylamine. 21. In 14 above, substances whose contact angle with water is 70 ° or less
R-Si (OR ′) ₃ or Si (OR ′) ₄ (where R is a linear or branched alkyl group or vinyl group having 1 to 18 carbon atoms, and an aminoalkyl group having 1 to 3 carbon atoms in the alkyl group) , A tolyl group, or a phenyl group, OR 'is a methoxy group or an ethoxy group), or R-Si (OR') ₃ or Si (OR ') ₄ (R and OR' are as defined above. A) a reaction product of water and a surface having a contact angle of 150 ° or more with water. twenty two. In the above 14 to 21, in a member forming a surface having a contact angle with water of 150 ° or more, Rf- (R) z wherein Rf has the following structure: F (CF (CF ₃ ) -CF ₂ -O-) m-CF (CF ₃ ) CONH-; F (CF ₂ -CF ₂ -CF ₂ -O-) m'-CF ₂ -CF ₂ -CONH-; or -HNOC-[(-CF _{2 -CF 2 -O-) n- (CF 2} -O-) n '] - it is selected from CF ₂ -CONH-, wherein, m and m' is an average 9 to 54, n is an average of 8 to 28 And n 'is on average 10 to 40, R is the following structure:

[0008]

Embedded image And z is 1 or 2.], wherein z is 1 or 2.]. 23. In the concavo-convex formation technology, the surface with a contact angle with water of 150 ° or more is irradiated with light to partially adjust the contact angle with water to 80 to 130.
The method of forming irregularities, wherein a part having a surface having a contact angle with water of 70 ° or less is formed on the part, and a substance having a surface having a contact angle with water of 70 ° or less is attached to the part. 24. The method according to the above item 23, wherein the light irradiation is performed by a laser, a xenon lamp or a mercury lamp. 25. In 23 or 24 above, the operation of attaching a substance having a surface having a contact angle of 70 ° or less with water is performed by attaching an aqueous solution or aqueous suspension of a substance having hydrophilicity. how to. 26. In the above item 23 or 24, an operation of bonding a substance having a surface having a contact angle with water of 70 ° or less is performed by contacting with a vapor of a material forming a substance having hydrophilicity. Method.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION If a portion which does not exhibit super water repellency is selectively formed on a surface exhibiting super water repellency with water, it functions as a letterpress for aqueous ink. However, in the case of fine characters (10 points or less), if the contact angle with water of a portion that does not exhibit super water repellency is large (110 ° or more), the resolution is reduced, and it is difficult to reproduce the fine portions in a kanji having many strokes. At present, the resolution of ink jet printers and electrophotographic printers is at least about 300 dpi, so in order to aim for such a resolution, the contact angle of the part that does not show super water repellency in the study of the present inventors is 70 ° or less. Turned out necessary. In view of this point, the present invention describes producing a surface having a contact angle of 70 ° or less in a portion not exhibiting super water repellency.

First, a method for selectively attaching a coating film of a substance having a contact angle with water of 70 ° or less on a surface exhibiting super water repellency will be described. First, a surface exhibiting super water repellency is formed on a predetermined surface of an article for producing a letterpress or the like of the present invention. Next, a compound (photoreactive substance) which increases hydrophilicity by being irradiated with light is applied to the surface. Thereafter, light is applied to the portion where the water repellency is to be reduced. In this case, light is emitted at a wavelength necessary for the photoreactive substance to change to a structure that increases hydrophilicity, and at a light intensity sufficient to change to a structure that increases hydrophilicity. As a result, the super-water repellency of the irradiated portion is lost. At this time, the contact angle of the light-irradiated portion with water varies depending on the photoreactive substance described later, but the value is about 80 ° even if it gives a low contact angle. 130 ° for some
Some of the photoreactive substances have a contact angle of 130 ° or less, because the adhesion of hydrophilic substances becomes insufficient during the operation (1) or (2) described below. What you give is desirable.

Next, a hydrophilic substance is attached to the light-irradiated portion. There are various methods as this method, and here, two of them ((1) and (2) below) are shown. (1): A method of attaching an aqueous solution or suspension of a substance having hydrophilicity. (2): A method in which a material that forms a substance having hydrophilicity is exposed to vapor. (1) can be performed as follows. First, an aqueous solution or suspension of a substance having hydrophilicity is applied to the surface after light irradiation. This aqueous solution or aqueous suspension adheres only to the portion irradiated with light. The type of the substance is not particularly limited as long as the contact angle with water becomes 70 ° or less when the aqueous solution or the aqueous suspension is dried.
However, when the fine particles described below are mixed, it is necessary to retain the fine particles in the attached matter, so that a resin is preferable. By drying this surface, a coating film of a substance having a contact angle with water of 70 ° or less can be selectively adhered to the surface exhibiting super water repellency.

By the way, the portion where the substance having hydrophilicity is attached by the operation (1) rises from the super-water-repellent surface.
That is, this can be regarded as one of the concavo-convex forming techniques.
If the spot diameter of the irradiated light is reduced, fine irregularities can be formed, and it is also important as a method of a new fine processing technology. If the addition amount of the fine particles is too small, the fine particles are completely buried in a hydrophilic substance such as a resin, so that no irregularities are formed. If the addition amount is too large, the hydrophilic substance cannot retain the fine particles. Also, even if it can be held, that part becomes brittle. Therefore, the strength is too low to be used for letterpress of a printing apparatus. In consideration of these, it is appropriate that the addition amount of the fine particles is about 10 to 100% by weight based on the hydrophilic substance.

(2) can be performed as follows. First, a fine-grained sponge or tissue paper moistened with water is brought into contact with the light-irradiated surface. Since the light-irradiated portion has high hydrophilicity, water adheres thereto. In this case, the amount of adhered water may be very small. Next, it is exposed to the vapor of the material forming the hydrophilic substance. As this material, R-Si (OR ') ₃ or Si (OR') ₄ (where R
18 linear or branched alkyl groups or phenyl groups, and OR 'is a methoxy group or an ethoxy group). These materials react with water to form SiO ₂ ,
Reacts with hydroxyl groups present on the super water repellent surface and is fixed to the surface.

The substance used in the case of (1) includes a resin having hydrophilicity. Examples of the resin include polyvinyl alcohol, polyacrylic acid, polyethylene imine, and polyallylamine. In addition, a polyamic acid salt having an ammonium salt structure in the molecule is also exemplified. A part of the polyamic acid salt is changed into polyimide by heating, and thus, the attached matter includes polyimide. In order to improve the flatness of the deposit after the deposition, it is desirable that the average molecular weight of these substances is large. For example, in the case of using polyvinyl alcohol as the resin, if the resin having an average molecular weight of 22,000 is used, the one dried after attachment is physically brittle, and peels off when rubbed with a finger. However, the average molecular weight is 66,0
When the one having a molecular weight of 00 is used, the resin has more flexibility than the one having an average molecular weight of 22,000. Therefore, the average molecular weight is stronger than that of 22,000. It is preferable to use those having an average molecular weight of 88,000 because the degree of flexibility is further improved. The higher the resin content, the easier it is to retain the fine particles described later, and the higher the physical strength. Therefore, it is desirable that the resin is contained in an amount of 50 wt% or more of the total amount of the deposit.

It is also possible to enhance the hydrophilicity by forming regular irregularities on the surface. In this case, a method of dispersing fine particles having a certain particle size in an aqueous solution or aqueous suspension of a hydrophilic substance can be used. In this case, if the particle size is too large, the particle cannot be held by the hydrophilic substance. On the other hand, if it is too small, it will not be possible to form irregularities. Therefore, the average particle size is preferably around 0.01 to 3 μm. Incidentally, an acid such as polyacrylic acid forms a salt with a base such as polyethyleneimine and polyallylamine. In the case of a high molecular salt, a salt is formed by a plurality of acidic expressed residues and basic expressed residues (a carboxyl group in the case of polyacrylic acid, an amino group in the case of polyethyleneimine or polyallylamine) in the molecule. This salt is insoluble in water and has a feature of high hydrophilicity due to its salt structure. Therefore, when the article of the present invention is used as a water-based ink letterpress, there is an advantage that the hydrophilic deposit is not easily attacked by the ink when the hydrophilic deposit has a high-molecular salt structure. Polyimide is also a preferable substance in the above use because of its high water resistance. However, since the hydrophilicity is lower than that of the polyamic acid salt, in this case, it is desirable to use the fine particles of 0.01 to 3 μm. The material of the fine particles is not particularly limited as long as it does not dissolve in water or swell with water. Specifically, inorganic materials such as Au, Pt, Ag, Cu, SiO ₂ , Al ₂ O ₃ , TiO ₂ , toner used in copying machines and printers, and carbon used in adsorbents and the like Black and the like are also included. Of these, inorganic oxides such as SiO ₂ , Al ₂ O ₃ , and TiO ₂ are particularly preferred because they tend to increase the hydrophilicity of the deposit. In addition, since Fe etc. gradually corrodes when put in water,
In such a case, it is better to use the solution immediately after adding it to the aqueous solution or suspension of the hydrophilic substance.

The general formula of the substance to be used in the case of (2) is R-Si (OR ') ₃ or Si (OR') ₄ (where R is 1 to ₄ carbon atoms).
18 linear or branched alkyl group or vinyl group, an alkyl group having 1 to 3 carbon atoms, an aminoalkyl group, a tolyl group,
Or OR 'is a methoxy or ethoxy group). Specifically, in the case of R-Si (OR ') ₃ ,
For example, trimethoxymethylsilane, trimethoxyethylsilane, trimethoxy-n-propylsilane, trimethoxy-n-butylsilane, trimethoxy-n-hexylsilane, trimethoxy-n-octylsilane, trimethoxy-n-
Decylsilane, trimethoxy-n-dodecylsilane, trimethoxy-n-hexadecylsilane, trimethoxy-n-octadecylsilane, trimethoxyvinylsilane, trimethoxytolylsilane, 3- (trimethoxysilyl) propylamine, trimethoxyisopropylsilane, trimethoxy- Examples include t-butylsilane, trimethoxycyclopropylsilane, trimethoxycyclohexylsilane, trimethoxycyclooctylsilane, triethoxymethylsilane, and triethoxyethylsilane. In the case of Si (OR ′) ₄ , for example, tetramethylorthosilicate, tetraethylorthosilicate, tetra-n-propylorthosilicate, tetra-n-butylorthosilicate may be mentioned. The reactivity with water tends to be higher as the carbon number of R 'is smaller. Specifically, when OR ′ is a methoxy group, the reactivity is higher than that of an ethoxy group. However, from the viewpoint of storage stability, the lower the reactivity, the less the change due to moisture and the like.

Examples of the photoreactive substance include a triphenylmethane derivative which forms a salt structure in a molecule by irradiation with ultraviolet light, including a malachite green carbinol base, and a spiropyran derivative which forms a salt structure in a molecule by irradiation with ultraviolet light. And photochromic compounds such as 4,5-epoxy-2-cyclopentene derivatives. In addition, a photoacid generator that generates an acid when irradiated with light, a photobase generator that generates a base, and the like can also be used. By the way, as described above, the contact angle of the light irradiation part with water should not exceed 130 °. In this regard, the contact angle with water is reduced to at least about 80 ° when the triphenylmethane derivative is used. However, the spiropyran derivative is reduced to at least about 90 °, and the 4,5-epoxy-2-cyclopentene derivative is reduced to at least about 110 °. In addition, the contact angle is 130 even when the photoreactive substance is used depending on the coating concentration and the lifting speed from the coating layer.
° may be exceeded. However, when an aqueous solution or aqueous suspension of a hydrophilic substance is subsequently applied, the adhesion becomes insufficient, so that the photoreactive substance used and the application conditions are such that the contact angle of the part after light irradiation is 130 ° or less. Is desirable.

Examples of the triphenylmethane derivative include a malachite green compound. In particular,
Bis [4- (dimethylamino) phenyl] phenylmethanol, bis [4- (diethylamino) phenyl] phenylmethanol, bis [4- (dibutylamino) phenyl] phenylmethanol, bis [4- (dimethylamino) phenyl] phenylmethane , Bis [4- (diethylamino) phenyl] phenylmethane and the like.

As the spiropyran derivative, specifically,
1,3,3-trimethylindolinobenzopyrirospirane, 1,
3,3-trimethylindolino-6'-nitrobenzopyrrolospirane, 1,3,3-trimethylindolino-6'-bromobenzopyrrolospirane, 1-n-decyl-3,3-dimethylindolino- 6 '
-Nitrobenzopyrrolospirane, 1-n-octadecyl-3,3-
Dimethylindolino-6'-nitrobenzopyrrolospirane,
3 ', 3'-dimethyl-6-nitro-1'-[2- (phenylcarbamoyl) ethyl] spiro [2H-1-benzopyran-2,2'-indoline], 1,3,3-trimethylindolino- 8'-methoxybenzopyrrolospirane, 1,3,3-trimethylindolino-b-naphthopyrrolospirane and the like.

The 4,5-epoxy-2-cyclopentene derivatives include 2,3-diphenyl-1-indenone oxide and 2,3-diphenyl-1-indenone oxide.
Dimethyl-1-indenone oxide and the like. Examples of the photoacid generator include those used in ordinary photosensitive resin compositions. These basic structures include onium salts, halogen compounds, sulfonic acid esters, sulfonyl compounds, and diazonaphthoquinones. Examples of the onium salt system include diphenyliodonium trifluoromethanesulfonate and triphenylsulfonium trifluoromethanesulfonate. As the halogen compound, for example, 2,6-bis (trichloromethyl) -4- (methoxyphenyl) -1,3,5-
Triazine, 1,3,5-tris (2,3-dibromopropyl)-
1,3,5-triazine-2,4,6- (1H, 3H, 5H) trione and the like. Examples of the sulfonic acid ester type include tris (methanesulfonyloxy) benzene, tris (ethanesulfonyloxy) benzene, methyl a-hydroxymethylbenzoin sulfonate, p-nitrobenzylsulfonic acid benzoate, p-nitrobenzylsulfonic acid naphthalate, -Nitrobenzylsulfonic acid anthrate, p-
Nitrobenzylsulfonic acid-9 ', 10'-anthlate, trifluoromethanesulfonyloxynaphthalimide, trifluoromethanesulfonyloxybenzimide and the like can be mentioned. Examples of the sulfonyl compound system include disulfonyldiazomethane, disulfone and the like. Examples of the diazonaphthoquinone type include 3,4,4′-tris (diazonaphthoquinonesulfonyloxy) -2-hydroxybenzophenone, 2,3,4,4′-tetra (diazonaphthoquinonesulfonyloxy) benzophenone, and the like. These compounds are decomposed by light irradiation to generate an acid.

Examples of the photobase generator include those used in ordinary photosensitive resin compositions. Many of these basic structures include tosylamide and carbamate. In particular,
N-cyclohexyl paratoluenesulfonylamide, N- [1
-(3,5-dimethoxyphenyl) -1-methylethoxycarbonyl] cyclohexylamide, N-[(2,6-dinitrophenyl) methoxycarbonyl] cyclohexylamide, N- [1-
(2,6-dinitrophenyl) ethoxycarbonyl] cyclohexylamide, N- [bis (2,6-dinitrophenyl) methoxycarbonyl] cyclohexylamide, N- [bis (2-
Nitrophenyl) methoxycarbonyl] octadecylamide, N-[(2-nitrophenyl) methoxycarbonyl] octadecylamide, N- [1- (2-nitrophenyl) ethoxycarbonyl] octadecylamide, N- [1- (4,5 -Dimethyl-2-nitrophenyl) ethoxycarbonyl] octadecylamide, N- [1- (4-methyl-2-nitrophenyl) ethoxycarbonyl] octadecylamide and the like. These compounds are discussed in the Journal of the American Chemical Society, 1991, 113, 4303.
It can be synthesized by referring to the description on page -4313. These compounds are decomposed by light irradiation to generate a base.

As a method for irradiating light, a laser, a xenon lamp, a mercury lamp and the like can be mentioned. The apparatus is not particularly limited as long as the irradiation light irradiates light having a wavelength accompanied by a structural change of the photoreactive substance. Xenon lamps, mercury lamps, and the like can cause a structural change of a reactive substance by irradiating the surface with light of a required wavelength using a monochromator, a filter, or the like. When the irradiation energy is small, the irradiation time is increased by increasing the irradiation time.

Next, a method of constructing a super water repellent surface will be described. There are several reports on how to construct a super water repellent surface. The super-water-repellent surface used in the present invention is not limited to the above, as long as the super-water-repellent surface is not lost with a substance used for attaching a compound that increases hydrophilicity by light. When the super water repellency is lost, for example, when applying a compound that increases hydrophilicity with light,
It is conceivable that the super-water-repellent surface undergoes a change such as dissolution with the solvent used. One method of constructing a surface exhibiting super water repellency (super water repellent surface) satisfying the above conditions will be described below.
This is a method using a paint that forms a coating film exhibiting super water repellency (hereinafter abbreviated as super water repellent paint). The paint is basically made of a fluorinated compound for expressing water repellency, fine particles for expressing surface irregularities, a fluorinated compound, a resin for holding fine particles, etc., and a solvent for dissolving and dispersing these. Become. This includes some of those described in JP-A-9-279056.

As a resin, it is preferable not to use an acrylic resin whose super-water-repellent surface is likely to undergo a change such as dissolution by a solvent to be used when a compound which increases hydrophilicity by light is applied. It is preferable to use a resin that is cured or crosslinked by heat or the like, such as an epoxy resin, polyimide, or glass resin. Fine particles which are partially or completely dissolved in the solvent used for the super-water-repellent paint are not preferred because they may not be able to form the necessary irregularities on the super-water-repellent surface. Fine particles that are difficult to dissolve in a solvent are preferred. Such compounds include inorganic compounds such as SiO ₂ , Al ₂ O ₃ , and TiO ₂ (oxides are more stable). Further, a carrier such as ferrite in a developing machine of a copying machine or a printer, and carbon black used as an adsorbent and the like are also included. Fine particles having an average particle size of about 0.01 to 3 μm are used. If it is less than 0.01 μm, it hardly contributes to the formation of surface irregularities. If it is larger than 3 μm, the physical strength of the super water-repellent coating film tends to decrease. In particular, in order to improve the super water repellency, it is preferable to use those having different average particle sizes. When this point was specifically examined, the ratio of the average particle size of the large fine particles to the small fine particles was 50: 1 to 1000: 1.
When it was in the range, the super water repellency of the surface was good.

Examples of the fluorine-containing compound include a compound having a perfluoroalkyl chain, a compound having a perfluoropolyether chain, and a compound having a fluoro group or a trifluoromethyl group on an aromatic ring. Among them, a compound having a perfluoroalkyl chain and a compound having a perfluoropolyether chain are more effective for improving water repellency. When preparing a super water-repellent paint by mixing it with a resin or the like, it is preferable to dissolve it in a solvent to be used or to mix it even if it is not dissolved, since it is uniformly distributed when forming a coating film. However, a compound having a perfluoroalkyl chain or a compound having a perfluoropolyether chain and having a high molecular weight is preferably an organic solvent which dissolves the resin well (acetone, ethyl methyl ketone, dichloromethane, N, N-dimethylformamide, N-methylpyrrolidone). , Isophorone). Therefore, it is desirable to ensure the solubility in these organic solvents by binding an appropriate residue to the terminal.

As the method, the terminal of the perfluoroalkyl chain or perfluoropolyether chain is CH ₂ I or CH ₂
Alkyl halide materials such as ₂ Br (where the CH ₂ Br material is less reactive than the CH ₂ I material) include linear or branched hexanol, octanol, cis or trans cyclohexanol, catechol derivatives, By reacting a hydroxyl group such as ONa or OK with a material converted into an alcoholate, and bonding it via an ether bond, it becomes possible to improve the solubility in an organic solvent. In addition, it is possible to improve the solubility in an organic solvent by reacting with a material having an amino group at a terminal (for example, aniline, linear or branched hexylamine, octylamine, decylamine, etc.) and binding via an amine bond. It becomes possible. Examples of the material having an alkyl halide at the end of the perfluoroalkyl chain include 2- (perfluorobutyl) ethyl iodide, 2- (perfluorohexyl) ethyl iodide, 2- (perfluorooctyl) ethyl iodide, -(Perfluorodecyl) ethyl iodide, 2- (perfluoro-5-methylhexyl)
Ethyl iodide, 2- (perfluoro-5-methyloctyl) ethyl iodide, 2- (perfluoro-5-methyldecyl) ethyl iodide, 2,2,3,3-tetrafluoropropyl iodide, 1H, 1H , 7H-decafluoroheptyl iodide and the like. A material having a perfluoroalkyl chain or a perfluoropolyether chain at the end of CH ₂ OH is
Improving solubility in organic solvents by reacting with a material having an alkyl halide at the end (for example, benzyl bromide, linear or branched hexyl bromide, octyl bromide, decyl bromide, etc.) and bonding via an ether bond. Becomes possible. Further, by reacting with a material having a carboxyl group at a terminal (for example, benzoic acid, linear or branched hexylic acid, octylic acid, decylic acid, etc.) and the like, and binding through an ester bond, solubility in an organic solvent is improved. It can also be improved. As a material having a perfluoroalkyl chain or a perfluoropolyether chain having CH ₂ OH at the end, for example, 2-
(Perfluorohexyl) ethanol, 2- (perfluorooctyl) ethanol, 2- (perfluorodecyl) ethanol, 3- (perfluorohexyl) ethanol, 3-
(Perfluorooctyl) ethanol, 3- (perfluorodecyl) ethanol, Demnum SA manufactured by Daikin Industries, Fomblin Z-DOL manufactured by Audimont, and the like. The material of Krytox 157FS series manufactured by DuPont is a perfluoropolyether having a terminal carboxyl group. This terminal is reduced by lithium aluminum hydride to CH ₂ OH
Can be converted to Therefore, this reduced material can also be used as a material having the above-mentioned terminal CH ₂ OH.

The material having a CO ₂ H terminal at the end of the perfluoroalkyl chain or the perfluoropolyether chain is a material having an amino group at the terminal (for example, aniline, linear or branched hexylamine, octylamine, decylamine, etc.).
And via an amide bond to improve the solubility in an organic solvent. Further, by reacting with a material having a hydroxyl group at a terminal (for example, linear or branched hexanol, octanol, cis or trans cyclohexanol, a catechol derivative, etc.) and bonding via an ester bond, solubility in an organic solvent is improved. It becomes possible. Examples of a material having a CO ₂ H terminal at the end of a perfluoroalkyl chain or a perfluoropolyether chain include perfluorohexanoic acid, perfluorooctanoic acid, perfluorodecanoic acid, 7H-dodecafluoroheptanoic acid, 9H-hexadecafluorononane Acid, perfluoroazelaic acid, Daikin Industries Demnum SH, Audimont Fomblin Z-DIA
C, Dupont Krytox 157FS-L, also 157FS-
M, 157FS-H and the like.

A material having an epoxy group at the end of a perfluoroalkyl chain or a perfluoropolyether chain can be reacted with a material having an amino group at the end, a material having a hydroxyl group, or the like to form an organic compound by bonding through various bonds. It becomes possible to improve the solubility in a solvent. Examples of a material having an epoxy group at the end of a perfluoroalkyl chain or a perfluoropolyether chain include 3-perfluorohexyl-1,2-epoxypropane, 3-perfluorooctyl-1,2-epoxypropane, Fluorodecyl-
1,2-epoxypropane, 3- (perfluoro-5-methylhexyl-1,2-epoxypropane, 3- (perfluoro-5-methyloctyl-1,2-epoxypropane, 3- (perfluoro-5 -Methyldecyl-1,2-epoxypropane, 3- (1H, 1H,
7H-decafluoroheptyloxy) -1,2-epoxypropane, 3- (1H, 1H, 9H-hexadecafluorononyloxy)-
1,2-epoxypropane and the like.

A material having a CH = CH ₂ group at the end of a perfluoroalkyl chain or a perfluoropolyether chain can be converted into an organic solvent by polymerizing with a material having a CH = CH ₂ residue such as styrene or alkyl methacrylate. It becomes possible to improve solubility. However, since the number of reaction points per molecule is two or more, if the polymerization is excessive, the molecular weight may be increased and the solubility may be reduced. Examples of a material having a CH = CH ₂ group at the end of a perfluoroalkyl chain include (perfluorohexyl) ethylene, (perfluorooctyl) ethylene, (perfluorodecyl) ethylene, 1,6-divinyldodecafluorohexane, 8-divinylhexadecafluorooctane and the like.

Of the above-mentioned fluorine-containing compounds, they are easily soluble in organic solvents, have good compatibility with monomers of epoxy resin which is one of the resins used for forming the super-water-repellent surface, and have a super-water-repellent surface. The following compounds are mentioned as those which easily form

[0031]

Embedded image Of these compounds, compounds 1 to 11 shown below are particularly preferred because they have good compatibility with glass resins and the like in addition to epoxy resins.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

Embedded image The average molecular weight of the perfluorooxyalkylene chain is 1,500 to 5,000 for compounds 1 to 8 (m and m 'are 9 to 9 on average).
30), 2,000 to 9,000 of compounds 9 and 10 (m and m 'are 11 to 54 on average), and 11 of 2,000 to 5,
000 (n is an average of 8 to 28 and n 'is an average of 10 to 40) is preferable because of good compatibility with the monomer.

In the perfluoropolyether chains, those having a repeating unit of —CF (CF ₃ ) —CF ₂ O— are available from Krytox 157FS-L and Krytox 157FS manufactured by DuPont as raw materials.
-M or Krytox 157FS-H. When the repeating unit is —CF ₂ CF ₂ CF ₂ O—, Daikin Industries Demnum SH is used as a raw material. When the repeating unit is-(CF ₂ CF ₂ O) _x- (CF ₂ O) _y-, Fomblin Z-DIAC manufactured by Ausimont is used as a raw material.

An example of a method for synthesizing a fluorine-containing compound is as follows. (Synthesis of Compound 1) Krytox 157FS-L manufactured by DuPont
(Average molecular weight 2,500; m is 15 on average) (25 parts by weight)
Was dissolved in 3M Florinert FC-72 (100 parts by weight), and thionyl chloride (2 parts by weight) and dichloromethane (20 parts by weight) were added thereto. The mixture was refluxed for 48 hours with stirring. Thionyl chloride and FC-72 are volatilized by an evaporator to obtain Krytox 157FS-L acid chloride (25 parts by weight).

1,4-bis (4-aminophenoxy) benzene (29 parts by weight) and triethylamine (25 parts by weight) manufactured by Mitsui Toatsu Co., Ltd. were dissolved in dichloromethane (300 parts by weight) and stirred.
A solution obtained by dissolving benzoyl chloride (14 parts by weight) in dichloromethane (100 parts by weight) was added dropwise thereto over 2 hours, followed by stirring for 20 hours. The reaction solution is filtered with filter paper,
The filtrate was concentrated with an evaporator, and then separated and purified by column chromatography (Wako Pure Chemical Industries, Ltd., Wakogel C-200).
Compound 12 (20 parts by weight) having a benzene ring on one of the amino groups is obtained.

[0046]

Embedded image Krytox 157FS-L acid chloride (25 parts by weight),
Compound 12 (4 parts by weight), triethylamine (2 parts by weight),
And dichloromethane (20 parts by weight) with FC-72 (100 parts by weight)
And refluxed for 48 hours with stirring. The reaction solution is filtered with a filter paper, and the filtrate is allowed to stand for 12 hours. Remove the upper layer of dichloromethane layer and add 20 parts by weight of dichloromethane.
After stirring for 12 hours, it is allowed to stand for 12 hours. Excluding the upper dichloromethane layer, FC-72 in the lower FC-72 layer is an evaporator,
Volatilize with a vacuum pump to obtain the desired compound 1 (25 parts by weight; m
Is an average of 15). (Synthesis of Compound 2) Krytox 157FS-L manufactured by DuPont
(Average molecular weight: 2,500) (25 parts by weight) Instead of using Daikin Industries 'Demnum SH (average molecular weight: 3,500; m' is 21 on average) (35 parts by weight) Compound 2 (35 parts by weight; m 'average 21) was obtained. (Synthesis of Compound 3) Benzoyl chloride (14 parts by weight)
Instead of phenoxybenzoic acid chloride (23 parts by weight)
Compound 13 was prepared in the same manner as in the synthesis of compound 12, except that
(25 parts by weight).

[0047]

Embedded image Next, compound 3 was prepared in the same manner as in the synthesis of compound 1 except that compound 13 (5 parts by weight) was used instead of compound 12 (4 parts by weight).
(25 parts by weight; m is an average of 15). (Synthesis of Compound 4) Krytox 157FS-L manufactured by DuPont
(Average molecular weight 2,500) (25 parts by weight) instead of Daikin Industries Demnum SH (Average molecular weight 3,500) (35 parts by weight)
Compound 4 (35
Parts by weight; m 'averages 21). (Synthesis of Compound 5) Instead of 1,4-bis (4-aminophenoxy) benzene (29 parts by weight), 1,3-bis (4-aminophenoxy) benzene (29 parts by weight) manufactured by Mitsui Toatsu is used. Compound 14 (20 parts by weight) was obtained in the same manner as in the synthesis of compound 12, except for the above.

[0048]

Embedded image Next, compound 5 was prepared in the same manner as in the synthesis of compound 1 except that compound 14 (4 parts by weight) was used instead of compound 12 (4 parts by weight).
(25 parts by weight; m is an average of 15). (Synthesis of Compound 6) Krytox 157FS-L manufactured by DuPont
(Average molecular weight 2,500) (25 parts by weight) instead of Daikin Industries Demnum SH (Average molecular weight 3,500) (35 parts by weight)
Compound 6 was synthesized in the same manner as in the synthesis of compound 5, except that
(35 parts by weight; m 'is an average of 21). (Synthesis of Compound 7) Benzoyl chloride (14 parts by weight)
Instead of benzenesulfonic acid chloride (18 parts by weight)
Compound 15 was synthesized in the same manner as in the synthesis of compound 12, except that
(21 parts by weight).

[0049]

Embedded image Next, compound 7 was prepared in the same manner as in the synthesis of compound 1 except that compound 15 (5 parts by weight) was used instead of compound 12 (4 parts by weight).
(25 parts by weight; m is an average of 15). (Synthesis of Compound 8) Krytox 157FS-L manufactured by DuPont
(Average molecular weight 2,500) (25 parts by weight) instead of Daikin Industries Demnum SH (Average molecular weight 3,500) (35 parts by weight)
Compound 8 was synthesized in the same manner as in the synthesis of compound 7, except that
(35 parts by weight; m 'is an average of 21). (Synthesis of Compound 9) Instead of 1,4-bis (4-aminophenoxy) benzene (29 parts by weight), 2,2-bis
Compound 16 (30 parts by weight) is obtained in the same manner as in the synthesis of compound 12, except that [(4-aminophenoxy) phenyl] propane (41 parts by weight) is used.

[0050]

Embedded image Next, compound 9 was prepared in the same manner as in the synthesis of compound 1 except that compound 16 (7 parts by weight) was used instead of compound 12 (4 parts by weight).
(25 parts by weight; m is an average of 15). (Synthesis of Compound 10) Krytox 157FS- manufactured by DuPont
Instead of L (average molecular weight 2,500) (25 parts by weight), Daikin Industries Demnum SH (average molecular weight 3,500) (35 parts by weight)
Compound 10 was prepared in the same manner as in the synthesis of compound 9 except that
(35 parts by weight; m 'is an average of 21). (Synthesis of Compound 11) Z-DIAC (Average molecular weight: 4,000; n is 21 on average, n 'is 22 on average) (40 parts by weight) dissolved in FC-72 (200 parts by weight) manufactured by Ausimont Co. Dicyclohexylcarbodiimide (5 parts by weight), compound 16 (13 parts by weight), and dichloromethane (100 parts by weight) are added, and the mixture is stirred for 120 hours. After the reaction solution is filtered through filter paper, the filtrate is allowed to stand for 12 hours. FC-72 in the lower FC-72 layer is volatilized by an evaporator and a vacuum pump, excluding the upper dichloromethane layer, and the target compound 11 (40 parts by weight; n is 21 on average and n 'is 22 on average) I got When the compounds 1 to 11 or similar materials are used, the materials of the present invention can be used without using a photoreactive substance separately depending on the wavelength of light irradiation, because the materials themselves change their structure by receiving light near 250 nm. It can be. In these materials, amide bonds and the like are cleaved by receiving light near 250 nm, leaving residues that are more hydrophilic than amide bonds such as carboxyl groups. Get higher. Therefore, it is considered that the water repellency is reduced.

A super-water-repellent surface can also be formed by applying a fluorine-containing compound after forming an uneven surface. A method for forming a surface having irregularities can be produced by dispersing fine particles of an appropriate size in a paint and applying the resultant to the surface of a target article. Paints can be applied to the exterior walls of buildings, indoor paints, automobiles, motorcycles,
There are no particular restrictions on paints for bicycles and the like, paints for the outside and inside of ships, and the like. The fine particles used here are preferably the above-mentioned materials in consideration of the solvent resistance. Next, a fluorine-containing compound is applied.
The above-mentioned thing is mentioned as a fluorine-containing compound. In addition, a terminal SiR ₃ (where R is OCH ₃ , OC ₂ H ₅ , CH ₃ or C
Since _{those 2} is H ₅₎ is present scientifically binds to the surface by heating after coating preferable because of keeping the superhydrophobic long. Such materials include, for example, Silaace manufactured by Chisso Corporation (one end is SiR ₃ and the other end is an amino group or an epoxy group) and a perfluoroalkyl chain or a perfluoropolyether chain has a hydroxyl group or It is obtained by condensing an amino group material.

The use of the present invention includes letterpress.
In addition, accessories such as brooches, bracelets, rings, vases,
Decorative articles such as pictures and decorative plate glass are included. It is also considered that application to microfabrication technology is possible. This is because a hydrophilic resin solution is applied to the portion where the water repellency is reduced by light irradiation and then dried, and as a result, it becomes possible to process the light irradiated portion as a mountain and the light non-irradiated portion as a valley. It is.
This may be applied to pattern formation using a resist. If a colorant (dye or pigment) is mixed with the resin solution, a three-dimensional coating can be achieved. This can also be used when drawing the pattern of the ornament.

If the sheet is left in a room or the like after image formation (or after patterning), the portion not irradiated with light may lose super water repellency. This is because the photoreactive substance changes into a hydrophilic structure by a wavelength of 280 nm or more generated from a fluorescent lamp or the like in a room. Therefore, after forming an image (or after patterning), by removing the photoreactive substance, it is possible to prevent a change in the image (or pattern) even when the image is left in a room or the like. The removal may be performed by, for example, washing with an organic solvent in which the photoreactive substance is soluble, but is not particularly limited as long as the formed image (or pattern) does not change. By doing this,
It is considered that convenience in handling this article as letterpress or the like is enhanced.

[0054]

The present invention is illustrated by the following examples, which are for explanation only, and do not limit the present invention. Example 1 In this example, a method for producing a paint for forming a surface exhibiting super water repellency will be described. Yuka Shell Epoxy Co., Ltd. epoxy resin (EP1004) (44 parts by weight), Maruzen Petrochemical Co., Ltd. phenolic resin Marukalinker M (30 parts by weight), Hokuko Chemical's curing accelerator triethyl Ammonium caribol salt (trade name: TEA-K) (1 part by weight) is dissolved in a mixed solvent of ethyl methyl ketone (950 parts by weight) and ethylene glycol mono-n-butyl ether acetate (50 parts by weight), and the mixture is fluorinated. Compound 1 (2 parts by weight)
And mix well. Next, Aerosil 130 (average particle size 0.016 μm) (8 parts by weight) manufactured by Nippon Aerosil Co., Ltd. and Nipsil E-220A (average particle size 1.5 mm) manufactured by Nippon Silica Industry Co., Ltd.
(8 parts by weight) and stir well. In this way, a paint for forming a surface exhibiting super water repellency (described as a super water repellent paint in Example 28 described later) is produced. Aerosil
130 is about 1/94 of the particle size of Nipsil E-220A.

A glass plate having a length of 3 cm, a width of 2 cm and a thickness of 1 mm is immersed in the paint for 10 seconds, and then pulled up at a speed of 3 cm / sec. The glass plate is kept at 120 ° C. for 30 minutes and then at 200 ° C. for 45 minutes.
By heating for a minute, a glass plate having a surface having a contact angle with water of 150 ° or more, that is, a super water-repellent surface is produced. Next, a photoreactive substance is applied to the surface of the glass plate.
Bis [4- (dimethylamino) phenylene] phenylmethane (hereinafter, referred to as compound 17) (1 part by weight) which is a malachite green photochromic compound is dissolved in dichloromethane (99 parts by weight).

[0056]

Embedded image In the dichloromethane solution of compound 17 thus prepared,
The glass plate having a super water repellent surface prepared above is immersed for 10 seconds, and then pulled up at a speed of 3 cm / sec. The glass plate is dried at 40 ° C. for 30 minutes. Thus, the compound 17 is applied on the surface having super water repellency. Even after the application of Compound 17, the surface showed super water repellency.

The surface is partially passed through a color glass filter UV-D36B manufactured by Toshiba Glass Co., Ltd.
Irradiate light with a W xenon lamp for 2 minutes. Light intensity is 6.6
Milliwatt / cm2. As a result, the light-irradiated portion had a contact angle with water reduced to 90 °. However, the non-light-irradiated part had super water repellency. UV-D
36B transmits light with a wavelength of 300-400 nm.

Then, polyacrylic acid (average molecular weight: about 450,000) (0.01 parts by weight) manufactured by Aldrich is dissolved in water (999.99 parts by weight) to prepare a 0.001% by weight aqueous solution of polyacrylic acid (1,000 parts by weight). After immersing the glass plate irradiated with the above light in this aqueous solution for 10 seconds, the speed of 3 cm
Raise in / sec. The aqueous solution of polyacrylic acid adheres to the portion irradiated with light. The glass plate is dried at 120 ° C. for 30 minutes. Next, Nitto Boseki's polyallylamine PAA-10C
(1 part by weight) (average molecular weight about 10,000) to water (999 parts by weight)
In a 0.01% by weight aqueous solution of polyallylamine (1,00
0 parts by weight). (Originally PAA-10C is a 10% by weight aqueous solution.) The glass plate irradiated with the above light is immersed in this aqueous solution for 10 seconds, and then pulled up at a speed of 3 cm / second. The aqueous solution of polyallylamine adheres to the adhered portion of polyacrylic acid. At this attachment portion, polyallylamine and polyacrylic acid form a salt. Wash the glass plate with water to remove excess polyallylamine (which did not form salts with polyacrylic acid). The salt of polyallylamine and polyacrylic acid has high hydrophilicity but hardly dissolves in water. Therefore, the cleaning does not completely remove the glass plate. Thereafter, the glass plate is dried at 120 ° C. for 30 minutes.

After drying, the contact angle of water between the portion where polyallylamine and polyacrylic acid were adhered was reduced to 60 °. However, the other parts maintained super water repellency. After the drying, the portion where the polyallylamine and polyacrylic acid were adhered had a convex portion of the resin made of polyacrylic acid and polyallylamine having a maximum height of 10 μm. From this, it was also found that this method could be a technique for forming unevenness. Example 2 A glass plate having a portion to which polyallylamine and polyacrylic acid prepared in Example 1 were attached was washed with dichloromethane to remove Compound 17 on the surface. 40 of this glass plate
After drying at 30 ° C for 30 minutes, filter the UV-D36B onto Pyrex glass (280 n
irradiating light with the same light source and irradiation time except that light of a wavelength of at least m was transmitted, but the surface irradiated with light remained super-water-repellent. This is considered to be due to the removal of compound 17, which is a photoreactive substance.

On the other hand, the glass plate which was not washed with dichloromethane was lost the super water repellency by the light irradiation, and the contact angle of the irradiated portion with water became 90 °. From the above, the light of the image on the glass plate (280
It was shown that it is possible to prevent the change due to the wavelength (nm or more). Light of fluorescent light for general office use is 280 nm
It is light of the above wavelength. Therefore, if the image is stabilized by light having a wavelength of 280 nm or more, preparation of a dark room or the like becomes unnecessary, and it is considered that convenience in handling this article as letterpress or the like is improved. Example 3 Nippon Aerosil Co., Ltd. Aerosil 200 (average particle diameter 0.012 parts) was added to a 0.001% by weight aqueous solution of polyacrylic acid (1,000 parts by weight).
μm) (50 parts by weight), except that a glass plate having a portion where polyallylamine and polyacrylic acid were attached was prepared in the same manner as in Example 1. The contact angle between the portion where polyallylamine and polyacrylic acid were attached to water was reduced to 30 °. However, the other parts maintained super water repellency. This indicates that the addition of the fine particles (Aerosil 200) can lower the contact angle of the portion where polyallylamine and polyacrylic acid are adhered. Example 4 Nipsil E-200 manufactured by Nippon Silica Kogyo Co., Ltd.
m) A glass plate having a portion to which polyallylamine and polyacrylic acid were attached was prepared in the same manner as in Example 1 except that (50 parts by weight) was added. The contact angle between the portion where polyallylamine and polyacrylic acid were attached to water was reduced to 30 °. However, the other parts maintained super water repellency. This indicates that the addition of fine particles (Nipsil E-200) can lower the contact angle of the portion where polyallylamine and polyacrylic acid are adhered. Comparative Example 1 Nippon Aerosil Co., Ltd. Aerosil 300 (average particle diameter 0.007%) was added to a 0.001% by weight aqueous solution of polyacrylic acid (1,000 parts by weight).
μm) (50 parts by weight), except that a glass plate having a portion where polyallylamine and polyacrylic acid were attached was prepared in the same manner as in Example 1. The contact angle between water and the portion where polyallylamine and polyacrylic acid were attached was reduced to 50 °. However, the other parts maintained super water repellency. This indicates that the addition of the fine particles (Aerosil 300) can lower the contact angle of the portion where polyallylamine and polyacrylic acid are adhered. However, the degree of decrease in the contact angle was smaller than that using Aerosil 200. Comparative Example 2 Nipsil E-150J manufactured by Nippon Silica Kogyo Co., Ltd. (average particle diameter 4.0
μm) (50 parts by weight), except that a glass plate having a portion where polyallylamine and polyacrylic acid were attached was prepared in the same manner as in Example 1. The contact angle between water and the portion where polyallylamine and polyacrylic acid were attached was reduced to 50 °. However, the other parts maintained super water repellency. This indicates that the addition of fine particles (Nipsil E-150J) can lower the contact angle of the portion where polyallylamine and polyacrylic acid are adhered. But Nipsil
The degree of decrease in the contact angle was smaller than that using E-200. Example 5 In the same manner as in Example 1 except that bis [4- (dibutylamino) phenyl] phenylmethanol (hereinafter referred to as compound 18) (1 part by weight) was used instead of compound 17 (1 part by weight),
A glass plate having a portion where polyallylamine and polyacrylic acid were attached was prepared.

[0061]

Embedded image The contact angle between water and the portion of the glass plate where polyallylamine and polyacrylic acid were attached was reduced to 60 °. However, the other parts maintained super water repellency. The synthesis of compound 18 was carried out according to the method described in Bulltin of the Chemical Society of Japan, 1988, vol. 61, p. 2321. Example 6 1-n-octadecyl-3,3-in place of compound 17 (1 part by weight)
Glass having a portion to which polyallylamine and polyacrylic acid are adhered in the same manner as in Example 1 except that dimethylindolino-6'-nitrobenzospirane (hereinafter referred to as compound 19) (1 part by weight) is used. A plate was made.

[0062]

Embedded image The contact angle between water and the portion of the glass plate where polyallylamine and polyacrylic acid were attached was reduced to 70 °. However, the other parts maintained super water repellency. Compound 19 was synthesized according to the method described in Chemistry Letters, 1990, page 555. Example 7 A polyallylamine was prepared in the same manner as in Example 1 except that 2,3-diphenyl-1-indenone oxide (hereinafter referred to as compound 20) (1 part by weight) was used instead of compound 17 (1 part by weight). And a glass plate having a portion to which polyacrylic acid was attached.

[0063]

Embedded image The contact angle between water and the portion of the glass plate where polyallylamine and polyacrylic acid were attached was reduced to 70 °. However, the other parts maintained super water repellency. Compound 20 was synthesized according to the method described in Journal of the Chemical Education, 1971, Vol. 48, p. 554. Example 8 Instead of compound 17 (1 part by weight), trifluoromethanesulfonyloxybenzimide (hereinafter referred to as compound 21)
Example 1 except that UV-D33S (manufactured by Toshiba Glass Co., Ltd.) was used instead of UV-D36B for the color glass filter.
A glass plate having a portion where polyallylamine and polyacrylic acid were adhered was produced in the same manner as described above.

[0064]

Embedded image The contact angle between water and the portion of the glass plate where polyallylamine and polyacrylic acid were attached was reduced to 70 °. However, the other parts maintained super water repellency. Example 9 Polyallylamine and polyacrylic acid were prepared in the same manner as in Example 8 except that tris (benzenesulfonyloxy) benzene (hereinafter referred to as compound 22) (1 part by weight) was used instead of compound 21 (1 part by weight). A glass plate having a portion to which was adhered was produced.

[0065]

Embedded image The contact angle between water and the portion of the glass plate where polyallylamine and polyacrylic acid were attached was reduced to 70 °. However, the other parts maintained super water repellency. Example 10 Instead of compound 21 (1 part by weight), N-cyclohexyl paratoluenesulfonylamide (hereinafter referred to as compound 23) (1
(Parts by weight) in the same manner as in Example 8, to produce a glass plate having a portion to which polyallylamine and polyacrylic acid were attached.

[0066]

Embedded image The contact angle between water and the portion of the glass plate where polyallylamine and polyacrylic acid were attached was reduced to 70 °. However, the other parts maintained super water repellency. Example 11 Glass resin GR650 (50 parts by weight, manufactured by Showa Denko KK) was used instead of the following three materials (EP1004 (44 parts by weight), Marcalinker M (30 parts by weight), and TEA-K (1 part by weight)). A glass plate having a portion to which polyallylamine and polyacrylic acid were adhered was produced in the same manner as in Example 1 except for using ()).

The contact angle between water and the portion of the glass plate where polyallylamine and polyacrylic acid were attached was reduced to 60 °. However, the other parts maintained super water repellency. Example 12 EP1004 (44 parts by weight) manufactured by Yuka Shell Epoxy Co., Ltd.
Maruzerinka M (30 parts by weight) manufactured by Maruzen Petrochemical Co., Ltd., TEA-K (1 part by weight) manufactured by Hokuko Chemical, ethyl methyl ketone (950 parts by weight) and ethylene glycol mono-n-butyl ether acetate (50 parts by weight) Of Compound 1) (2 parts by weight) as a fluorine-containing compound, and stirred well. Next, Nippon Aerosil Co., Ltd. Aerosil 130 (8
Parts by weight) and Nipsil E-220A (8
Parts by weight) and thoroughly stirred. Thus, a paint for forming a surface exhibiting super water repellency is produced.

A glass plate having a length of 3 cm, a width of 2 cm and a thickness of 1 mm is immersed in the paint for 10 seconds, and then pulled up at a speed of 3 cm / sec. The glass plate is kept at 120 ° C. for 30 minutes and then at 200 ° C. for 45 minutes.
By heating for a minute, a glass plate having a surface having a contact angle with water of 150 ° or more, that is, a super water-repellent surface is produced. Next, compound 12 (1 part by weight) is dissolved in dichloromethane (99 parts by weight). After immersing the glass plate having a super water-repellent surface prepared above in this solution for 10 seconds, a speed of 3 cm
Raise in / sec. The glass plate is dried at 40 ° C. for 30 minutes. Even after the application of Compound 12, the surface showed super water repellency.

The surface is partially passed through a color glass filter UV-D36B manufactured by Toshiba Glass Co., Ltd.
Irradiate light with a W xenon lamp for 2 minutes. Then, the contact angle with water of the light-irradiated portion was reduced to 90 °. However, the non-light-irradiated part had super water repellency. Next, Tokyo Chemical Industry's trimethoxymethylsilane is placed in a glass container having an inner dimension of 3 cm in length, 2 cm in width and 5 mm in height. The amount to be filled is up to 4 mm in height. That is, 1 mm is left above. A water-absorbing sponge is pressed against the surface of the glass plate having a light-irradiated portion and a non-irradiated portion, and then placed on a container containing trimethoxymethylsilane so as to cover it. At this time, the surface having the light irradiation part and the non-light irradiation part is set to the inside. That is, the vapor of the trimethoxymethylsilane comes into contact with the surface having the light-irradiated portion and the non-irradiated portion. Leave for 1 day in this state. When pressing a sponge,
The amount of water adhering to the surface is moderately small enough that the presence of water cannot be confirmed by the naked eye. The glass plate is fixed to the back surface and the container with tape or the like so as not to fall into the container.

After the standing, the light-irradiated portion had a contact angle with water reduced to 60 °. However, the non-irradiated part of the light maintained super water repellency. Example 13 A treatment was carried out in the same manner as in Example 12, except that trimethoxy-n-octadecylsilane manufactured by Tokyo Chemical Industry was used instead of trimethoxymethylsilane, and the standing time was changed to 10 days instead of 1 day. As a result, the light-irradiated portion of the glass plate had a contact angle with water reduced to 70 °. However, the non-irradiated part of the light maintained super water repellency. Example 14 A treatment was carried out in the same manner as in Example 12, except that trimethoxy-n-phenylsilane manufactured by Tokyo Chemical Industry was used instead of trimethoxymethylsilane, and the standing time was changed to 3 days instead of 1 day. As a result, the light-irradiated part of the glass plate has a contact angle with water.
Dropped to 70 °. However, the non-irradiated part of the light maintained super water repellency. Example 15 A treatment was performed in the same manner as in Example 12, except that triethoxymethylsilane manufactured by Tokyo Chemical Industry Co., Ltd. was used instead of trimethoxymethylsilane, and the standing time was changed to 2 days instead of 1 day. As a result, the light-irradiated portion of the glass plate had a contact angle with water reduced to 60 °. However, the non-irradiated part of the light maintained super water repellency. Example 16 A treatment was carried out in the same manner as in Example 12 except that tetramethyl orthosilicate manufactured by Tokyo Chemical Industry was used instead of trimethoxymethylsilane. As a result, the light-irradiated portion of the glass plate had a contact angle with water reduced to 50 °. However, the non-irradiated part of the light maintained super water repellency. Example 17 Tokyo Chemical Industry Co., Ltd. instead of trimethoxymethylsilane
The treatment was carried out in the same manner as in Example 12, except that -n-butyl orthosilicate was used and the standing time was changed to 10 days instead of 1 day. As a result, the light-irradiated portion of the glass plate had a contact angle with water reduced to 70 °. However, the non-irradiated part of the light maintained super water repellency. Example 18 A glass plate having a portion to which polyallylamine and polyacrylic acid were attached was prepared in the same manner as in Example 1 except that Compound 2 (2 parts by weight) was used instead of Compound 1 (2 parts by weight). .

The contact angle between water and the portion of the glass plate where polyallylamine and polyacrylic acid were attached was reduced to 55 °. However, the other parts maintained super water repellency. Example 19 A glass plate having a portion to which polyallylamine and polyacrylic acid were attached was produced in the same manner as in Example 1 except that Compound 3 (2 parts by weight) was used instead of Compound 1 (2 parts by weight). .

The contact angle between water and the portion of the glass plate where polyallylamine and polyacrylic acid were attached was reduced to 60 °. However, the other parts maintained super water repellency. Example 20 A glass plate having a portion to which polyallylamine and polyacrylic acid were attached was prepared in the same manner as in Example 1 except that Compound 4 (2 parts by weight) was used instead of Compound 1 (2 parts by weight). .

The contact angle between water and the portion of the glass plate where polyallylamine and polyacrylic acid were attached was reduced to 55 °. However, the other parts maintained super water repellency. Example 21 A glass plate having a portion to which polyallylamine and polyacrylic acid were attached was prepared in the same manner as in Example 1 except that Compound 5 (2 parts by weight) was used instead of Compound 1 (2 parts by weight). .

The contact angle between water and the portion of the glass plate where polyallylamine and polyacrylic acid were attached was reduced to 60 °. However, the other parts maintained super water repellency. Example 22 A glass plate having a portion to which polyallylamine and polyacrylic acid were attached was produced in the same manner as in Example 1 except that Compound 6 (2 parts by weight) was used instead of Compound 1 (2 parts by weight). .

The contact angle between water and the portion of the glass plate where polyallylamine and polyacrylic acid were attached was reduced to 55 °. However, the other parts maintained super water repellency. Example 23 A glass plate having a portion to which polyallylamine and polyacrylic acid were attached was prepared in the same manner as in Example 1 except that Compound 7 (2 parts by weight) was used instead of Compound 1 (2 parts by weight). .

The contact angle between water and the portion of the glass plate where polyallylamine and polyacrylic acid were attached was reduced to 60 °. However, the other parts maintained super water repellency. Example 24 A glass plate having a portion where polyallylamine and polyacrylic acid were attached was prepared in the same manner as in Example 1 except that Compound 8 (2 parts by weight) was used instead of Compound 1 (2 parts by weight). .

The contact angle between water and the portion of the glass plate where polyallylamine and polyacrylic acid were attached was reduced to 55 °. However, the other parts maintained super water repellency. Example 25 A glass plate having a portion to which polyallylamine and polyacrylic acid were attached was prepared in the same manner as in Example 1 except that Compound 9 (2 parts by weight) was used instead of Compound 1 (2 parts by weight). .

The contact angle between water and the portion of the glass plate where polyallylamine and polyacrylic acid were attached was reduced to 60 °. However, the other parts maintained super water repellency. Example 26 A glass plate having a portion to which polyallylamine and polyacrylic acid were attached was prepared in the same manner as in Example 1 except that Compound 10 (2 parts by weight) was used instead of Compound 1 (2 parts by weight). .

The contact angle between water and the portion of the glass plate where polyallylamine and polyacrylic acid were attached was reduced to 55 °. However, the other parts maintained super water repellency. Example 27 A glass plate having a portion to which polyallylamine and polyacrylic acid were attached was prepared in the same manner as in Example 1 except that Compound 11 (2 parts by weight) was used instead of Compound 1 (2 parts by weight). .

The contact angle between water and the portion of the glass plate where polyallylamine and polyacrylic acid were adhered was reduced to 50 °. However, the other parts maintained super water repellency. Example 28 A printing experiment was performed by the printing apparatus shown in FIG. As a result, it was confirmed that printing was possible by the method of the present invention. The method for producing the drum-shaped letterpress 1 will be described later.

The principle of the printing apparatus is as follows. The aqueous ink 3 in the aqueous ink reservoir 2 is adhered to a required portion of the drum-shaped letterpress 1 via an ink source roller 4 and an inking roller 5. The ink adhered to the letterpress adheres to the paper 8 transported by the paper transport belt 7 driven by the paper transport belt roll 6, and printing is completed.

The method for producing the drum-shaped letterpress 1 is as follows. Example of an aluminum cylinder with a diameter of 10 cm and a length of 21 cm
The super-water-repellent paint prepared in 1 was applied by the same dipping method as in Example 1, and further dried under the same conditions as in Example 1. Next, the dichloromethane solution of compound 12 prepared in Example 1 was applied by the same dipping method as in Example 1, and further dried under the same conditions as in Example 1.

Next, the aluminum cylinder 9 coated with the super water-repellent paint and the compound 12 is processed into a letterpress by a letterpress making apparatus shown in FIG. The method is as follows. First, the aluminum cylinder 9 is mounted on a carrier 10 on which the cylinder can rotate. This is placed on the conveyor belt 11. Laser 13 on cylindrical surface
Is radiated through the mirror 14 and the polygon mirror 15 to form a latent image. After spraying the 0.001% by weight aqueous solution of polyacrylic acid used in Example 1 on the surface after the formation of the latent image by the sprayer 16, the surface is dried by the hot air blower 19. Next, after spraying the 0.01% by weight aqueous solution of polyallylamine used in Example 1 with the sprayer 20, water is sprayed with the water sprayer 22 to remove excess polyallylamine (which does not form a salt with polyacrylic acid). Finally, it is dried in constant temperature layer 23 (internal temperature is 120 ° C),
A letterpress used in the printing apparatus of FIG. 1 was obtained. Example 29 Irregularities were formed on the super water-repellent surface by the method shown in FIG. Example 1
The glass plate 25 having the super-water-repellent surface prepared in the above (coated with the compound 12) is irradiated with ultraviolet light emitted from an ultraviolet lamp 27 via a mask 26. After irradiation with ultraviolet light, the glass plate was immersed in a 0.001% by weight aqueous solution of polyacrylic acid prepared in Example 1 and in a 0.01% by weight aqueous solution of polyallylamine prepared in Example 1 under the same conditions as in Example 1. Dry under the same conditions as in Example 1. By the above operation, a resin hill 28 made of polyacrylic acid and polyallylamine having a height of about 10 μm was formed on the super water-repellent surface. It was shown that the use of this method makes it possible to form irregularities on the surface.

[0084]

According to the present invention, it is possible to provide an article having a super water-repellent surface having a portion having a contact angle with water of 70 ° or less by treatment such as light irradiation. By using this technology, it has become possible to provide a new printing technology.

[Brief description of the drawings]

FIG. 1 is a schematic view of a printing apparatus according to the present invention.

FIG. 2 is a schematic view of an apparatus for producing a letterpress used in the printing apparatus of the present invention.

FIG. 3 is an explanatory view of a method for forming unevenness according to the present invention.

[Explanation of symbols]

1 Letterpress 2 Ink reservoir 3 Water-based ink 4 Ink roller 5 Inking roller 6 Roller for paper transport belt 7 Paper transport belt 8 Paper 9 Aluminum cylinder coated with super water-repellent paint and compound 12 10 Carrier 11 Carrier conveyor belt 12 Roller for conveyor belt 13 Laser 14 Mirror 15 Polygon mirror 16 Sprayer 17 Spray liquid shield plate 18 Hot air shield plate 19 Hot air blower 20 Sprayer 21 Spray liquid shield plate 22 Sprinkler 23 Constant temperature layer 24 Butt 25 Implement Glass plate having super water repellent surface prepared in Example 1
(Compound 12 is coated) 26 Mask 27 UV lamp 28 Resin consisting of polyacrylic acid and polyallylamine (projected to the super water repellent surface)

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yutaka Ito 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Within Hitachi Research Laboratory, Hitachi, Ltd.

Claims (8)

[Claims] 1. An article having a surface having a contact angle with water of 150 ° or more, wherein the surface has a water contact angle of 80
~ 130 ° part, then the part has a contact angle with water of 7
An article characterized by binding or adhering a substance having a surface of 0 ° or less. 2. A substance having a contact angle of 70 ° or less with water is R-Si
(OR ′) ₃ or Si (OR ′) ₄ (where R is a linear or branched alkyl or vinyl group having 1 to 18 carbon atoms, an aminoalkyl group having 1 to 3 carbon atoms in the alkyl group, a tolyl group Or a phenyl group, and OR 'is a methoxy group or an ethoxy group), or R-Si (OR') ₃ or Si (OR ') ₄ (where R
And OR ′ is as defined above) and water or a reaction product of said surface with a contact angle of 150 ° or more with water. 3. In a member forming a surface having a contact angle with water of 150 ° or more, the following formula: Rf- (R) z wherein Rf has the following structure: F (CF (CF ₃ )- _{CF 2 -O-) m-CF (} CF 3) CONH-; F (CF 2 -CF 2 -CF 2 -O-) m'-CF 2 -CF 2 -CONH-; or -HNOC - [(- CF ₂ -CF ₂ -O-) n- (CF ₂ -O-) n ']-CF ₂ -CONH-, wherein m and m' average 9 to 54, and n average 8 to 54 28, n 'is an average of 10 to 40, R is the following structure: And z is 1 or 2.], wherein the fluorine-containing compound is represented by the formula: 4. A method for producing an article having a portion having a contact angle with water of 70 ° or less on a surface having a contact angle with water of 150 ° or more, wherein the surface is partially irradiated with light by irradiating the surface with light. The contact angle of
A method comprising forming a portion having an angle of 80 to 130 °, and then bonding or attaching a substance having a surface having a contact angle with water of 70 ° or less to the portion. 5. A printing apparatus using a letterpress formed using light, wherein a contact angle of water of the letterpress used in the apparatus is 150 ° or more in an unexposed portion, and a contact angle of water on an exposed portion is reduced. A printing device, wherein a substance having an angle of 70 ° or less is attached or bonded. 6. A substance having a contact angle of 70 ° or less with water is R-Si
(OR ′) ₃ or Si (OR ′) ₄ (where R is a linear or branched alkyl or vinyl group having 1 to 18 carbon atoms, an aminoalkyl group having 1 to 3 carbon atoms in the alkyl group, a tolyl group Or a phenyl group, and OR 'is a methoxy group or an ethoxy group), or R-Si (OR') ₃ or Si (OR ') ₄ (where R
6. The printing apparatus according to claim 5, wherein OR and OR ′ are as defined above), and water or a reaction product of the surface with water having a contact angle of 150 ° or more. 7. In a member forming a surface having a contact angle with water of 150 ° or more, the following formula: Rf- (R) z, wherein Rf has the following structure: F (CF (CF ₃ )- _{CF 2 -O-) m-CF (} CF 3) CONH-; F (CF 2 -CF 2 -CF 2 -O-) m'-CF 2 -CF 2 -CONH-; or -HNOC - [(- CF _{2 -CF 2 -O-) n- (CF} 2 -O-) n '] - is selected from CF ₂ -CONH-, wherein, m and m' is an average 9 to 54, n is an average of 8 to 28, n 'is an average of 10 to 40, R is the following structure: And z is 1 or 2.], wherein the fluorine-containing compound represented by the formula (1) or (2) is contained. 8. In the unevenness forming technique, the contact angle with water is
By irradiating light on a surface of 150 ° or more, a part having a contact angle with water of 80 to 130 ° is partially formed, and then a substance having a surface with a contact angle of 70 ° or less with water is formed on the part. A method for forming concavities and convexities, which comprises bonding or attaching.