JPH09165459A - Method for producing surface-hydrophobic molded article and surface-hydrophobic molded article - Google Patents

Abstract

(57) Abstract: A fluorine-containing polymerizable monomer and / or oligomer (A) and a polymerizable monomer and / or oligomer (B) having a hydrophilic structural portion are contained as essential components, and Content of (A) is 0.01 to 10
A method for producing a surface-hydrophobic molded article in which the polymerizable resin composition (I) is polymerized and cured by weight, and a polymerized cured resin having a fluorine-containing polymerizable monomer unit and / or oligomer unit as an essential component It is a molded product, the percentage of the number of fluorine atoms on the surface in the total number of atoms is 5% or more, and the surface segregation ratio of fluorine atoms is 10%.
A surface-hydrophobic molding that is up to 2000 times. [Effect] An excellent surface-hydrophobic molded article having a large number of fluorine atoms on the surface and a small component inside and having less fluorine atoms can be easily produced with high productivity in one step. In addition, the surface-hydrophobic molded article has excellent surface hydrophobicity, but the physical properties thereof are not significantly deteriorated, and the fluorine atoms are hardly released.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to the chemical industry, coating,
In various fields such as packaging, printing, automobile industry, spinning, medicine, artificial organs, adhesion, friction, abrasion resistance, lubrication, water repellency, oil repellency, peelability, antistatic, chemical resistance, stain resistance,
The present invention relates to a surface-hydrophobic molded article having excellent surface physical properties such as biocompatibility and antithrombogenicity, and a method for producing the same.

[0002]

2. Description of the Related Art Surface properties of molded products are one of the most important properties for use in various fields, and the surface properties of molded products such as polymer materials, coatings, papers, fibers, etc. Often hydrophobized. The most common surface hydrophobic molding is polymethylmethacrylate (PMM).
Polymers such as A), polycarbonate (PC), and polyurethane, and a hydrophobic polymer having a hydrophobic group or a hydrophobic atom in the molecule such as a silicone-based polymer or a fluorine-based polymer are dissolved in a solvent and mixed. Examples include those molded by blending by a method or a method of melt-kneading.

For example, Macromolecules
Vol. 18, No. 3, pp. 580 (1985) reports a method for producing a surface-hydrophobic molded article by blending a silicone-based polymer with polymethylmethacrylate (PMMA) to form a film. Macromolecules
Volume 18, page 2675 (1985), Surface hydrophobic molding in which a block copolymer is synthesized by changing the mixing ratio of polycarbonate (PC) and polydimethylsiloxane (PDMS) and a film is produced by compression molding or casting method. The manufacturing method of the product has been reported.

[0004]

However, according to the above report, the content of siloxane groups on the film surface depends only on the amount of the silicone-based polymer blended with PMMA, and in order to increase the content of siloxane groups on the surface, Large amounts of silicone-based polymer must be blended. In this case, since a large amount of the silicone-based polymer that does not contribute to the surface hydrophobicity is present inside the film, various physical properties such as film strength and rigidity are deteriorated.
On the other hand, in such a method, since both polymers are not chemically bonded to each other, when exposed to heat treatment or chemicals, the hydrophobic polymer on the surface undergoes layer transition or elution, and the hydrophobicity on the surface suddenly increases. There is a big problem that the hydrophobic polymer inside the film is eluted at the same time and the physical properties of the entire film are changed. For example, it is pointed out in the above report that when a blended film of a silicone-based polymer and PMMA was treated with hexane, the silicone-based polymer on the surface was largely or completely removed.

According to the above report, the surface of the film is subjected to photoelectron spectroscopy by X-ray excitation (Electron spectroscopy).
Spectroscopy for Chemica
(Analysis = ESCA), the average PDMS content in the film was 25% by weight, and the PDMS surface segregation ratio was as low as about 3.1 times.
There was also a lot of PDMS inside the film.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the content rate is 0.01
A polymerizable resin composition (I) containing as an essential component 10 to 10% by weight of a fluorine-containing polymerizable monomer and / or oligomer (A) and a polymerizable monomer and / or oligomer (B) having a hydrophilic structural portion. Is formed and then polymerized and cured, and the like, and the fluorine-containing polymerizable monomer and // in the polymerizable resin composition (I) are produced.
Or, most of the oligomer (A) moves to the surface after being shaped and before being polymerized and cured to form a component-gradient structure on the surface and in a large amount on the inside, and then a structural unit of the resin by polymerization and curing. As a result of being copolymerized with the polymerizable monomer and / or oligomer (B) having a hydrophilic structural part as the component, the surface fluorine atom concentration of the molded article and the degree of the fluorine atom component gradient can be adjusted to those of both components (A) and (B). A wide range can be easily adjusted simply by appropriately changing the type and content ratio, and an excellent surface-hydrophobic molded product with a large number of fluorine atoms on the surface and a small component gradient structure inside, with little deterioration in physical properties, can be obtained in one step. Since it can be easily produced, and the obtained molded product contains a fluorine atom as a part of the monomer unit and / or oligomer unit of the resin constituting the molded product, I found that hard to Nugashi.

Further, in the above-mentioned manufacturing method, the polymerization and curing are substantially instantaneously completed, so that the productivity is high, the moldability, especially the surface application of a complicated shape is easy, and the molding is crosslinked. Since the structure can be easily introduced, it is possible to improve the mechanical strength, heat resistance and chemical resistance of the molded product.

Further, the present inventors have a component-gradient structure in which the content ratio of the fluorine-containing polymerizable monomer unit and / or oligomer unit continuously changes from the surface to the inside among the surface-hydrophobic molded products. It is a polymerized and cured resin molded product, and photoelectron spectroscopy (ES
Surface hydrophobic molded article satisfying the conditions that the percentage of the number of fluorine atoms in the total number of atoms measured by CA) is 5% or more and the surface segregation ratio of fluorine atoms is 10 to 2000 times. Is not limited to the above-mentioned manufacturing method, and even if it is manufactured by any other manufacturing method, fluorine atoms are present on the surface of the molded article in a large amount, but since they are few inside, it is excellent in surface hydrophobicity. The deterioration of physical properties is extremely small, and since the fluorine atom is contained as a part of the monomer unit and / or oligomer unit of the polymerized and cured resin constituting the molded product, the extremely excellent effect that the fluorine atom is hard to be released is obtained. The present invention was completed by discovering that the surface-hydrophobic molded article is effective.

That is, the present invention contains (1) a fluorine-containing polymerizable monomer and / or oligomer (A) and a polymerizable monomer and / or oligomer (B) having a hydrophilic structural portion as essential components, The content of the fluorine-containing polymerizable monomer and / or oligomer (A) in all the monomers and / or oligomer components is 0.0
1 to 10% by weight of the polymerizable resin composition (I) is shaped, and then polymerized and cured, and a method for producing a surface-hydrophobic molded article, (2) the polymerizable resin composition (I) The content of the fluorine-containing polymerizable monomer and / or oligomer (A) in all the contained monomers and / or oligomer components is 0.03 to 5% by weight, and the polymerizable monomer and / or oligomer has a hydrophilic structural portion. The ratio (B / A) of (B) to the fluorine-containing polymerizable monomer and / or oligomer (A) is 15 to 250.
The production method according to (1) above, which is 0 times by weight, (3) the polymerizable resin composition (I) has a fluorine-containing polymerizable monomer and / or oligomer (A), and a polymerizable monomer having a hydrophilic structural portion. And / or an oligomer (B),
The above (1) or (2) containing other polymerizable monomer and / or oligomer (C)
The production method described in (4) above, wherein the energy ray-curable resin composition is used as the polymerizable resin composition (I), and after shaping this, the above-mentioned (1), (2) or polymerizing and curing by energy ray irradiation or (3) Production method, (5) Fluorine-containing polymerizable monomer and / or oligomer (A) is a fluorine-containing vinyl monomer and / or oligomer, and a polymerizable monomer and / or oligomer (B having a hydrophilic structure portion) ) Is a (meth) acrylic monomer and / or oligomer having a hydrophilic structure portion, the production method according to the above (1), (2), (3) or (4), (6) a fluorine-containing vinyl monomer and / or
Alternatively, the oligomer is a fluorine-containing (meth) acrylic monomer and / or oligomer, and the production method according to the above (5), (7) The fluorine-containing (meth) acrylic monomer and / or oligomer is a fluorinated alkyl group-containing (meth). The production method according to (6) above, which is an acrylate, and (8) the (meth) acrylic monomer and / or oligomer having a hydrophilic structural portion has a hydroxyl group and / or a polyethylene glycol structural unit as a hydrophilic structural portion (meth) acrylic. The production method according to the above (5), (6) or (7), which is a monomer and / or oligomer, and (9) the polymerizable resin composition (I) contains a polyfunctional monomer and / or oligomer. All monomers and / or oligomers contained in the polymerizable resin composition (I) The production method according to any one of (1) to (8) above, wherein the content of the polyfunctional monomer and / or oligomer in the component is 5 to 100% by weight, and (10) the polymerizable resin composition ( After shaping I), the percentage of the number of fluorine atoms in the total number of atoms measured by photoelectron spectroscopy (ESCA) by X-ray excitation on the surface after polymerization and curing is 3% or more, and The production method according to any one of the above (1) to (9), which is allowed to stand until the surface segregation ratio of atoms becomes 3.5 times or more, and then polymerized and cured, (11) the polymerizable resin composition (I ) Is shaped into a film and is polymerized and cured, the production method according to any one of (1) to (10) above,

(12) A polymerized and cured resin molded product having a component gradient structure in which the content of fluorine-containing polymerizable monomer units and / or oligomer units continuously changes from the surface to the inside, and the surface is X-ray excited. The percentage of the number of fluorine atoms in the total number of fluorine atoms measured by photoelectron spectroscopy (ESCA) is 5% or more, and the surface segregation ratio of fluorine atoms is 10 to 2000 times. Surface-hydrophobic molded article, (13) The percentage of the number of fluorine atoms in the total number of atoms measured by X-ray excited photoelectron spectroscopy (ESCA) on the surface is 5 to 7
0%, and the surface segregation ratio of fluorine atoms is 10 to 150.
The molded product of (12) and the molded product of (14), which are 0 times, are molded products made of a vinyl-based copolymer.
The molded product according to 2) or (13), or the molded product (15) is
(12) or (13), which is a molded article produced by the production method according to any one of (1) to (11) above.
The molded product according to the above (12), (13), (14) or (15), and the molded product according to (17), wherein the molded product according to (16) is a molded product comprising a crosslinked polymer, The molded article according to any one of the above (12) to (16), which is a film-shaped molded article, is provided.

The surface, the total number of atoms, and the surface segregation ratio of fluorine atoms referred to in the present invention are as follows. Surface means Shimadzu X-ray photoelectron analyzer ESCA 850 type [X
Ray gun anode material: Magnesium, analyzer: blocking electric field analyzer, analyzer energy resolution: A
g3d5 / 2 1.15 eV (half-value width)], and the angle between the surface of the molded product and the photoelectron detector (θ): 15 ° X
It refers to a thin layer on the surface of a molded article that is subjected to elemental analysis by photoelectron spectroscopy (ESCA) by line excitation. The total number of atoms means the total number of various atoms which can be measured by elemental analysis by photoelectron spectroscopy (ESCA) by X-ray excitation. The surface segregation ratio of fluorine atoms means photoelectron spectroscopy (ESC) by X-ray excitation.
Percentage of the ratio of the number of fluorine atoms on the surface of the molded product to the total number of atoms measured by elemental analysis according to A) [X = (the number of fluorine atoms on the surface of the molded product / the total number of atoms on the surface of the molded product) × 10
0 (%)] and the percentage of the number of fluorine atoms in the entire molded product calculated from the composition of the polymerizable resin composition (I) in the total number of atoms [Y = (number of fluorine atoms in the entire molded product. / (Total number of atoms in the entire molded product) x 100 (%)] ratio (X / Y)
Say

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The polymerizable resin composition (I) used in the present invention includes a fluorine-containing polymerizable monomer and / or oligomer (A) and a polymerizable monomer and / or oligomer (B) having a hydrophilic structural moiety. ) And as an essential component, and the content of the fluorine-containing polymerizable monomer and / or oligomer (A) in all the monomer and / or oligomer components is 0.01 to 10% by weight, For example, it contains the above-mentioned (A) and (B) and, if necessary, other polymerizable monomer and / or oligomer (C), and these (A) and (B)
And the content of the fluorine-containing polymerizable monomer and / or oligomer (A) in the total monomer and / or oligomer component consisting of (C) is 0.01 if necessary.
Examples of the energy ray-curable resin composition and the thermosetting resin composition are 10% by weight. Among them, the energy ray-curable resin composition is preferable because it cures in a short time.

The fluorine-containing polymerizable monomer and / or oligomer (A) used here is not particularly limited, and any polymerizable monomer and / or oligomer containing a fluorine atom can be mentioned, but usually a fluorine-containing polymerizable monomer and / or oligomer is used. Vinyl monomers and / or oligomers are used.

The fluorine-containing vinyl monomer and / or oligomer is preferably a fluorine-containing vinyl monomer, for example, trifluoroethyl (meth).
Acrylate, tetrafluoropropyl (meth) acrylate, hexafluorobutyl (meth) acrylate,
Hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, perfluoro (meth) acryloylfluoride, bis- (trifluoromethylformate) -methyl (meth) acrylate,
Fluorinated alkyl group-containing (meth) acrylates such as bis- (tetrafluoroethyl formate) -methyl (meth) acrylate and bis- (heptafluoropropyl formate) -methyl (meth) acrylate, vinyl fluoride, vinylidene fluoride And the like, and a fluorinated alkyl group-containing (meth) acrylate is particularly preferable because of its high reaction rate. These fluorine-containing vinyl monomers and / or oligomers may be used alone or in combination. Here, (meth) acrylic means acrylic and / or methacrylic, and the same applies below.

Further, the polymerizable monomer and / or oligomer (B) having a hydrophilic structure portion is not particularly limited, and any polymerizable monomer and / or oligomer having a hydrophilic structure portion can be mentioned. Usually, a (meth) acrylic monomer and / or oligomer having a hydrophilic structural portion is used.

Examples of the (meth) acrylic monomer and / or oligomer having the hydrophilic structure portion include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butanediol mono (meth) acrylate, 2 -Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 3-chloro-2-hydroxy Propyl (meth) acrylate,
Glycerin di (meth) acrylate, 2-hydroxy-
3-acryloyloxypropyl (meth) acrylate, epichlorohydrin-modified ethylene glycol di (meth) acrylate, epichlorohydrin-modified 1,6-hexanediol di (meth) acrylate, epichlorohydrin-modified propylene glycol di (meth) ) Those having a hydroxyl group such as acrylate, triglycerol di (meth) acrylate, epichlorohydrin-modified glycerol tri (meth) acrylate, epichlorohydrin-modified trimethylol tri (meth) acrylate,

Diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, nonaethylene glycol mono (meth) acrylate, tetradecaethylene glycol mono (meth) acrylate, trieicosa Ethylene glycol mono (meta)
Acrylate, polyethylene glycol mono (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth)
Acrylate, methoxytetraethylene glycol (meth) acrylate, methoxynonaethylene glycol (meth) acrylate, methoxytetradecaethylene glycol (meth) acrylate, methoxytrieicosa ethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxy Diethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate,
Phenoxyhexaethylene glycol (meth) acrylate, phenoxynonaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth)
Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate,
Tetradeca ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
Those having a polyethylene glycol structural unit such as ethylene oxide-modified bisphenol A di (meth) acrylate and polyethylene glycol-modified trimethylolpropane tri (meth) acrylate,

Methoxydipropylene glycol (meth)
Polypropylene glycol such as acrylate, tetrapropylene glycol mono (meth) acrylate, nonapropylene glycol mono (meth) acrylate, dodecapropylene glycol mono (meth) acrylate, tripropylene glycol diacrylate, polypropylene glycol modified trimethylolpropane tri (meth) acrylate Having structural units,

2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hexahydrohydrogen phthalate, (meth) acrylic acid dimer, ω-carboxycaprolactone mono Those having a carboxyl group such as (meth) acrylate and 2- (meth) acryloyloxyethylsuccinic acid,

N, N-dimethylaminoethyl (meth) acrylate, trimethylaminoethyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, (meth) acryloylmorpholine, etc.,
Having an amino group or an amide group,

Further, a urethane oligomer (meth) acrylate, an epoxy oligomer (meth) acrylate,
Oligomers such as bisphenol A-containing (meth) acrylates containing hydrophilic groups such as hydroxyl groups, polyethylene glycol chains, polypropylene glycol chains, carboxyl groups, amino groups, amide groups, etc.

Among them, (meth) acrylic monomers and / or oligomers having a hydroxyl group and / or a polyethylene glycol structural unit as a hydrophilic structural part are preferred. These monomers and / or oligomers having a hydrophilic structure portion may be used alone or in combination.

The polymerizable resin composition (I) used in the present invention contains the above-mentioned fluorine-containing polymerizable monomer and / or oligomer for the purpose of adjusting strength, elongation, rigidity and the like of the molded product, if necessary. Other polymerizable monomers and / or oligomers (C) other than (A) and the polymerizable monomer and / or oligomer (B) having a hydrophilic structure portion can be contained.

The type of other polymerizable monomer and / or oligomer (C) used as required is not particularly limited, but the above-mentioned fluorine-containing polymerizable monomer and / or oligomer (A) and hydrophilic structural moiety are used. Those which are compatible with the polymerizable monomer and / or oligomer (B) having OH are usually used, and other vinyl monomers and / or oligomers other than these (A) and (B) are usually used.

Examples of the above-mentioned other vinyl monomers include ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth). ) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, phenyl cellosolve (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate,
Dicyclopentenyloxyethyl (meth) acrylate,
Monofunctional monomers such as vinyl methacrylate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, vinyl crotonate, vinyl 2-ethylhexanoate, and styrene,

1,6-hexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,2'-bis (4- (meth) acryloyloxy polypropyleneoxyphenyl) Bifunctional monomers such as propane, dicyclopentanyl di (meth) acrylate, phenylglycidyl ether acrylate tolylene diisocyanate and divinyl adipate,

Trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tris [(meth) acryloxyethyl] isocyanate, pentaerythritol tri (meth) acrylate
Trifunctional monomer such as G

Tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate and glycerin di (meth) acrylate hexamethylene diisocyanate, dipentaerythritol monohydroxypenta (meth) acrylate. And pentafunctional monomers such as dipentaerythritol hexa (meth) acrylate, and the like.

Other vinyl oligomers include, for example, those having a weight average molecular weight of 500 to 50,000, which can be polymerized by irradiation with energy rays or heating, and specifically, bisphenol A-diepoxy- (meth). Acrylic acid adducts, (meth) acrylic acid ester of epoxy resin, (meth) acrylic acid ester of polyether resin, (meth) acrylic acid ester of polybutadiene resin, polyurethane resin having (meth) acrylic group at the molecular end, etc. Can be mentioned.

These other polymerizable monomers and / or oligomers (C) may be used alone or as a mixture, for example, the oligomers may be mixed and used, or the monomer and the oligomer may be mixed. Can also be used.

The fluorine-containing polymerizable monomer and / or oligomer (A) contained in the polymerizable resin composition (I) used in the present invention, and the polymerizable monomer and / or oligomer (B) having a hydrophilic structure portion. In addition, the amount of the other polymerizable monomer and / or oligomer (C) used, if necessary, depends on the required degree of surface hydrophobicity, (A), (B), and if necessary. The content of (A) in all the monomer and / or oligomer components contained in the polymerizable resin composition (I) is 0.01 to 10% by weight, which varies depending on the type of each component of (C). On the other hand, the total content of (B) and (C), which is optionally used, is appropriately selected within the range of 99.99 to 90% by weight. Above all, a molded product having an excellent balance of required surface properties of the molded product, such as water repellency, stain resistance, solvent resistance, and peelability, and physical properties of the entire molded product, such as strength and rigidity, can be obtained. Therefore, the content of (A) in all the monomer and / or oligomer components is 0.03 to 5% by weight, and the ratio (B / A) of (B) to (A) is 15 to 2500 times by weight. The range is preferably 0.03 to 3% by weight, and the range in which the ratio (B / A) of (B) to (A) is 20 to 2000 times by weight is particularly preferable. In addition, other polymerizable monomers and /
Alternatively, the amount of the oligomer (C) used is such that the content of (C) in all the monomers and / or oligomer components is 0 to 9
The range of 0% by weight is preferable.

The polymerizable resin composition (I) used in the present invention includes (A) and (B) contained therein.
And a part or all of all the monomer and / or oligomer components consisting of (C) and optionally used (C) are polyfunctional monomers and / or oligomers,
Crosslinking by polymerization curing gives a molded article with excellent physical properties such as heat resistance, weather resistance, abrasion resistance, and chemical resistance, and the introduction of a crosslinked structure makes it more difficult for fluorine atoms on the surface to dissociate, resulting in surface hydrophobicity. It is preferable because the durability of is improved.
The content of the polyfunctional monomer and / or oligomer contained in the total monomer and / or oligomer component varies depending on the required physical properties of the molded article and the durability of surface hydrophobicity, but is usually 5 to 100. % By weight,
Above all, 60 to 99.95% by weight is preferable because a molded product excellent in physical properties and surface hydrophobicity can be obtained. Examples of the polyfunctional monomer and / or oligomer used here include (A), (B) and (C) described above.
Of these, those having two or more functional groups can be used, but normally, a monomer and / or an oligomer having two to six functional groups is appropriately selected.

In the polymerizable resin composition (I) used in the present invention, other compounds other than the polymerizable monomers and / or oligomers (C) other than the above (A) and (B), if necessary, For example, a non-polymerizable resin, a surfactant, a polymerization initiator, a sensitizer, an antioxidant, a lubricant, an antifungal agent, an anti-fouling agent, an inorganic filler, a coloring agent, a fiber and the like can be contained. Also, the polymerizable resin composition (I) can be used by impregnating fibers or the like.

To produce a surface-hydrophobic molded article using the above-mentioned polymerizable resin composition (I), the polymerizable resin composition (I) is used.
After being shaped into a desired shape, it may be polymerized and cured by various curing means.

The method for shaping the polymerizable resin composition (I) is not limited, but for shaping into a film, for example, a method of coating or casting the polymerizable resin composition (I) on a substrate or slits. The method of extruding from, to shape into a fibrous shape,
For example, a method of extruding the polymerizable resin composition (I) from a nozzle and the like can be exemplified by a method of dropping the polymerizable resin composition (I) from a nozzle and a method of spraying the particle. Furthermore, a method of impregnating a pre-shaped impregnable substrate with the polymerizable resin composition (I), or a substrate such as fibers is impregnated with the polymerizable resin composition (I) and then mechanically shaped. The method or the like may be used. When the viscosity of the polymerizable resin composition (I) is high, after adding a solvent to reduce the viscosity,
It is also possible to remove the solvent by shaping and then heating.

When the shaped polymerizable resin composition (I) is shaped and then left to stand, the concentration of fluorine atoms on the surface of the shaped polymerizable resin composition (I) increases, and The surface segregation ratio is improved, which is preferable. For example, photoelectron spectroscopy (ES) by X-ray excitation on the surface after polymerization and curing.
The percentage of the number of fluorine atoms in the total number of atoms measured by CA) is 3% or more, preferably 5% or more, particularly preferably 5 to 70%, and the surface segregation ratio of fluorine atoms is 3. It is left to stand 5 times or more, preferably 10 to 2000 times, particularly preferably 10 to 1500 times. The standing time is usually 10 seconds to 1 hour, preferably 20 to 20 at room temperature.
5 to 180 seconds under heating at 40 to 150 ° C. (however, less than the boiling point of each component contained in the polymerizable resin composition (I))
120 seconds.

There is no limitation on the method for polymerizing and curing the shaped polymerizable resin composition (I), but a method for polymerizing and curing by irradiating with energy rays and / or heating is usually employed. Therefore, the energy ray curable resin composition is used as the polymerizable resin composition (I),
A method of polymerizing and curing by irradiation with energy rays is preferable. The energy ray curable resin composition used here is preferably an ultraviolet curable resin composition, and the ultraviolet curable resin composition contains an ultraviolet polymerization initiator or a photosensitizer in order to accelerate the polymerization and curing rate. Is preferably contained.

When the energy ray-curable resin composition is used as the polymerizable resin composition (I) and the polymerization and curing is effected by irradiation with energy rays and the polymerization and curing are inhibited by oxygen, for example, a shaped ultraviolet-curable resin is used. When the composition is irradiated with ultraviolet rays, irradiation with energy rays is preferably performed in an atmosphere of an inert gas such as nitrogen, carbon dioxide, or argon, because the polymerization and curing rate can be accelerated, and further, the polymerizable resin composition ( It is also preferable to accelerate the polymerization and curing rate by removing oxygen dissolved in I).

Further, the molded product after being polymerized and cured by irradiation with energy rays can be further heat-treated. By heat treatment, removal of unreacted monomer, curing, and dimensional stability can be achieved.

Examples of the energy rays used for polymerization and curing of the shaped polymerizable resin composition (I) include electron beams, γ rays, X rays, ultraviolet rays and visible rays. Ultraviolet rays are most preferable because of easy handling. The intensity of ultraviolet rays to be irradiated is 10 to 5000 m
W / cm ² is preferable, and the exposure time is about 0.01 to 180 seconds. An electron beam is also a preferable energy beam, is not affected by the presence or absence of an additive for the polymerization curability, and a polymerization initiator is unnecessary. Therefore, it is particularly preferable when the residual polymerization initiator is a problem.

The surface-hydrophobic molded article obtained as described above is a molded article containing the same fluorine-containing polymerizable monomer unit and / or oligomer unit as the constitutional unit of the polymerizing and curing resin on the surface and inside thereof. Content of the fluorine-containing polymerizable monomer unit and / or oligomer unit continuously changes from the surface to the inside, and the content of the fluorine-containing polymerizable monomer unit and / or oligomer unit on the surface Is a polymerized and cured resin molded product having a higher level than the inside.

Among these surface-hydrophobic moldings, polymerization-curing resin moldings having a component gradient structure in which the content of fluorine-containing polymerizable monomer units and / or oligomer units continuously changes from the surface toward the inside Yes, the percentage of the number of fluorine atoms in the total number of fluorine atoms measured by photoelectron spectroscopy (ESCA) by X-ray excitation on the surface [(the number of fluorine atoms on the surface of the molded product / the total number of atoms on the surface of the molded product) X100 (%)] is 5% or more, and the surface hydrophobic molded article of the present invention which satisfies the condition that the surface segregation ratio of fluorine atoms is 10 to 2000 times shows extremely excellent surface hydrophobicity, and Fluorine-containing polymerizable monomer and /
Alternatively, it is preferable because addition of the oligomer (A) causes less deterioration in physical properties and the effect that the fluorine atom is less likely to be released. Here, a vinyl-based copolymer containing a fluorine-containing vinyl monomer unit and / or an oligomer unit is preferable as the polymerization-curable resin constituting the molded product, and a fluorine-containing (meth) acrylic monomer unit and / or an oligomer unit is particularly preferable. The (meth) acrylic copolymer contained is preferable.

The method for producing the above-mentioned surface-hydrophobic molded article of the present invention is not particularly limited as long as it is a method capable of producing a molded article satisfying the above-mentioned conditions. The method for producing a surface-hydrophobic molded article of the invention, that is, a polymerization containing a fluorine-containing polymerizable monomer and / or oligomer (A) and a polymerizable monomer and / or oligomer (B) having a hydrophilic structural portion as essential components The method for producing the resin composition (I), polymerizing and curing the resin composition is such that the fluorine atom-containing polymerizable monomer and / or oligomer (A) can be used to determine the surface fluorine atom concentration and the degree of fluorine atom component inclination. And easily and widely adjusting the kind and content of the polymerizable monomer and / or oligomer (B) having a hydrophilic structural part by appropriate changes. Possible, preferable since the surface-hydrophobic molded product fluorine atom excellent have less component gradient structure inside many on the surface can be easily manufactured in a single step.

The component gradient structure of the surface-hydrophobic molded article of the present invention may be a component gradient structure in which the content of fluorine-containing polymerizable monomer units and / or oligomer units continuously changes from the surface toward the inside. For example, the content of the fluorine-containing polymerizable monomer unit and / or oligomer unit or the fluorine atom concentration may be gradually decreased from the surface to the inside, or may be rapidly decreased from a certain thickness. The content of fluorine-containing polymerizable monomer units and / or oligomer units or the distribution state of fluorine atom concentration in the entire thickness direction is not particularly limited.

Further, the state of containing fluorine atoms in the surface-hydrophobic molded article of the present invention is as described above, in the total number of fluorine atoms measured by X-ray excited photoelectron spectroscopy (ESCA) on the surface. The percentage of the number of the fluorine atoms is 5% or more, and the surface segregation ratio of fluorine atoms is 10 to 2
000 times, but in order to maintain good surface characteristics such as water repellency, stain resistance, and peelability, photoelectron spectroscopy (ESC) by X-ray excitation on the surface is preferable.
The percentage of the number of fluorine atoms in the total number of fluorine atoms measured in A) is preferably 5 to 70%, and the surface segregation ratio of fluorine atoms is 10 to 1500 times, particularly 10 to 10. It is preferably 1300 times. If the percentage of the number of fluorine atoms in the total number of fluorine atoms measured on the surface is less than 5% or the surface segregation ratio of fluorine atoms is less than 10, the surface hydrophobicity cannot be sufficiently exhibited. The ratio of the number of fluorine atoms to the total number of atoms on the surface and the upper limit of the surface segregation ratio of fluorine atoms are preferably higher in view of the characteristics of the molded product, but it is not possible to increase the surface segregation ratio of fluorine atoms to more than 2000 times. It's difficult.

Further, the surface-hydrophobic molded article of the present invention is made of a cross-linked polymer and has excellent physical properties such as heat resistance, weather resistance, abrasion resistance and chemical resistance, and fluorine atoms on the surface are released. It is preferable because it is difficult to do and has excellent durability of surface hydrophobicity. Degree of crosslinked structure (crosslink density)
Is not particularly limited, and may be appropriately selected in consideration of required physical properties of the molded product and durability of surface hydrophobicity. The method for introducing a crosslinked structure into the molded product is arbitrary, such as a post-crosslinking method after molding such as photocrosslinking or water crosslinking, or curing using a polyfunctional monomer and / or oligomer as a part or all of the polymerizable resin component. And the like. Among them, the crosslinking method at the time of curing is preferable from the viewpoint of improvement in molding speed and productivity. The polymerizable resin component used in the crosslinking method at the time of curing is, for example, all the monomer and / or oligomer components contained in the polymerizable resin composition (I) used in the method for producing a surface-hydrophobic molded article of the present invention. Then, the thing containing a polyfunctional monomer and / or oligomer as a part or all of it is mentioned. In this case, the method of adjusting the degree of introduction of the crosslinked structure includes a method of adjusting the addition ratio of the polyfunctional monomer and / or oligomer, and a method of using a monomer and / or oligomer having a higher functional number at the same addition ratio. .

The surface-hydrophobic molded article of the present invention may be in the form of a film, a fiber, a particle, or any other shape, with the film being preferred. The thickness of the film is not particularly limited, and may be a thin film shape or a thick plate shape. Further, the film may be applied to the substrate. The substrate may be flat or may have any other shape.

[0048]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited thereto.

Example 1 Octafluoropentyl acrylate (biscoat 8
F: 0.5 part of a fluorine-containing acrylic monomer manufactured by Osaka Organic Chemical Industry Co., Ltd., methoxynonaethylene glycol acrylate (NK-ester AM-90G: acrylic monomer having a polyethylene glycol structural unit manufactured by Shin Nakamura Chemical Co., Ltd.) -) 60 parts, dicyclopentanyl diacrylate (Kayarad R-684: acrylic monomer manufactured by Nippon Kayaku Co., Ltd.) 39.5 parts, and 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184 UV polymerization start manufactured by Ciba Geigy). 2 parts of the agent) were uniformly mixed to obtain a polymerizable resin composition (I-1).

The polymerizable resin composition (I-1) was applied to a glass plate with a film applicator so that the thickness was 120 μm.
And then leaving it under a nitrogen stream for 30 seconds, and then irradiating it with ultraviolet rays for 20 seconds with a 100 mW / cm ² ultraviolet lamp, peeling the obtained transparent film from the glass, and then removing the surface hydrophobic film (1 ) Got. Here, the side in contact with the nitrogen atmosphere is defined as the vapor phase side, and the side in contact with the glass (substrate) is defined as the substrate side (the same applies hereinafter).

Shimadzu X-ray photoelectron analyzer ESCA 850
Type [anode material of X-ray gun: magnesium, analyzer: blocking electric field type analyzer, energy resolution of analyzer: 1.15 eV (half width) at Ag3d5 / 2], and the angle (θ) between the film surface and the photoelectron detector: 15 °, 30
Surface hydrophobic film (1) obtained under the conditions of 90 ° and 90 °
Spectroscopy (ES) by X-ray excitation of gas phase side and substrate side of
CA) to perform elemental analysis to determine the percentage (X) of the number of fluorine atoms in the total number of atoms under each condition,
Further, from the composition of the polymerizable resin composition (I-1), the percentage (Y) of the number of fluorine atoms in the entire surface hydrophobic film (1) in the total number of atoms was calculated, and the surface segregation of fluorine atoms was calculated. The magnification (X / Y) was determined. The results are shown in Tables 1 and 2.

Example 2 Octafluoropentyl acrylate (biscoat 8
F) 0.5 part, methoxynonaethylene glycol acrylate (NK-ester AM-90G) 20 parts, dicyclopentanyl diacrylate (Kayarad R-684)
79.5 parts and 1-hydroxycyclohexyl phenyl ketone (Irgacure 184) 2 parts were uniformly mixed to obtain a polymerizable resin composition (I-2).

A surface hydrophobic film (2) was obtained in the same manner as in Example 1 except that the polymerizable resin composition (I-2) was used instead of the polymerizable resin composition (I-1).

The angle (θ) between the film surface and the photoelectron detector on the gas phase side of the obtained surface hydrophobic film (2): 15 °, 30 ° and 90 °, and on the substrate side, the film surface and the photoelectron. The percentage (X) of the ratio of the number of fluorine atoms in the total number of atoms was determined in the same manner as in Example 1 except that the elemental analysis was performed under the conditions of the detector angle (θ): 15 °. Further, the percentage (Y) of the ratio of the number of fluorine atoms in the total number of fluorine atoms in the entire surface hydrophobic film (2) and the surface segregation ratio (X / Y) of fluorine atoms were calculated. Tables 1 and 2 show the results.
Shown in

Example 3 Heptadecafluorodecyl acrylate (biscoat 1
7F: 0.5 part of a fluorine-containing acrylic monomer manufactured by Osaka Organic Chemical Industry Co., Ltd., 99.5 parts of phenoxydiethylene glycol acrylate (P-200A: acrylic monomer having a polyethylene glycol structural unit manufactured by Kyoeisha Chemical Co., Ltd.) and 1- 2 parts of hydroxycyclohexyl phenyl ketone (Irgacure 184) were uniformly mixed to obtain a polymerizable resin composition (I-3).

A surface was prepared in the same manner as in Example 1 except that the polymerizable resin composition (I-3) was used in place of the polymerizable resin composition (I-1) and the obtained film was not peeled from the substrate. A hydrophobic membrane (3) was obtained.

Only on the gas phase side of the obtained surface hydrophobic film (3), the angle between the film surface and the photoelectron detector (θ): 15 °,
In the same manner as in Example 1 except that the elemental analysis was performed under the conditions of 30 ° and 90 °, the percentage (X) of the number of fluorine atoms in the total number of atoms was determined, and the surface hydrophobic film ( 3) Percentage (Y) of the ratio of the total number of fluorine atoms to the total number of atoms, and the surface segregation ratio of fluorine atoms (X /
Y) was calculated. The results are shown in Tables 1 and 2.

Example 4 Heptadecafluorodecyl acrylate (biscoat 1
7F) 0.5 part, phenoxytetraethylene glycol acrylate (M-102: an acrylic monomer having a polyethylene glycol structural unit manufactured by Toagosei Co., Ltd.) 99.5 parts and 1-hydroxycyclohexyl phenyl ketone (Irgacure 184) 2 parts Were uniformly mixed to obtain a polymerizable resin composition (I-4).

A surface was prepared in the same manner as in Example 1 except that the polymerizable resin composition (I-4) was used in place of the polymerizable resin composition (I-1) and the obtained film was not peeled from the substrate. A hydrophobic membrane (4) was obtained.

Only on the gas phase side of the obtained surface hydrophobic film (4), the angle between the film surface and the photoelectron detector (θ): 15 °,
In the same manner as in Example 1 except that the elemental analysis was performed under the conditions of 30 ° and 90 °, the percentage (X) of the number of fluorine atoms in the total number of atoms was determined, and the surface hydrophobic film ( 4) Percentage (Y) of the total number of fluorine atoms in the total number of atoms and the surface segregation ratio of fluorine atoms (X /
Y) was calculated. The results are shown in Tables 1 and 2.

Example 5 Tetrafluoropropyl acrylate (biscoat 4
F: 0.1 part of a fluorine-containing acrylic monomer manufactured by Osaka Organic Chemical Industry Co., Ltd., ethylene oxide-modified bisphenol A diacrylate (New Frontier BPE-
4: acrylic acid monomer having a hydroxyl group manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) (99.9 parts) and 1-hydroxycyclohexyl phenyl ketone (Irgacure 184) (2 parts) were uniformly mixed to obtain a polymerizable resin composition (I-5). Got

A surface was prepared in the same manner as in Example 1 except that the polymerizable resin composition (I-5) was used in place of the polymerizable resin composition (I-1) and the obtained film was not peeled from the substrate. A hydrophobic membrane (5) was obtained.

Only on the gas phase side of the obtained surface hydrophobic film (5), the angle (θ) between the film surface and the photoelectron detector: 15 °,
In the same manner as in Example 1 except that the elemental analysis was performed under the conditions of 30 ° and 90 °, the percentage (X) of the number of fluorine atoms in the total number of atoms was determined, and the surface hydrophobic film ( 5) Percentage (Y) of the proportion of the total number of fluorine atoms in the total number of atoms and the surface segregation ratio of fluorine atoms (X /
Y) was calculated. The results are shown in Tables 1 and 2.

Next, the surface on the gas phase side of the surface hydrophobic film (5) was cut to a thickness of about 60 μm, and elemental analysis was carried out under the condition that the angle between this surface and the photoelectron detector (θ): 90 °. Otherwise in the same manner as in Example 1, except that the surface hydrophobic film (5) was used.
The percentage (x) of the ratio of the number of fluorine atoms in the inside of the total number of atoms was determined to be 0.5%, and the inside of the surface hydrophobic film (5) had very few fluorine atoms.

After immersing the surface hydrophobic film (5) in water at 25 ° C. for 1 week, the water contact angles of the surfaces of the gas phase side of the surface hydrophobic film (5) before and after the immersion were measured by Kyowa Scientific Co., Ltd. Manufactured by the droplet method CA-B type contact angle meter, and the elemental analysis was performed under the condition that the angle (θ) between the film surface and the photoelectron detector was 15 °, and the total number of fluorine atoms was calculated. The percentage (X) of the number occupied in the inside is calculated, and the surface hydrophobic film (5)
The percentage (Y) of the ratio of the total number of fluorine atoms to the total number of atoms and the surface segregation ratio (X / Y) of fluorine atoms were calculated. Table 3 shows the results.

Further, after the surface hydrophobic film (5) was left in a vacuum dryer at 250 ° C. for 8 hours to be heat-treated, the surface of the surface hydrophobic film (5) before and after the heat treatment was contacted with water. The angle was measured by using a droplet method CA-B type contact angle meter manufactured by Kyowa Kagaku Co., Ltd., and an elemental analysis was performed under the condition that the angle (θ) between the film surface and the photoelectron detector was 15 °, and fluorine was measured. The percentage (X) of the number of atoms in the total number of atoms is calculated, and the percentage of the number of fluorine atoms in the total number of fluorine atoms in the surface hydrophobic film (5) in the total number of atoms (Y), The surface segregation ratio (X / Y) of fluorine atoms was calculated. Table 3 shows the results.

Example 6 Heptadecafluorodecyl acrylate (biscoat 1
7F) 0.1 part, trifluoroethylmethacrylate (biscoat 3FM: a fluorine-containing methacrylic monomer manufactured by Osaka Organic Chemical Industry Co., Ltd.) 0.1 part, 2-hydroxy-3-phenoxypropyl acrylate (Aronix M-5700: Toagosei) Acrylic monomer having hydroxyl group manufactured by Ltd.) 99.8 parts and 1-hydroxycyclohexyl phenyl ketone (Irgacure 184)
Two parts were uniformly mixed to obtain a polymerizable resin composition (I-6).

A surface was prepared in the same manner as in Example 1 except that the polymerizable resin composition (I-6) was used in place of the polymerizable resin composition (I-1) and the obtained film was not peeled from the substrate. A hydrophobic membrane (6) was obtained.

Only on the gas phase side of the obtained surface hydrophobic film (6), the angle (θ) between the film surface and the photoelectron detector: 15 °,
In the same manner as in Example 1 except that the elemental analysis was performed under the conditions of 30 ° and 90 °, the percentage (X) of the number of fluorine atoms in the total number of atoms was determined, and the surface hydrophobic film ( 6) Percentage (Y) of the ratio of the total number of fluorine atoms in the total number of atoms and the surface segregation ratio of fluorine atoms (X /
Y) was calculated. The results are shown in Tables 1 and 2.

Example 7 Heptadecafluorodecyl acrylate (biscoat 1
7F) 0.1 part, epoxy acrylate (epoxy ester 70PA: Kyoeisha Chemical Co., Ltd. hydroxyl group-containing acrylic oligomer) 99.9 parts and 1-hydroxycyclohexyl phenyl ketone (IRGACURE 18)
4) 2 parts were mixed uniformly to give a polymerizable resin composition (I-7).
I got

A surface was prepared in the same manner as in Example 1 except that the polymerizable resin composition (I-7) was used in place of the polymerizable resin composition (I-1) and the obtained film was not peeled from the substrate. A hydrophobic membrane (7) was obtained.

On the gas phase side of the obtained surface hydrophobic film (7), the angle (θ) between the film surface and the photoelectron detector was 15 °, 30 ° and 90 °, and on the substrate side, the film surface and the photoelectron were detected. The percentage (X) of the ratio of the number of fluorine atoms in the total number of atoms was determined in the same manner as in Example 1 except that the elemental analysis was performed under the conditions of the detector angle (θ): 15 °. Further, the percentage (Y) of the number of fluorine atoms in the total number of fluorine atoms in the entire surface hydrophobic film (7) and the surface segregation ratio (X / Y) of fluorine atoms were calculated. Tables 1 and 2 show the results.
Shown in

Example 8 Heptadecafluorodecyl acrylate (biscoat 1
7F) 3 parts, 2-acryloyloxyethyl hydrogen phthalate (Aronix M-5400: an acrylic oligomer having a carboxyl group manufactured by Toagosei Co., Ltd.) 97.0 parts and 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184) 2 parts. The mixture was uniformly mixed to obtain a polymerizable resin composition (I-8).

The polymerizable resin composition (I-8) thus obtained was extruded into the air through a slit-shaped nozzle having a slit width of 0.5 mm and a length of 30 mm at a discharge rate of 30 ml / min. Was irradiated with ultraviolet rays from a 6 KW metal halide lamp using a condenser mirror to obtain a belt-shaped surface hydrophobic film (8). The thickness of the obtained strip-shaped surface hydrophobic film (8) was 0.3 mm.

The angle (θ) between the film surface and the photoelectron detector on only one side of the obtained strip-shaped surface hydrophobic film (8): 15
The percentage (X) of the ratio of the number of fluorine atoms to the total number of atoms was determined in the same manner as in Example 1 except that the elemental analysis was performed under the conditions of °, 30 ° and 90 °. The percentage (Y) of the number of fluorine atoms in the total number of fluorine atoms in the entire hydrophobic film (8) and the surface segregation ratio (X / Y) of fluorine atoms were calculated. The results are shown in Tables 1 and 2.

Example 9 Heptadecafluorodecyl acrylate (biscoat 1
7F) 0.5 part, epoxy acrylate (epoxy ester 80MFA: acrylic oligomer having hydroxyl group manufactured by Kyoeisha Chemical Co., Ltd.) 99.5 parts and 1-hydroxycyclohexyl phenyl ketone (IRGACURE 18)
4) 2 parts were mixed uniformly to give a polymerizable resin composition (I-9).
I got

The polymerizable resin composition (I-9) thus obtained was extruded into the air from a nozzle having a diameter of 0.5 mm at a discharge rate of 32 ml / min, and the range from 30 to 60 cm below the nozzle was 6 KW.
Ultraviolet rays were radiated from a metal halide lamp using a condenser mirror to obtain surface hydrophobic yarn (9). The diameter of the obtained surface hydrophobic yarn (9) was 0.3 mm.

Angles (θ) between the surface of the surface hydrophobic yarn (9) thus obtained and the photoelectron detector: 15 °, 30 ° and 90 °. ,
The percentage (X) of the ratio of the number of fluorine atoms in the total number of atoms is calculated, and the percentage (Y) of the ratio of the number of fluorine atoms in the total surface hydrophobic yarn (9) to the total number of atoms (Y) is calculated. The surface segregation ratio (X / Y) of fluorine atoms was calculated. The results are shown in Tables 1 and 2.

Comparative Example 1 35 parts of polyvinylidene fluoride (KF1000: manufactured by Kureha Chemical Industry Co., Ltd.), polymethylmethacrylate (PMM)
A) (65 parts) and 350 parts of N, N-dimethylacetamide (DMAc) as a solvent were uniformly mixed to obtain a polymerizable resin composition (I-1 ′).

The polymerizable resin composition (I-1 ') having a thickness of 250 μm was applied onto a glass plate by a film applicator.
m, and apply N, under conditions of 150 ° C and vacuum.
N-Dimethylacetamide (DMAc) was volatilized, and the obtained transparent film was peeled from the glass to obtain a surface hydrophobic film (1 ').

On the gas phase side and the substrate side of the obtained surface hydrophobic film (1 '), the conditions were such that the angle (θ) between the sample surface and the photoelectron detector was 15 °, except that elemental analysis was performed. In the same manner as in Example 1, the content ratio (X) of the number of fluorine atoms to the total number of atoms was determined, and the surface hydrophobic film (2 ')
Content of total number of fluorine atoms to total number of atoms (Y)
Then, the surface segregation ratio (X / Y) of fluorine atoms was calculated.
Table 2 shows the results.

Comparative Example 2 Heptadecafluorodecyl acrylate (biscoat 1
7F) 1 part, 99 parts nonylphenoxyethyl acrylate (Aronix M-111: acrylic monomer having no hydrophilic group manufactured by Toagosei Co., Ltd.) and 1-hydroxycyclohexyl phenyl ketone (IRGACURE 1
84) 2 parts are mixed uniformly, and the polymerizable resin composition (I-
2 ') was obtained.

In the same manner as in Example 1 except that the polymerizable resin composition (I-2 ′) was used in place of the polymerizable resin composition (I-1) and the obtained film was not peeled from the substrate. A surface hydrophobic membrane (2 ') was obtained.

On the gas phase side of the obtained surface hydrophobic film (2 '), the same procedure as in Example 1 was carried out except that the elemental analysis was carried out under the condition that the angle (θ) between the film surface and the photoelectron detector was 15 °. hand,
Calculate the content (X) of the number of fluorine atoms with respect to the total number of atoms,
Further, the content (Y) of the number of fluorine atoms in the entire surface hydrophobic film (2 ′) with respect to the total number of atoms and the surface segregation ratio (X / Y) of fluorine atoms were calculated. Table 2 shows the results.

Comparative Example 3 Octafluoropentyl acrylate (biscoat 8
F) 0.5 part, 99.5 parts of lauryl acrylate and 2 parts of 1-hydroxycyclohexyl phenyl ketone (Irgacure 184) were uniformly mixed to obtain a polymerizable resin composition (I-3 ′).

In the same manner as in Example 1 except that the polymerizable resin composition (I-3 ') was used instead of the polymerizable resin composition (I-1) and the obtained film was not peeled from the substrate. A surface hydrophobic membrane (3 ') was obtained.

On the gas phase side and the substrate side of the obtained surface hydrophobic film (3 '), the conditions were such that the angle (θ) between the sample surface and the photoelectron detector was 15 °, except that elemental analysis was performed. In the same manner as in Example 1, the content ratio (X) of the number of fluorine atoms to the total number of atoms was determined, and the surface hydrophobic film (3 ')
Content of total number of fluorine atoms to total number of atoms (Y)
Then, the surface segregation ratio (X / Y) of fluorine atoms was calculated.
Table 2 shows the results.

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

[Table 3]

[0091]

INDUSTRIAL APPLICABILITY According to the method for producing a surface-hydrophobic molded article of the present invention, it is possible to easily and widely adjust the surface fluorine atom concentration and the degree of the fluorine atom component gradient, and a large number of fluorine atoms are present on the surface. An excellent surface-hydrophobic molded product having a small component gradient structure inside and less likely to release fluorine atoms can be easily manufactured with high productivity in one step. In addition, this manufacturing method can easily introduce a crosslinked structure into the molded product, and thereby can improve the mechanical strength, heat resistance, chemical resistance and the like of the molded product. Further, the surface-hydrophobic molded article of the present invention is excellent in surface-hydrophobicity, but its physical properties are not significantly deteriorated, and fluorine atoms are hard to be released.

Claims (17)

[Claims] 1. A fluorine-containing polymerizable monomer and / or oligomer (A) and a polymerizable monomer and / or oligomer (B) having a hydrophilic structure portion as essential components, and all monomers and / or oligomers. The polymerizable resin composition (I) having a content of the fluorine-containing polymerizable monomer and / or oligomer (A) in the component of 0.01 to 10% by weight is shaped and then polymerized and cured. A method for producing a surface-hydrophobic molded article. 2. The content of fluorine-containing polymerizable monomer and / or oligomer (A) in all the monomer and / or oligomer components contained in the polymerizable resin composition (I) is 0.03 to 5% by weight, And a fluorine-containing polymerizable monomer and / or oligomer (A) of a polymerizable monomer and / or oligomer (B) having a hydrophilic structure part
The manufacturing method according to claim 1, wherein the magnification (B / A) is 15 to 2500 times by weight. 3. The polymerizable resin composition (I) comprises a fluorine-containing polymerizable monomer and / or oligomer (A), a polymerizable monomer and / or oligomer (B) having a hydrophilic structural portion, and other polymerization. A polymerizable monomer and / or oligomer (C) is contained.
Or the production method according to 2. 4. The method according to claim 1, 2 or 3, wherein an energy ray-curable resin composition is used as the polymerizable resin composition (I), which is shaped and then polymerized and cured by irradiation with energy rays. 5. The fluorine-containing polymerizable monomer and / or oligomer (A) is a fluorine-containing vinyl monomer and / or oligomer, and the polymerizable monomer and / or oligomer (B) having a hydrophilic structure portion is a hydrophilic structure portion. The method according to claim 1, 2, 3 or 4, which is a (meth) acrylic monomer and / or oligomer having 6. The method according to claim 5, wherein the fluorine-containing vinyl monomer and / or oligomer is a fluorine-containing (meth) acrylic monomer and / or oligomer. 7. The method according to claim 6, wherein the fluorine-containing (meth) acrylic monomer and / or oligomer is a fluorinated alkyl group-containing (meth) acrylate. 8. The (meth) acrylic monomer and / or oligomer having a hydrophilic structural portion is a (meth) acrylic monomer and / or oligomer having a hydroxyl group and / or a polyethylene glycol structural unit as a hydrophilic structural portion. The method according to claim 6, 6 or 7. 9. The polymerizable resin composition (I) contains a polyfunctional monomer and / or oligomer,
Polyfunctional monomer in all monomers and / or oligomer components contained in the polymerizable resin composition (I), and / or
Alternatively, the production method according to any one of claims 1 to 8, wherein the content of the oligomer is 5 to 100% by weight. 10. After the polymerizable resin composition (I) has been shaped, the number of fluorine atoms measured by X-ray excitation photoelectron spectroscopy (ESCA) on the surface after polymerization and curing is determined by the number of fluorine atoms in the total number of atoms. 10. The production method according to claim 1, wherein the percentage is 3% or more and the surface segregation ratio of fluorine atoms is 3.5 times or more, followed by polymerization and curing. 11. The polymerizable resin composition (I) is shaped into a film, and then polymerized and cured, to thereby form a film.
Manufacturing method described in. 12. A polymerized and cured resin molded product having a component gradient structure in which the content of fluorine-containing polymerizable monomer units and / or oligomer units continuously changes from the surface to the inside, and the surface is formed by X-ray excitation. A surface characterized by a percentage of the number of fluorine atoms in the total number of fluorine atoms measured by photoelectron spectroscopy (ESCA) of 5% or more, and a surface segregation ratio of fluorine atoms of 10 to 2000 times. Hydrophobic molding. 13. The percentage of the number of fluorine atoms in the total number of fluorine atoms measured by X-ray excitation photoelectron spectroscopy (ESCA) on the surface is 5 to 70%, and the surface segregation ratio of fluorine atoms is It is 10 to 1500 times.
The molded article according to 2. 14. The molded product according to claim 12, wherein the molded product is a molded product made of a vinyl-based copolymer. 15. The molded product according to claim 12 or 13, which is a molded product manufactured by the manufacturing method according to any one of claims 1 to 11. 16. The molded product according to claim 12, 13, 14 or 15, which is a molded product made of a crosslinked polymer. 17. The molded product according to claim 12, wherein the molded product is a film-shaped molded product.