JPH107986A - Stain-proofing agent and stain-proof article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a stain-proofing agent having high stain-proofing performances, being easily amenable to stain removal and having permanent effect by using a copolymer comprising a specified polydimethylsiloxane compound, a polymerizable silane compound and a polymerizable compound having a double bond as the principal component. SOLUTION: This agent consists mainly of a copolymer comprising 2-50wt.% (meth)acryloyl-containing polydimethylsiloxane compound (A) represented by formula I (wherein R<1> is H or a 1-10C aliphatic hydrocarbon group; a is 1-5; and b is 10-500), 2-30wt.% polymerizable silane compound (B) being copolymerizable with A and represented by formula II [wherein R<2> is vinyl or (meth)acryloylalkyl; R<3> is a hydrolyzable group; R<4> is H or an inert monovalent organic group; and n is 0-2] and 20-96wt.% double-bond-containing polymerizable compound (C) being copolymerizable with A and B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used for surface treatment of an inorganic material such as glass, ceramic, metal or the like, or a resin material having a layer containing an inorganic compound formed on a surface thereof, and to provide excellent antifouling property. Antifouling agent and antifouling article.

[0002]

2. Description of the Related Art Inorganic materials such as glass, ceramics, and metals have been applied to various fields such as building materials by utilizing their mechanical strength and appearance, particularly transparency of glass. However, various stains adhere to such materials over a long period of use. For example, the appearance of window glass and the like deteriorates due to rain, mud, dirt in the air due to dust and the adhesion of dust. Also, in the case of a show window or the like, there is often a case where a person comes into contact with it and stains, sweat, cosmetics and the like adhere thereto, thereby impairing the beautiful appearance.

[0003] Therefore, many methods have been proposed for modifying the surface properties, particularly the hydrophilic surface, to be hydrophobic by treating the surface with various surface treatment agents. For example, JP-A-6-184527 proposes a treating agent comprising a fluoroalkylsilane compound, a long-chain aliphatic silane compound and a silicon isocyanate compound. JP-A-6-256756 proposes a treating agent comprising a fluoroalkylsilane compound and a methylpolysiloxane containing a Si-H group.

[0004] On the other hand, resin materials are used in many fields, but there is a problem of adhesion of dirt like glass. In particular, optical components such as spectacle lenses and anti-reflection filters have anti-reflection treatment on their surfaces,
Hand stains, fingerprints, sweat, cosmetics, and the like attached during use by humans are very conspicuous and difficult to remove. Therefore, in order to make it difficult to attach dirt or to easily wipe off dirt, a device for further providing an antifouling layer on the surface of the antireflection film has been devised. For example, Japanese Patent Application Laid-Open No. 64-86101 discloses an antireflection film mainly composed of silicon dioxide or the like provided on the surface of a base material, and further, the surface thereof is treated with a compound containing an organic silicon substituent to prevent contamination and resistance. Scratched antireflective articles have been proposed. Japanese Patent Application Laid-Open No. 4-338901 proposes a stain-resistant and scratch-resistant CRT filter in which an anti-reflection film is similarly coated with an organic polysiloxane having a silanol group at a terminal.

[0005]

However, although the conventional antifouling agents have a certain effect, they are still not satisfactory. In particular, since it wipes vigorously to remove the adhered contaminants or by using water, an organic solvent, and a mixture thereof, a substance exhibiting stain resistance is easily removed, and the antifouling property is poor in permanence. In view of such circumstances, the present inventor has conducted intensive studies on an antifouling treatment agent which not only has higher contamination prevention properties but also is easy to remove contaminants and has a long-lasting effect. As a result, the (meth) acryloyl group A polydimethylsiloxane compound, a polymerizable silane compound copolymerizable therewith, and a treating agent containing a copolymer obtained by polymerizing the polymerizable compound copolymerizable therewith impart excellent antifouling properties And found that it is durable, and completed the present invention.

[0006]

That is, the present invention provides a polydimethylsiloxane compound (A) containing a (meth) acryloyl group represented by the following general formula (3):

Embedded image (In the formula, R ¹ represents a hydrogen atom or a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms, a represents an integer of 1 to 5, and b represents an integer of 10 to 500.) 4, a polymerizable silane compound (B) copolymerizable with the polydimethylsiloxane compound,

Embedded image (Wherein, R ² is a vinyl group or a (meth) acryloylalkyl group, R ³ is a hydrolyzable group, R ⁴ is a hydrogen atom or an inert monovalent organic group, and n represents an integer of 0 to 2. ) And an antifouling agent containing, as a main component, a copolymer of a silane compound represented by Formula 3 or 4 and a polymerizable compound (C) having a double bond capable of copolymerization. An antifouling article formed by applying a coating on the surface of a material.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polydimethylsiloxane compound containing a (meth) acryloyl group represented by the general formula 3 is for imparting an excellent antifouling function. R ¹ in the formula is a hydrogen atom or a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group. The polydimethylsiloxane compound containing this (meth) acryloyl group is 2 to 50 wt% in the copolymer.
%, Preferably 5 to 40 wt%. If it is less than 2 wt%, no sufficient antifouling effect is exhibited. Also 50wt%
If it exists in a larger amount, it becomes a gel-like compound, which is not preferable in applying the compound to a substrate.

[0008] The polymerizable silane compound having a group represented by the above general formula (4) is used to form a strong bond with the substrate to form an antifouling layer on the substrate with high durability. . R ² in the formula is a vinyl group or a (meth) acryloylalkyl group. Examples of the (meth) acryloylalkyl group include a (meth) acryloylethyl group, a (meth) acryloylpropyl group, and a (meth) acryloylbutyl group. Although a (meth) acryloylpropyl group is preferably used. Examples of the hydrolyzable group of R ^{3 in} the formula include a halogen atom, —OR ⁵ , and —OCO.
^{R 5, -OC (R 5)} = C (R 6) 2, -ON = C (R
⁵ ) ₂ , -ON = CR ⁷ is preferred. (Where R ⁵ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R ⁶ is a hydrogen atom or a lower aliphatic hydrocarbon group, and R ⁷ is a carbon atom having 3 to 6 carbon atoms.
Is a divalent aliphatic hydrocarbon group. ) More preferably, chlorine, -OCH _3, is -OC ₂ H _5. R ⁴ is a hydrogen atom or an inert monovalent organic group, and is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms.

As the polymerizable silane compound, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxymethylsilane, vinylmethoxydimethylsilane, γ- (meth) acryloylpropyltrimethoxysilane, γ- (meth) acryloyl Propyldimethoxymethylsilane and the like. This polymerizable silane compound accounts for 2 to 30 wt%, preferably 5 to 20 wt% in the copolymer. If the amount is less than 2 wt%, sufficient bonding with the base material cannot be obtained, resulting in poor durability. Also 30
The effect does not change even if it is more than wt%, which is not preferable in terms of cost.

The compound having a double bond copolymerizable with the above two silane compounds is not particularly limited, and examples thereof include an ethylenically unsaturated monomer.
Examples of the ethylenically unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, Monofunctional (meth) acrylates such as ethylhexyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate; unsaturated acids such as methacrylic acid and acrylic acid; styrene, α-
Examples include, but are not limited to, methylstyrene, acrylonitrile, methacrylonitrile, maleic anhydride, phenylmaleimide, cyclohexylmaleimide, and the like.

[0011] Further, ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate,
Polyfunctional (meth) such as neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetrapropylene glycol diacrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate
Aromatic polyfunctional compounds such as acrylates, divinylbenzene and diallyl phthalate may be contained.

Further, for the purpose of imparting high water repellency to the copolymer, an ethylenically unsaturated monomer containing a fluoroalkyl group may be contained. Examples of the ethylenically unsaturated monomer containing a fluoroalkyl group include, for example,
2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluoro Octyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl ( (Meth) acrylate, 2- (perfluoro-9-methyldecyl) ethyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-8-methyldecyl) ) -2-hydroxypropyl (meth) acrylate and the like.

The copolymerizable compound having a double bond is contained in the copolymer in an amount of 20 to 96% by weight. Also, a mixture of two or more kinds may be used.

The polymerization of the polymerizable compounds (A), (B) and (C) is carried out in the presence of a radical initiator by a general polymerization method such as a solution polymerization method, a suspension polymerization method and an emulsion polymerization method. It is done by law. Among them, the solution polymerization method is preferable because the produced copolymer solution can be used as it is as an antifouling treatment agent by diluting it with a solvent.

As radical initiators, peroxides such as benzoyl peroxide, acetyl peroxide, lauroyl peroxide, etc .; and azo compounds such as azobisisobutyronitrile, azobisdimethylvaleronitrile, azobismethylbutyronitrile, etc. And the like.

In the production of the polymer, mercaptans or the like can be used as a chain transfer agent in order to control the molecular weight.

The obtained copolymer is diluted with a solvent, if necessary, and used as an antifouling agent. As the solvent, for example, methanol, ethanol, 1-propanol, 2-
Alcohols such as propanol, 1-butanol and 2-butanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate and propyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene Compounds, hexane, heptane, aliphatic hydrocarbons such as cyclohexane, dichloromethane, chloroform, carbon tetrachloride, dichloroethane,
Examples include, but are not limited to, alkyl halides such as trichloroethane.

Various antifouling agents such as dilute hydrochloric acid aqueous solution, dilute sulfuric acid aqueous solution, phosphoric acid aqueous solution, fatty acid metal salt, metal alkoxide and the like are used to promote hydrolysis of the silane compound and stabilize the generated silanol groups. May be included.

The substrate to be used is not particularly limited, but inorganic materials and resin materials such as glass, ceramic and metal, among which glass and transparent resin materials are suitable for this application. As the transparent resin material, for example, acrylic resin,
Examples thereof include a polycarbonate resin, a polyester resin, a cellulose resin, and a styrene resin. Among them, acrylic resins are suitable from the viewpoints of light transmittance and weather resistance. In addition, optical films or sheets provided with polarization characteristics as these transparent substrates are also exemplified. Further, on a glass surface, a transparent resin, an optical film, a single layer of an inorganic compound, or a multi-layer anti-reflection layer is formed, on which a film is formed using the present anti-fouling agent, the present invention The effect is further exhibited. The shape of the substrate is not particularly limited, such as a film, a sheet, and a molded product.

As a method for forming an antifouling film on the surface of a substrate by using the antifouling agent, a usual coating method used industrially can be used. Examples of the coating method include spin coating, dip coating, roll coating, gravure coating, curtain flow coating, and the like. After application, it is necessary to perform drying at room temperature and / or heat to sufficiently perform a binding reaction with the substrate. Thus, an antifouling article is obtained.

The thickness of the antifouling coating can be selected depending on the substrate used, but is preferably 0.001 to 0.1 μm. 0.
If it is less than 001 μm, sufficient antifouling properties are not exhibited, and it is difficult to form a uniform film. If the thickness exceeds 0.1 μm, abrasion may occur, which is not preferable. When a transparent substrate having an antireflection layer formed of an inorganic compound is used as the substrate, the thickness of the antifouling film is 0.00
1 to 0.03 μm is preferred. If the thickness exceeds 0.03 μm, the antireflection effect is undesirably reduced.

[0022]

According to the antifouling agent of the present invention, the surface of an inorganic material or an organic material can be easily made water-repellent to impart antifouling performance. Above all, by forming a thin film of the present composition on an optical article having an anti-reflection film, it is possible to make fingerprints and other stains less sticky and less noticeable, and it is possible to easily remove attached stains. Therefore, the present invention can be applied to a VDT surface or a front panel of a CRT display, a projection television, a plasma display, or the like.

[0023]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. In the examples, various performance evaluation test methods are as follows. (1) Contact angle with water: Using a contact angle meter (CA-A type: Kyowa Interface Science Co., Ltd.), a water droplet having a diameter of 1.0 mm was formed at the needle tip at room temperature, and this was touched to the surface of the sample. Drops were made. The angle between the droplet and the surface generated at this time was measured and defined as the contact angle. (2) Durability: After wiping the surface of the sample 20 times with a cellulose nonwoven fabric (Bencott: manufactured by Asahi Kasei),
A durability test was performed by measuring the contact angle with water by the method described above. (3) Fingerprint adhesion: The right thumb was pressed against the surface of the sample for 3 seconds to attach the fingerprint, and the ease of sticking or standing out was visually determined. The criteria were as follows. ：: Fingerprint adhesion is small, and the attached fingerprint is inconspicuous. ×: Fingerprint adhesion can be clearly recognized. (4) Fingerprint wiping property: The attached fingerprint was wiped off with a cellulose nonwoven fabric, and the ease of removing the fingerprint was visually determined. The criteria were as follows. ：: The fingerprint can be completely wiped off. Δ: Fingerprint wiping remains. X: The trace of wiping off the fingerprint spreads, and it is difficult to remove it.

Reference Example (1) Substrate (I) Urethane acrylate hard coat agent (KOEI M-
101: Koei Chemical Co., Ltd.) is diluted so as to have a solid content of 40%, and a 50 × 100 × 0.25 mm impact-resistant acrylic film (Technoloy: manufactured by Sumitomo Chemical Co., Ltd.) is immersed in the diluted solution and 45 cm / min. Raised at the speed of. After evaporating the solvent, a hard coat layer was formed by irradiating a 120 W metal halide lamp (UB0451 manufactured by Eye Graphics Co., Ltd.) from a distance of 20 cm for 10 seconds. This hard coat layer was coated in order of silicon dioxide, titanium dioxide, silicon dioxide, titanium dioxide, and silicon dioxide by a vacuum deposition method to form a multilayer antireflection film. (2) Substrate (II) A glass plate of 50 × 100 × 1 mm was used as a substrate.

Examples 1 to 4 and Comparative Examples 1 to 2 The following formulas were used as polydimethylsiloxane compounds (A).
(Cyplane FM-0725, molecular weight: about 10,000, manufactured by Chisso Corporation),

Embedded image CH ₂ CC (CH ₃ ) COO (CH ₂ ) _3- (Si (CH ₃ ) ₂ O—) n-Si (CH ₃ ) _{3 As a} polymerizable silane compound (B), The compound shown (TSL-8370, manufactured by Toshiba Silicone Co., Ltd.),

Embedded image As a polymerizable compound (C) of the formula CH ₂ CC (CH ₃ ) COO (CH ₂ ) ₃ —Si (OCH ₃ ) ₃ (C-18) (M-1820, Daikin Chemicals sales ( Co., Ltd.) and / or methyl methacrylate (MMA),

Embedded image CH ₂ CC (CH ₃ ) COO (CH ₂ ) _2- (CF ₂ ) ₇ CF _{3 As} azobisisobutyronitrile (AIBN) as a polymerization initiator,
Toluene was mixed in an amount shown in Table 1 as an organic solvent, placed in a glass flask, and polymerized at 80 ° C. for 6 hours under a nitrogen stream.

1.6 g of the obtained copolymer solution was taken and mixed with a toluene / isopropyl alcohol mixed solvent (mixing ratio: 30).
/ 70) to obtain a solution of 0.2 wt%. 6 cc of 0.1N diluted hydrochloric acid aqueous solution is added to this solution.
The mixture was added and stirred at room temperature for 1 hour or more to obtain a solution of an antifouling agent. The substrate (I) and the substrate (II) prepared in the reference example were immersed in the solution of the antifouling agent, and were applied at a speed of 15 cm / min. After evaporating the solvent, 8
It was dried by heating at 0 ° C. for 1 hour. The substrate on which the obtained antifouling coating was formed was evaluated. The results are shown in Table 2.

[0027]

[Table 1] FM-0725: Polydimethylsiloxane compound (A) TSL-8370: Polymerizable silane compound (B) M-1820: Polymerizable compound (C) MMA: Polymerizable compound (C) (methyl methacrylate) AIBN: Azobisiso Butyronitrile

[0028]

[Table 2]

Claims (4)

[Claims] 1. A polydimethylsiloxane compound (A) containing a (meth) acryloyl group represented by the general formula: (In the formula, R ¹ represents a hydrogen atom or a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms, a represents an integer of 1 to 5, and b represents an integer of 10 to 500.) 2, a polymerizable silane compound (B) copolymerizable with the polydimethylsiloxane compound; (Wherein, R ² is a vinyl group or a (meth) acryloylalkyl group, R ³ is a hydrolyzable group, R ⁴ is a hydrogen atom or an inert monovalent organic group, and n represents an integer of 0 to 2. ) And a copolymer of a silane compound represented by the general formula 1 or 2 and a polymerizable compound (C) having a double bond copolymerizable therewith. 2. The copolymer has a polydimethylsiloxane compound (A) content of 2 to 50% by weight and a polymerizable silane compound content of 2 to 50% by weight.
The antifouling agent according to claim 1, wherein 30 wt% and the polymerizable compound (C) copolymerizable with these compounds are 20 to 96 wt%. 3. An antifouling article obtained by applying the antifouling agent according to claim 1 to the surface of a substrate and drying to form a film. 4. A single-layer or multi-layer antireflection film whose outermost layer made of an inorganic compound is silicon dioxide is formed on the surface of a transparent substrate, and the antifouling agent according to claim 1 is formed on the antireflection film. An antireflection filter formed by coating and forming a coating having a thickness of 0.001 to 0.03 μm.