JP2016175981A - Organic-inorganic hybrid coating agent and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic-inorganic hybrid coating agent formed of a silica-based particle dispersion which is excellent in dispersion stability, exhibits high hydrophobicity and is surface-treated, and a polymer resin material; and a method for producing the same.SOLUTION: An organic-inorganic hybrid coating agent contains a silica-based particle dispersion (A) which is surface-treated with a trialkoxysilane compound having a (meth)acryloyl group and a trialkoxysilane compound having an alkyl group, a polyfunctional (meth)acrylate compound (B) having two or more (meth)acryloyl groups, and a polymerization initiator (C); and is produced by surface-treating the silica-based particle dispersion (A), adding and dispersing the polyfunctional (meth)acrylate compound (B) thereto, adding the polymerization initiator (C) thereto, and curing the resultant substance.SELECTED DRAWING: None

Description

  The present invention relates to an organic-inorganic hybrid coating agent obtained by mixing surface-treated silica-based particles and a polyfunctional (meth) acrylate compound, and a method for producing the same.

  Plastics are excellent in light weight, moldability, impact properties, etc., but lack the surface hardness and wear resistance and have the disadvantage of being easily damaged. Therefore, there is a demand for a hard coating method that imparts surface hardness and wear resistance to plastics.

  In order to solve the above problems, a method of applying, curing, and coating a material such as siloxane, (meth) acryl, urethane, or the like as a hard coating composition is used. Among them, siloxane materials are particularly excellent in terms of surface hardness and wear resistance, but are thermosetting and have problems with their productivity. On the other hand, for acrylic materials, improvements such as wear resistance by photocuring have been proposed (see, for example, Patent Document 1). However, the photo-curing acrylic resin composition has not yet fully satisfied the surface hardness and the wear resistance.

JP 2004-277512 A

  An object of the present invention is to provide a (meth) acrylic organic-inorganic hybrid coating agent capable of forming a film not only excellent in both surface hardness and wear resistance but also excellent in optical transparency, and a method for producing the same. It is in.

  The organic-inorganic hybrid coating agent of the present invention includes a silica-based particle dispersion (A) surface-treated with a trialkoxysilane compound having a (meth) acryloyl group and a trialkoxysilane compound having an alkyl group, and two or more A polyfunctional (meth) acrylate compound (B) having a (meth) acryloyl group and a polymerization initiator (C) are included.

In the silica-based particle dispersion (A), silica particles having an average particle diameter of 1 to 50 nm obtained by a wet method are dispersed in a hydrophilic organic solvent, and the general formula (1) (M) A _{- (CH 2) n-Si} (OR 1) 3 ( wherein, (M) a is a (meth) acryloyl group, _{R 1} is an alkyl group having 1 to 4 carbon atoms, n is 1 A trialkoxysilane compound having a (meth) acryloyl group represented by formula (2) R ₂ —Si (OR ₃ ) ₃ (wherein R ₂ has 10 or less carbon atoms). And R ₃ is an alkyl group having 1 to 4 carbon atoms) and a surface-treated with a silane coupling agent comprising a trialkoxysilane compound having an alkyl group represented by To do.

  In addition, the method for producing the organic-inorganic hybrid coating agent of the present invention includes a silane coupling agent comprising a trialkoxysilane compound having a (meth) acryloyl group and a trialkoxysilane compound having an alkyl group, and a dispersion in which silica particles are dispersed. A step of mixing a liquid to surface-treat the silica-based particle dispersion, and a step of adding and dispersing a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in the silica-based particle dispersion. And a step of adding a polymerization initiator to the mixture of the silica-based particle dispersion and the polyfunctional (meth) acrylate compound and curing the mixture.

The surface treatment of the silica-based particle dispersion includes a step of dispersing silica particles obtained by a wet method and having an average particle diameter of 1 to 50 nm in a hydrophilic organic solvent, and obtained by a wet method. and dispersion particles dispersed, the general formula _{(1) (M) A- (} CH 2) n-Si (OR 1) 3 ( wherein, (M) a is a (meth) acryloyl group, _{R 1} is A trialkoxysilane compound having a (meth) acryloyl group represented by an alkyl group having 1 to 4 carbon atoms and n is an integer of 1 to 4, and a general formula (2) R ₂ —Si (OR ₃ ) ₃ (wherein R ₂ is an alkyl group having 10 or less carbon atoms, and R ₃ is an alkyl group having 1 to 4 carbon atoms), and a trialkoxysilane compound having an alkyl group Coupling agent and silica Wherein the surface treatment of child dispersion.

  The organic-inorganic hybrid coating agent according to the present invention is sufficiently imparted with a reactive group on the surface of silica particles and hydrophobized, and can be dissolved in any ratio to a hydrophobic resin material. When added to a copolymerizable resin material and allowed to undergo a photo-curing reaction, an organic-inorganic hybrid material can be obtained, and since it is not heat-curing but photo-curing, it can be hardened without degrading plastic with low heat resistance. Coating is possible.

It shows below about the 1st process of the manufacturing method of the organic inorganic hybrid coating agent in connection with embodiment of this invention.
First, production of a surface-treated silica-based particle dispersion will be described below.
As the surface-treated silica-based particle dispersion of the present embodiment, a dispersion in which silica particles obtained by a wet method are dispersed in a hydrophilic organic solvent is used, and the general formula (1) (M) is used for this dispersion. A- _(CH 2) in _{n-Si (OR 1) 3} ( wherein, (M) a is a (meth) acryloyl group, _{R 1} is an alkyl group having 1 to 4 carbon atoms, n is And a compound having a (meth) acryloyl group represented by formula (2) R ₂ —Si (OR ₃ ) ₃ (wherein R ₂ is an alkyl having 10 or less carbon atoms). A surface treatment by simultaneously adding a silane coupling agent comprising a trialkoxysilane compound having an alkyl group represented by: R ₃ is an alkyl group having 1 to 4 carbon atoms, Manufactured.

The silica particles are shown below.
The silica particles subjected to the surface treatment have a predetermined nano-sized average particle diameter, specifically 1 to 50 nm, preferably 1 to 35 nm, and most preferably 5 to 25 nm. What is necessary is just to be obtained.

  In addition, those having a particle size smaller than the above range are difficult to produce and surface treatment with a silane coupling agent is difficult, and particles larger than the above range have a large scattering of visible light. When blended with a transparent resin, the transparency is lowered.

  Many methods such as a hydrolysis method, a neutralization method, an ion exchange method, and a precipitation method have been proposed and implemented as a wet method, but fine particles dispersed in a solvent are easily and relatively small in particle size. From the viewpoint that it can be obtained in a uniform form, it is most preferable to use a sol-gel method in which a silane compound is hydrolyzed and condensed.

The silane coupling agent is shown below.
As the surface treatment agent for the silica particles in the dispersion described above, a trialkoxysilane compound having a (meth) acryloyl group and a trialkoxysilane compound having an alkyl group are used. The former silane coupling agent is a (meth) acryloyl functional group having a copolymerizability with the monomer constituting the resin in that the compatibility with the active energy ray-curable resin composition is directly improved. And a hydrolyzable functional group that generates a group capable of reacting with a silanol group on the surface of silica particles. The latter is a compound having an alkyl group that is essentially a hydrophobic functional group and a hydrolyzable functional group that generates a group that can react with a silanol group on the surface of the silica particles similar to the former. Therefore, from the viewpoints of reactivity with the silica particle surface and compatibility with the active energy ray-curable resin composition and hydrophobicity, each molecule has one (meth) acryloyl group or alkyl group and is hydrolyzed. A silane compound having three functional groups is preferably used.

Formula _{(1) (M) A- (} CH 2) n-Si (OR 1) 3 ( wherein, (M) A is a (meth) acryloyl group, _{R 1} is 1 to 4 carbon atoms 3-acryloxypropyltrimethoxysilane or 3-methacryloxypropyltrimethoxysilane is preferably used as the compound having a (meth) acryloyl group represented by the following formula: n is an alkyl group, and n is an integer of 1 to 4. Used.

In general formula _{(2) R 2 -Si (OR} 3) 3 ( wherein, _{R 2} is an alkyl group having 10 or less carbon atoms, _{R 3} is an alkyl group having 1 to 4 carbon atoms) in Examples of the trialkoxysilane compound having an alkyl group include methyltrimethoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, and isooctyltri A methoxysilane, n-decyltrimethoxysilane, etc. can be mentioned, These can also be used individually by 1 type and can also be used in combination of 2 or more type.

  Further, a compound in which the methoxy group in the compound exemplified above is substituted with an ethoxy group (for example, 3-methacryloxypropyltriethoxysilane, methyltriethoxysilane, etc.) is also used as a hydrophobic silane coupling agent in the same manner as described above. It can be used suitably.

The surface treatment is shown below.
By mixing the silane coupling agent and the dispersion liquid in which the fine silica particles are dispersed, the surface treatment of the particles is performed. In general, it is recommended that the mixing be performed by dropping a silane coupling agent into a dispersion in which silica particles are dispersed.

Incidentally, the amount of the silane coupling agent used for the surface treatment is limited to the theoretical amount (g) for uniformly coating the fine silica particles with the silane coupling agent, and the following formula (3)
[Theoretical use amount of coupling agent] = A · B / C (3)
(In the formula, A is the weight (g) of the silica-based nanoparticles to be surface-treated, B is the specific surface area (m ² / g) of the nanoparticles, and C is the minimum coating of the coupling agent. Area (m ² / g)).

The minimum coating area C (m ² / g) of the above coupling agent is expressed by the following formula (4)
Minimum covering area C = (6.02 × 10 ²³ × 13 × 10 ⁻²⁰ ) / (Molecular weight of silane coupling agent)
... (4)
Sought by.

The surface-treated silica-based particle dispersion is shown below.
The surface-treated silica-based particle dispersion of the present embodiment has a very fine nano-order particle size, similar to the silica particles described above, and an average particle size of 1 to 50 nm as measured with an electron microscope. Preferably it is in the range of 1-35 nm, most preferably in the range of 5-25 nm, it is not agglomerated and the individual particles are coated with the silane coupling agent described above.

  In addition, since it exhibits high hydrophobicity and has a nano-order fine particle size and is not agglomerated, 2% by mass of particles in a mixed solvent of toluene and n-hexane having a weight ratio of 1: 1. In the containing dispersion, the visible light transmittance is 80% or more, particularly 85% or more, most preferably 90% or more, and the dispersion has high transparency.

It shows below about the 2nd process and the 3rd process of the manufacturing method of the organic inorganic hybrid coating agent of this embodiment.
The surface-treated silica-based particle dispersion of the present embodiment described above has a remarkably fine particle diameter, and hardly causes turbidity due to aggregation. It can be uniformly dispersed in the resin, which allows the adjustment of mechanical properties such as heat resistance (thermal expansion coefficient), surface hardness, and strength of the resin. Is uniformly dispersed without agglomeration, so that the excellent transparency is maintained.

  For example, in order to obtain an active energy ray-curable organic-inorganic hybrid coating agent containing the surface-treated silica-based particle dispersion (A) of the present embodiment, a compound having a polymerizable group such as a (meth) acryloyl group is used. A dispersion may be prepared. Moreover, in order to obtain hardened | cured material, it can be set as hardened | cured material by adding an active energy ray hardening | curing agent (polymerization initiator) to the said coating agent, and irradiating an active energy ray.

Examples of polyfunctional (meth) acrylates having two or more (meth) acryloyl groups used in the second step of this embodiment include, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate; Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) Examples thereof include acrylate, 1,6-hexamethylene glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and three or more (meth) acryloyl. Examples of polyfunctional (meth) acrylates having a group include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta Erythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, tetramethylol methane triacrylate, tetramethylol methane tetra Examples thereof include branched chain such as acrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, cyclic (meth) acrylates, urethane acrylates, etc., and polymers (oligomers, polymers) thereof. Can be made into one kind or a mixture of two or more kinds.
Moreover, although the following are mentioned as a radical photopolymerization initiator and a photocationic polymerization initiator used at the 3rd process of this embodiment, it is not limited to these.

  Examples of the photo radical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy- 2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2 , 4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butan-1-one, etc. Preferable since high coating the active energy ray curable resin composition is cured can be obtained. The amount used is not particularly limited, but is 0.05 to 20 masses per 100 parts by mass of the active energy ray-curable resin composition in order to maintain good sensitivity and prevent crystal precipitation, coating film property deterioration, and the like. It is preferable to use parts, particularly 1 to 10 parts by mass.

  Further, the cationic photopolymerization initiator includes a sulfonium salt type and an iodonium salt type. Examples thereof include diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, tri-p-tolylsulfonium trifluoromethanesulfonate, and tri-p. -Tolylsulfonium hexafluorophosphate, triphenylsulfonium tetrafluoroborate, 4-isopropyl-4'-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphate , Such as diphenyl iodonium trifluoromethane sulfonic acid. These may be used in combination of these one kind or two or more kinds. The addition amount is 20% by mass or less, preferably 1 to 5% by mass with respect to the acrylic resin.

  The resin composition obtained in the third step is applied to a substrate made of plastic or the like by a predetermined thickness using spin coating, spray coating, dip coating, bar coating, flow coating, etc., and then cured with active energy rays. As a result, the (meth) acrylolyl group is radically polymerized, and the surface-treated silica-based particles are also polymerized to form a three-dimensional crosslink, whereby organic-inorganic hybridization is performed. As a result, a coating having an effect of improving the surface hardness and scratch resistance having optical transparency can be performed. The substrate is coated, dried with a solvent, and irradiated with active energy rays to form a film by the above coating method. The film thickness at this time is 0.01 to 50 μm, preferably 0.05 to 10 μm. . In the active energy ray irradiation, an active energy ray emitted from a light source such as a mercury lamp, a xenon lamp, or a metal halide lamp is irradiated and cured to form a film. The active energy rays referred to here are those capable of photo radical polymerization such as ultraviolet rays and electron beams.

Examples Hereinafter, the present embodiment will be specifically described with reference to examples. However, the present embodiment is not limited to these examples.
In the following examples, various measurements were performed by the following methods.
The average particle diameter was obtained by analyzing data of 100 or more particles using a scanning image of a scanning electron microscope or a transmission electron microscope.

The surface-treated silica-based particles were dispersed in a mixed solvent of toluene and n-hexane having a mass ratio of 1: 1 so that the concentration as SiO 2 was 2% by mass. The dispersion was placed in a quartz cell having an optical path length of 1 cm and set in a spectrophotometer, and the transmittance at a wavelength of 593 nm was measured to obtain the visible light transmittance. An empty quartz cell having an optical path length of 1 cm was used as a reference cell.
As the surface characteristics of the cured film, the contact angle in 10 μl of water was measured using a contact angle meter.

It shows below about the 1st process of a present Example.
First, production of a surface-treated silica-based particle dispersion will be described below.
Example 1
As silica particles (B) produced by the sol-gel method, a commercially available silica dispersion (SiO ₂ concentration 30 mass%, average particle diameter 12 nm, particle density 2.0 g / cm ³ , maximum water content 3 mass%, isopropanol solvent) Was used. The theoretical amount used to uniformly coat 40 g of the silica particle dispersion (12 g as SiO 2) with a trialkoxysilyl-based silane coupling agent is calculated to be 0.0383 mol.

80 g of isopropanol and 40 g of toluene are added to 40 g of the silica dispersion, and 2.85 g (0.0115 mol) of 3-methacryloxypropyltrimethoxysilane and 3.65 g (0.0268 mol) of methyltrimethoxysilane are added with stirring. In addition, the mixture was heated to reflux for 24 hours or more. Then, the solvent was removed and concentrated with an evaporator to obtain 40 g of a toluene dispersion (30% by mass as SiO ₂ ).

  Next, using the above toluene dispersion, toluene, and n-hexane, the three solutions were mixed such that the mass ratio of toluene and n-hexane was 1: 1 and the SiO 2 concentration was 2%. As a result, a dispersion in which silica-based particles surface-treated at a concentration of 2% by mass in a 1: 1 (mass ratio) mixed solvent of toluene and n-hexane was prepared.

  The visible light transmittance of the dispersion was measured and found to be 96%. When the particles in the dispersion were observed with a transmission electron microscope, no coarse particles were observed, the particle shape was spherical, the average particle size was 12 nm, and the variation coefficient of the particle size was 10%. In particular, the average particle size was equivalent to the silica particles before the surface treatment.

Example 2
Example 1 except that 4.40 g (0.0268 mol) of n-propyltrimethoxysilane, which is a kind of trialkoxysilane having three alkoxy groups in the molecule, was used instead of methyltrimethoxysilane of Example 1. The surface treatment was performed in the same manner as described above.
As a result, the visible light transmittance was 93%.

Example 3
Similar to Example 1 except that 7.04 g (0.0268 mol) of decyltrimethoxysilane which is a kind of trialkoxysilane having three alkoxy groups in the molecule was used instead of methyltrimethoxysilane of Example 1. The surface treatment was performed.
As a result, the visible light transmittance was 90%.

Example 4
Surface treatment was carried out in the same manner as in Example 1 using 1.43 g (0.00575 mol) of 3-methacryloxypropyltrimethoxysilane and 4.43 g (0.0326 mol) of methyltrimethoxysilane as silane coupling agents. went.
As a result, the visible light transmittance was 96%.

It shows below about the 2nd process and 3rd process of a present Example.
Example 5
Using the surface-treated silica-based particle dispersion obtained in Example 1, a nanocomposite experiment was conducted.
An ultraviolet curable resin was prepared by mixing 20 g of pentaerythritol tetraacrylate and 0.2 g of a photopolymerization initiator.

  Using the toluene dispersion of the surface-treated silica-based particles obtained in Example 1, it was added to the ultraviolet curable resin so that the content of silica particles was 10% by weight, and sufficient To obtain an organic-inorganic hybrid coating agent containing silica-based particles. The coating agent was transparent.

  Next, the organic / inorganic hybrid coating agent was coated on a glass plate that had been washed with piranha cleaning solution and dried in air using a bar coater, and the resin was cured by irradiation with an 80 W high-pressure mercury lamp in a nitrogen atmosphere for 30 seconds. A membrane was obtained. The film was transparent, the water contact angle was 60 degrees, and the pencil hardness was 2H.

Example 6
Using the surface-treated silica-based particle dispersion obtained in Example 2, experiments on nanocomposites were conducted. In addition, the fluorine-containing acrylate was added to the ultraviolet curable resin of Experimental Example 5 as a polyfunctional acrylate.
An ultraviolet curable resin was prepared by mixing 1 g of a fluorine-containing acrylate, 20 g of pentaerythritol tetraacrylate, and 0.2 g of a photopolymerization initiator.

  Using the toluene dispersion of the surface-treated silica-based particles obtained in Example 2, it was added to the ultraviolet curable resin so that the content of silica particles was 30% by weight, and sufficient To obtain an organic-inorganic hybrid coating agent containing silica-based particles. The coating agent was transparent.

  Next, the organic / inorganic hybrid coating agent was coated on a polymethylmethacrylate resin plate washed with isopropanol and air-dried using a bar coater, and the resin was cured by irradiation with an 80 W high-pressure mercury lamp in a nitrogen atmosphere for 30 seconds. A coating film was obtained. The film was transparent, the water contact angle was 110 degrees, and the pencil hardness was 3H.

Comparative Example 1
A nanocomposite experiment was conducted in the same manner as in Example 5 except that a silica particle dispersion without surface treatment was used as the silica particles.
As a result, the above organic-inorganic hybrid coating agent was found to be markedly clouded, confirming that the silica particles were agglomerated. The cured film was not transparent and turbidity was observed.

  As described above, the organic-inorganic hybrid coating agent of this embodiment is a silica-based particle dispersion (A) surface-treated with a trialkoxysilane compound having a (meth) acryloyl group and a trialkoxysilane compound having an alkyl group. ), A polyfunctional (meth) acrylate compound (B) having two or more (meth) acryloyl groups, and a polymerization initiator (C).

The silica-based particle dispersion (A) is obtained by dispersing silica particles having an average particle diameter in the range of 1 to 50 nm obtained by a wet method in a hydrophilic organic solvent, and having the general formula (1) (M) A- (CH ₂ ) n—Si (OR ₁ ) ₃ (wherein (M) A is a (meth) acryloyl group, R ₁ is an alkyl group having 1 to 4 carbon atoms, and n is 1 to 1) A trialkoxysilane compound having a (meth) acryloyl group represented by the formula (2) R ₂ —Si (OR ₃ ) ₃ (wherein R ₂ has 10 or less carbon atoms) It is an alkyl group, and R ₃ is a surface-treated with a silane coupling agent comprising a trialkoxysilane compound having an alkyl group represented by a C 1-4 alkyl group.

  Moreover, the manufacturing method of the organic-inorganic hybrid coating agent of this embodiment has a silane coupling agent composed of a trialkoxysilane compound having a (meth) acryloyl group and a trialkoxysilane compound having an alkyl group, and silica particles dispersed therein. A step of mixing the dispersion with the surface treatment of the silica-based particle dispersion, and a step of adding and dispersing the polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in the silica-based particle dispersion. And a step of adding a polymerization initiator to a mixture of the silica-based particle dispersion and the polyfunctional (meth) acrylate compound and curing the mixture.

Further, the step of surface treating the silica-based particle dispersion includes a step of dispersing silica particles obtained by a wet method and having an average particle diameter of 1 to 50 nm in a hydrophilic organic solvent, and the silica particles obtained by a wet method the dispersion but being dispersed, the general formula _{(1) (M) A- (} CH 2) n-Si (OR 1) 3 ( wherein, (M) a is a (meth) acryloyl group, _{R 1} is carbon A trialkoxysilane compound having a (meth) acryloyl group represented by formula (2) R ₂ —Si (OR ₃ ) represented by formula (2), an alkyl group having 1 to 4 and n being an integer of 1 to 4. ₃ (wherein R ₂ is an alkyl group having 10 or less carbon atoms, and R ₃ is an alkyl group having 1 to 4 carbon atoms), and a trialkoxysilane compound having an alkyl group Silica-based particles mixed with a ring agent Chikarada surface-treating.

  The organic-inorganic hybrid coating agent according to the present embodiment is sufficiently imparted with a reactive group on the surface of the silica particles and made hydrophobic, and can be dissolved in any ratio with respect to the hydrophobic resin material. When added to a copolymerizable resin material and allowed to undergo a photo-curing reaction, an organic-inorganic hybrid material can be obtained, and since it is not heat-curing but photo-curing, it does not degrade plastics with low heat resistance. Hard coating is possible.

As described above, an organic-inorganic hybrid coating agent formed of a surface-treated silica-based particle dispersion having excellent dispersion stability and high hydrophobicity and a polymer resin material and a method for producing the same can be provided.

Claims (4)

A silica-based particle dispersion (A) surface-treated with a trialkoxysilane compound having a (meth) acryloyl group and a trialkoxysilane compound having an alkyl group;
A polyfunctional (meth) acrylate compound (B) having two or more (meth) acryloyl groups;
An organic-inorganic hybrid coating agent comprising a polymerization initiator (C). The silica-based particle dispersion (A) is obtained by dispersing silica particles having an average particle diameter in the range of 1 to 50 nm obtained by a wet method in a hydrophilic organic solvent,
Formula _{(1) (M) A- (} CH 2) n-Si (OR 1) 3 ( wherein, (M) A is a (meth) acryloyl group, _{R 1} is 1 to 4 carbon atoms A trialkoxysilane compound having a (meth) acryloyl group represented by formula (2) R ₂ —Si (OR ₃ ) ₃ (wherein n is an integer of 1 to 4). , R ₂ is an alkyl group having 10 or less carbon atoms, and R ₃ is an alkyl group having 1 to 4 carbon atoms), and a trialkoxysilane compound having an alkyl group represented by The organic-inorganic hybrid coating agent according to claim 1, which has been surface-treated with. A silica-based particle dispersion is surface-treated by mixing a silane coupling agent comprising a trialkoxysilane compound having a (meth) acryloyl group and a trialkoxysilane compound having an alkyl group and a dispersion in which silica particles are dispersed. Process,
Adding and dispersing a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in the silica-based particle dispersion;
And a step of adding a polymerization initiator to the mixture of the silica-based particle dispersion and the polyfunctional (meth) acrylate compound and curing the mixture, and a method for producing an organic-inorganic hybrid coating agent. The step of surface-treating the silica-based particle dispersion includes a step of dispersing silica particles obtained by a wet method and having an average particle diameter of 1 to 50 nm in a hydrophilic organic solvent,
A dispersion in which silica particles obtained by a wet method are dispersed, and a general formula (1) (M) A- (CH ₂ ) n-Si (OR ₁ ) ₃ (wherein (M) A is a (meth) acryloyl group. And R ₁ is an alkyl group having 1 to 4 carbon atoms and n is an integer of 1 to 4), and a trialkoxysilane compound having a (meth) acryloyl group represented by the general formula (2) R Trialkoxysilane having an alkyl group represented by _2- Si (OR ₃ ) ₃ (wherein R ₂ is an alkyl group having 10 or less carbon atoms, and R ₃ is an alkyl group having 1 to 4 carbon atoms). The method for producing an organic-inorganic hybrid coating agent according to claim 3, wherein the silica particle dispersion is surface-treated by mixing a compound and a silane coupling agent comprising the compound.