JP3340461B2 - Ionizing radiation-curable metal alkoxide and method for forming cured coating film using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal alkoxide compound having an ionizing radiation-curable reactive group introduced therein, and a polycondensation method utilizing the sol-gel method using the compound.

[0002]

2. Description of the Related Art Starting from a solution of an organic or inorganic compound of a metal, the solution is converted into a sol in which fine particles of a metal oxide or a hydroxide or a hydroxide are dissolved by hydrolysis and polymerization of the compound in the solution. A method in which the reaction proceeds to form a gel and the resulting porous gel is heated to produce an amorphous, glass, polycrystalline, or ceramic material is called a sol-gel method.

The general conventional sol-gel method will be described more specifically. A metal alkoxide corresponding to a target oxide is selected, and a solvent is added to form a mixed solution. When the metal alkoxide is a solid, an alcohol is selected as a solvent to form a solution. Next, water necessary for hydrolysis and an acid (or ammonia) as a catalyst are added to an alcohol solution of the alkoxide to prepare a starting solution. Alkoxide
When the starting solution consisting of water-acid-alcohol is stirred at room temperature to 80 ° C. under reflux to carry out hydrolysis and polycondensation of the alkoxide, particles of metal oxide are formed, the solution becomes a sol, and the reaction proceeds. And the whole becomes a solidified gel. In the polycondensation process, by using a form such as a bulk gel, a gel fiber, or a coating gel film, products having different forms of the final product can be manufactured. When these wet gels are dried and slowly heated to an appropriate temperature, glass, polycrystalline ceramics and the like are formed.

In addition, instead of the above polycondensation method, there is also a sol-gel method in which polycondensation is carried out with ozone O ₃ generated by irradiating ultraviolet rays in the presence of oxygen. Conventionally, the coating film by the sol-gel method is a coating film having a chemical and mechanical protection function such as prevention of oxidation of a metal substrate, improvement of acid resistance, passivation of a semiconductor, and acid resistance of a glass substrate, and light reflection. It has been applied to optical function coating films such as prevention films and absorption films, and electromagnetic function coating films such as electric conductivity, ferroelectricity and magnetism.

[0005]

However, conventionally,
The sol-gel method that has been used for coating inorganic materials requires a dehydration or dealcoholization reaction during polycondensation, and thus these reactions have to be performed by heating. However, the strength of the coating film cannot be increased only by ordinary polymerization at the time of hydrolysis.
The treatment had to be performed at a high temperature of about 00 ° C.

The conventional sol-gel method of performing polycondensation with ozone O ₃ generated by irradiating ultraviolet rays in the presence of oxygen is as follows:
It has the advantage that it can be processed at room temperature, but has the problem that the curing speed is slow and it takes a long time. Therefore, an object of the present invention is to provide a method for performing polycondensation by a sol-gel method, which can be performed at room temperature in a short time without requiring heating.

[0007]

In order to solve the above problems, the present invention provides the following general formula (1)

[0008]

[Of 5]

(Where R ₁ is any alkyl group; R ₂
Is H or CH ₃ ; n + m is the valence of the metal, n ≠ 0, m ≠
0; L is an integer) . Further, the present invention provides the following general formula (2)

[0010]

[Omitted]

(Where R ₁ is any alkyl group; R ₂
Is H or CH ₃ ; n + m is the valence of the metal, n ≠ 0, m ≠
0) is an ionizing radiation-curable metal alkoxide. Further, the present invention provides the following general formula (1)

[0012]

[Omitted]

Or the following general formula (2)

[0014]

[Of 8]

( Wherein R ₁ , R ₂ , L , m, and n are the same as those described above) to produce a hydrolyzate by hydrolysis in the presence of an ionizing radiation-curable metal alkoxide. An article is coated on a substrate to form a coating film, and the coating film is irradiated with ionizing radiation to form a cured metal alkoxide coating film. Further, the present invention provides the following general formula (1)

[0016]

[Omitted]

Alternatively, the following general formula (2)

[0018]

[Of 10]

( Wherein R ₁ , R ₂ , L , m, and n are the same as those described above) to produce a hydrolyzate by hydrolysis in the presence of an ionizing radiation-curable metal alkoxide. An article is coated on a substrate to form a coating film, and the coating film is irradiated with ionizing radiation to form a cured metal alkoxide coating film. Further, the present invention provides the following general formula (1)

[0020]

[Of 11]

Or the following general formula (2)

[0022]

[Of 12]

( Wherein R ₁ , R ₂ , L , m, and n are the same as those described above) to produce a hydrolyzate by hydrolysis in the presence of an ionizing radiation-curable metal alkoxide. Add another ionizing radiation-curable resin to the product to form a coating composition, coat the coating composition on a substrate to form a coating film, and irradiate the coating film with ionizing radiation to form a metal alkoxide. It forms a cured coating film.

Hereinafter, the present invention will be described in more detail.

R ₁ in the above general formula is generally CH
₃ , C ₂ H ₅ , C ₃ H _{7 and the} like are used. In general, when R ₂ is H, the reactivity with ionizing radiation is high, and
In the case of H ₃ slightly lower. Production of Metal Alkoxide The metal alkoxide in the present invention is generally produced as follows.

[Step 1. ]: A step of hydrolyzing W (OR ₁ ) _{n + m} . This reaction is a method similar to the usual hydrolysis of an alkoxide, and is a reaction of the following general formula (3).

[0027]

[Of 13]

[Step 2. ]: Dehydration-condensation (dehydration condensation described below) or de-alcohol condensation (dealcoholization condensation described below) using W (OR ₁ ) _n (OH) _m produced by the reaction of the general formula (3). . Dehydration condensation: an acid catalyzed _{CH 2 CR 2 CO C L H} 2L OH or CH ₂ CR ₂ COOH, dehydration condensation W generated in reaction (OR _{1) n} (OH) _m in the general formula (3) .
This reaction is represented by the following general formula (4) or general formula (5).

[0029]

[Of 14]

[0030]

[Of 15]

De-alcohol condensation: acid catalyzed CH ₂ CR
₂ CO C _L H _2L OR or the and CH ₂ CR ₂ COOR one
General formula (3) W produced by the reaction of (OR _{1) n} (OH)
_m is stirred at about 100 ° C. for about 1 minute to carry out dealcoholization condensation. The following general formula is the reaction (6) or one
Represented by general formula (7).

[0032]

[Of 16]

[0033]

[Of 17]

As the solvent used in the present invention, generally, alcohols such as methanol, ethanol, propanol and butanol, other glycols such as ethylene glycol, ethylene oxide, triethanolamine and the like can be used. Hydrolysis of metal alkoxide The ionizing radiation-curable metal alkoxide of the present invention is hydrolyzed in the presence of water using an acid or alkali as a catalyst to produce a hydrolyzate. Acids include, for example, HCl
However, NH ₄ OH can be used as the alkali. When an acid catalyst is used, all of the substituents present on the metal may be hydrolyzed and polymerized, so that hydrolysis is performed in the presence of a basic catalyst to protect the ionizing radiation curing reactive group. It is desirable to carry out.

Formation of Coating Film The hydrolyzate is coated on a substrate by any coating method such as spin coating, dip coating, roll coating, and gravure coating. Other ionizing radiation-curable resins As the other ionizing radiation-curable resins used in addition to the ionizing radiation-curable metal alkoxide of the present invention, those generally known as ionizing radiation-curable resins can be used. The purpose of using other ionizing radiation-curable resins is
This is for imparting other properties to the coating film. For example, when a plastic film is used as the base material, N-vinylpyrrolidone can be added to improve the adhesion, and DPHA or the like can be added to increase the coating film hardness. The addition amount of other ionizing radiation-curable resins is
The amount is 30 parts by weight or less based on 100 parts by weight of the ionizing radiation-curable metal alkoxide of the present invention. The reason is 30
If the amount is more than part by weight, the obtained coating film is simply a hard coating film, and the performance of the metal is reduced. That is, it is not a coating film of the sol-gel method.

The ionizing radiation-curable resin includes an electron beam-curable resin and an ultraviolet-curable resin, and both components are almost the same except that the ultraviolet-curable resin contains a photopolymerization initiator and a sensitizer. . Ionizing radiation-curable resins generally contain, as a film-forming component, polymers, oligomers, monomers, etc. having radically polymerizable double bonds in the solution, and other non-reactive polymers as necessary. , An organic solvent, a wax and other additives.

The film-forming component used in the ionizing radiation-curable resin used in the present invention is preferably one having an acrylate-based functional group, for example, a relatively low molecular weight polyester resin, polyether resin, acrylic resin, or the like. (Meth) of polyfunctional compounds such as epoxy resin, urethane resin, alkyd resin, spiro acetal resin, polybutadiene resin, polythiol polyene resin and polyhydric alcohol
Oligomers or prepolymers such as acrylates and monofunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone and the like as reactive diluents and polyfunctional monomers such as trimethylolpropanetriene (Meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate,
Dipentaerythritol hexa (meth) acrylate,
It contains relatively large amounts of 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like.

In order to make the above-mentioned ionizing radiation-curable resin an ultraviolet-curable resin, a photopolymerization initiator may be used therein.
Using a mixture of acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester, tetramethylthiuram monosulfide, thioxanthone, and n-butylamine, triethylamine, tri-n-butylphosphine, etc. as a photosensitizer Can be. Particularly, in the present invention, polyester acrylate to which diallyl phthalate is added is preferable.

Irradiation with Ionizing Radiation The ionizing radiation-curable metal alkoxide and the ionizing radiation-curable resin can be cured by a usual curing method, that is, by irradiation with an electron beam or ultraviolet rays. For example, in the case of electron beam curing, Cockloft-Walton type, Bande graph type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, 50 to 1000 KeV emitted from various electron beam accelerators such as high frequency type, Preferably 10
An electron beam having an energy of 0 to 300 KeV is used. In the case of ultraviolet curing, ultraviolet rays emitted from light beams such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used.

The curing reaction by the irradiation of ionizing radiation is
It may be performed in the presence of nascent oxygen O. This nascent oxygen O is obtained by irradiating carbon dioxide or nitrogen dioxide with ionizing radiation as shown in the following formulas (8) and (9).
Can be generated.

[0041]

[Of 18]

[0042]

[Of 19]

The polycondensation method in the sol-gel method of the present invention can be carried out at room temperature and does not require heating.
A wide range of substrates such as plastic films, glass plates, metal plates and plastic sheets can be used as the substrate.

[0044]

EXAMPLE 1 W (OC ₂ H ₅ ) ₆ was added to a mixture of ethyl alcohol C ₂ H ₅ OH and water, and hydrolysis was carried out using ammonia as a catalyst to obtain W (OC ₂ H ₅ ) _n (OH) _{6. Get -n} . Next, methacrylic acid CH ₂ C (CH ₃ ) COOH was added, sulfuric acid was added, and the mixture was stirred at 100 ° C. for 1 minute to be dehydrated and condensed to obtain W (OC ₂ H ₅ ) _n (OCOCCH).
₃ CH ₂ ) _6-n is obtained.

Next, a polyester film was used as a substrate, and a hydrolyzate solution W (O
_{H) n (OCOCCH 3 CH 2} ) a _6-n upon drying 0.5g
/ M ² by gravure reverse coating. This coating film is dried at 80 ° C. for 1 minute. For the dried coating film, 1
The coating film was cured by irradiating an electron beam accelerated at 75 keV to 10 Mrad. Thus, an organometallic amorphous film containing tungsten W was obtained.

[0046]

EXAMPLE 2 Instead of methacrylic acid of Example 1, CH_Two
C (CH_Three) COCH_TwoSame as Example 1 except for using OH
W (OC_TwoH_Five)_n(OCH_TwoCOCCH_Three
CH _Two)_6-nI got

[0047]

Example 3 In the method of Example 1, hydrolysis was carried out.
W (OH)_n(OCOCCH_ThreeCH _Two)_6-nAfter getting
Dipentaerythritol hexa (meth) acrylate
10 parts by weight, 5 parts by weight of N-vinylpyrrolidone were added,
1g / m when dried on a 50μm thick PET film^TwoTona
Coating by gravure reverse coating method
did. This coating film is dried at 80 ° C. for 1 minute.
Apply 175 keV to the dried coating film.
Irradiating the accelerated electron beam to 10 Mrad
To cure the coating. In this way, the tongue
Thus, an organometallic amorphous film containing tungsten W was obtained.

[0048]

Example 4 In the method of Example 1, the hydrolyzate solution W (OH) _n (OC
The same procedure as in Example 1 was carried out except that the conditions of electron beam irradiation for the coating film of OCCH ₃ CH ₂ ) _6-n were as follows. That is, an electron beam accelerated at 300 keV was irradiated under a CO ₂ gas stream so as to have a concentration of 20 Mrad. In this way,
An organometallic amorphous film containing tungsten W was obtained.

[0049]

The method for forming a cured coating film by a sol-gel method using the novel ionizing radiation-curable metal alkoxide of the present invention requires heating since the curing reaction of the coating film is carried out by irradiation with ionizing radiation. At room temperature and in a short time
A polycondensation reaction by a gel method can be performed.

In the method for forming a cured coating film by the sol-gel method of the present invention, an arbitrary ionizing radiation-curable resin can be added. Various properties can be imparted, such as increasing the strength of the film. Further, the method for forming a cured coating film by the sol-gel method of the present invention allows the polycondensation reaction to be carried out more efficiently, in a short time and at room temperature by performing the curing reaction in the presence of oxygen O at the nascent stage. Can be.

──────────────────────────────────────────────────の Continuation of front page (51) Int.Cl. ⁷ identification code FI C09D 5/00 C09D 5/00 Z 185/00 185/00 (58) Field surveyed (Int.Cl. ⁷ , DB name) B05D 3/06 C07C 31/28 C07F 11/00 C08F 20/06 C09D 4/02 C09D 5/00 C09D 185/00 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] ( 1) The following general formula (1) : (However, R ₁ is any alkyl group; R ₂ is H or CH
₃ ; n + m is the valence of the metal, n ≠ 0, m ≠ 0; L is an integer)
An ionizing radiation-curable metal alloy characterized by the formula:
Coxide or the following general formula (2) : (However, R ₁ is any alkyl group; R ₂ is H or CH
₃ ; n + m is the valence of the metal and is represented by n ≠ 0, m ≠ 0)
Ionizing radiation-curable metal alkoxide characterized by the following:
And hydrolyzed in the presence of water to form a hydrolyzate, by coating (2) the hydrolyzate onto a substrate quotes
Ingu film is formed, the irradiation with ionizing radiation (3) the coating film
A method for forming a cured metal alkoxide coating film. (1) The following general formula (1) : (However, R ₁ is any alkyl group; R ₂ is H or CH
₃ ; n + m is the valence of the metal, n ≠ 0, m ≠ 0; L is an integer)
An ionizing radiation-curable metal alloy characterized by the formula:
Coxide or the following general formula (2) : (However, R ₁ is any alkyl group; R ₂ is H or CH
₃ ; n + m is the valence of the metal and is represented by n ≠ 0, m ≠ 0)
Ionizing radiation-curable metal alkoxide characterized by the following:
The addition is hydrolyzed in the presence of water to form a hydrolyzate, other ionizing radiation-curable resin (2) hydrolyzate
And (3) coating the coating composition on a substrate to form a coating composition.
Ingu film is formed, the irradiation with ionizing radiation (4) the coating film
A method for forming a cured metal alkoxide coating film. 3. Irradiation with ionizing radiation in the presence of nascent oxygen.
The metal alloy according to claim 1, wherein the metal alloy is irradiated.
A method for forming a cured coating film of coxide.