JPH02251585A - Coating composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, consisting of a specific metal alkoxide hydrolyzate and hydrous aluminosilicate and capable of improving corrosion resistance of surfaces, such as plastic, wood and metal products, and simultaneously imparting functionality by application to the surfaces. CONSTITUTION:The objective composition containing (A) 100 pts.wt. hydrolyzate of a metal alkoxide expressed by the formula (M is metal, such as Si, Zr, Ti or Al; R' and R'' are 1 to 5C hydrocarbon; (n) is 1 to 4) and (B) 0.1 to 30 pts.wt. hydrous aluminosilicate with 5 to 50wt.% (preferably 15 to 25wt.%) moisture content. Furthermore, antimicrobial metal ions such as silver, copper, zinc or tin ions, are preferably contained in the component (B). The above-mentioned composition is capable of imparting functionality, such as electronic or electromagnetic, optical, thermal and biochemical function.

Description

Detailed Description of the Invention [Field of Industrial Application] This invention relates to a coating composition that is applied to the surfaces of plastic products, wood products, metal products, etc. to improve corrosion resistance and impart functionality. It is something.

[Conventional technology]

Several attempts have been made to coat the surfaces of plastic products, wood products, metal products, etc. with inorganic substances such as silicon oxide to improve their corrosion resistance against acids, alkalis, solvents, etc. (Japanese Patent Publication No. 51-2343, (Japanese Patent Publication No. 54-5860, etc.). These methods involve coexisting an organic acid as a hydrolyzing agent with an organosilicon compound and applying it to the surface. Hydrolysis of alkoxide is difficult to control, so it is difficult to control the desired film thickness, and it is easy to form a uniform film and increase resistance. It was difficult to strengthen the corrosive properties.

[Problem to be solved by the invention]

Conventionally, methods have been proposed to improve the corrosion resistance of plastic products, wood products, metal products, etc. that require corrosion resistance by applying metal oxides obtained by hydrolyzing metal alkoxides to the surfaces. ing. However, the hydrolysis conditions were unstable, the coating film was not uniform, and therefore the corrosion resistance was not sufficient.

Furthermore, no attempt has been made to impart functionality such as electromagnetic functionality, optical functionality, thermal functionality, or biochemical functionality to these coating compositions.

Therefore, the purpose of the present invention is to provide plastic products, wood products,
The object of the present invention is to provide a coating composition that can be applied to the surface of metal products and the like to improve corrosion resistance against acids, alkalis, solvents, etc., and to impart various functionalities.

[Means to solve the problem]

As a result of intensive research into the hydrolysis reaction of metal alkoxides with respect to coating compositions for various materials, the present inventors found that the general formula R″4-1I4-1I■)n (where M is metal and R■ is By coexisting a hydrated aluminosilicate with a metal alkoxide represented by a hydrocarbon residue having 1 to 5 carbon atoms (n is a coefficient of 1 to 4), the water contained in the hydrated aluminosilicate is gradually released. We have discovered that it is possible to form a uniform oxide coating film and provide stable corrosion resistance.Furthermore, by ion-exchanging the hydrated aluminosilicate, various cations are combined to form a highly insulating, ferroelectric, and
It is possible to provide many functionalities such as electromagnetic functions such as conductivity, optical functions such as light reflection and fluorescence, thermal functions such as heat resistance and heat conductivity, and biochemical functions such as antibacterial properties and biocompatibility. This discovery led to the completion of the present invention.

That is, the present invention provides a coating composition that can be applied to the surfaces of plastic products, wood products, metal products, etc. to improve corrosion resistance and impart functionality.

The present invention will be explained below.

In the present invention, the metal alkoxide has the general formula R'4-aM (
OR■)n (in the formula, M is a metal, R■ is a hydrocarbon residue having 1 to 5 carbon atoms, and n is a coefficient of 1 to 4), and the metals include silicon, zirconium, and titanium. ,
Aluminum can be mentioned. Examples where the metal is silicon include methyltrimethoxysilane, methyltriethoxysilane, ethyl silicate, propyl silicate,
Silanes such as methyltris(dimethylketoxime)silane, methyltris(methylethylketoxime)silane, methyltris(diethylketoxime)silane, their partial hydrolysates, and silanes with the number of aminoxy groups in the molecule being 1
polymethyl (diethylaminoxy) siloxane, with an average of 2 or more in the coating agent;
Examples include polymethylphenyl(diethylaminoxy)siloxane and polymethylbutyl(diethylaminoxy)siloxane. Examples where the metal is zirconium include zirconium isopropylate, mono-5ec-butoxyzirconium diisopropylate, zirconium ethylate, acetate, alkoxyzirconium diisopropylate, and the like. Examples of titanium metal include tetraisopropoxytitanium, tetra-n-butoxytitanium,
Tetrakis-2-ethylhexoxytitanium, tetrastearoxytitanium, diiso-propoxybis(acetylacetonato)titanium, iso-propoxy(2ethylhexanediorad)titanium, di-n-butoxybis(triethanolaminato)titanium, Hydroxybis(lactato)
Examples include titanium, isopropyltriisostearoyltitanate, bis(dioctylpyrophosphate)ethylsilicate, isopropyltri(n-aminoethylaminoethyl)titanate, and the like. Examples where the metal is aluminum include aluminum isopropylate, mono 5
Examples include ee-butoxyaluminum diisopropylate, aluminum ethylate, and acetalkoxyaluminum diisopropylate. Among these, -a
Hydrocarbon residue in the formula R', -, M (OR'') a, R
The number of carbon atoms in ' and R' is preferably from 1 to 5 from the viewpoint that the substance decomposes at a relatively low temperature and the hydrocarbon component loses consecutively.

The hydrous aluminosilicate, which is an essential component of the coating composition of the present invention, will be explained.

Any substance that has water absorption properties can be used as a substance that provides the water necessary for the hydrolysis of metal alkoxides, such as crystalline aluminosilicate, amorphous aluminosilicate, activated alumina, silica gel, activated carbon,
Calcium oxide, magnesium oxide, calcium sulfate,
Examples include phosphorus pentoxide, magnesium perchlorate, etc., and a coating film can be formed by adsorbing a certain amount of water to these and reacting with a metal alkoxide. However, aluminosilicates are preferred for binding various cations for the purpose of imparting further functionality to the coating film.

Examples of aluminosilicate include crystalline aluminosilicate commonly called zeolite, JP-A No. 53-30500,
Examples include amorphous aluminosilicates described in JP-A-61-174111 and the like.

Here, as the "zeolite", both natural zeolite and synthetic zeolite can be used.

Zeolites are generally aluminosilicates with a three-dimensional skeleton structure, and have the general formula XMI/-0・AIgO
It is displayed as i・YSiOg・ZHxO. Here M
is a metal ion that is an ion exchangeable ion.

n is the valence of the (metal) ion. X and Y represent the respective metal oxide and silica coefficients, and Z represents the number of crystal water. Specific examples of zeolites include A-type zeolide, X-type zeolide, Y-type zeolide, and T-type zeolide.
Examples include type zeolide, high silica zeolite, sodalite, mordenite, analcyme, clinoptilolite, chabasite, erionite, and the like. However, it is not limited to these.

In the present invention, hydrated amorphous aluminosilicate can also be used. Amorphous aluminosilicate (hereinafter referred to as AAS) generally has the composition formula xMzo・AItoz・ys
It is expressed as iQ, 1 z HxO, where M is an alkali metal element, typically sodium or potassium. Moreover, x and ySz each indicate the molar ratio of metal oxide, silica, and crystal water. Unlike crystalline aluminosilicate, which is called zeolite, AAS is an amorphous material that does not show any diffraction pattern even in XwA diffraction analysis, and several tens of microscopic zeolite crystals are produced during its synthesis process. However, it is thought to have a structure in which an amorphous material consisting of a complex combination of SiO□, AItoz, LO, etc. is attached to the surface.

AAS is generally manufactured by heating an aluminum salt solution, a silicon compound solution, and an alkali metal salt solution at a predetermined concentration at 60°C.
It is produced by reacting at the following low temperature range and washing with water before crystallization progresses. AAS produced by such a method has almost the same water adsorption performance and ion exchange performance as zeolite. As a manufacturing method, for example, Japanese Patent Application Laid-Open No. 53-3050
There are methods described in Japanese Patent Application Laid-Open No. 61-174111, etc.

It should be noted that the aluminosilicate used in the present invention must contain enough water to cause the hydrolysis of the metal alkoxide, and the water content should be 5 to 50%.
Preferably, it is 15 to 25% from the viewpoint of corrosion resistance and a suitable film thickness of 5 to 15 μm.Although there is no particular restriction on the particle size of alumino or silicate, it is more stable. From the viewpoint of obtaining a coated film, it is preferable that the particle size is relatively small.
can be.

The amount of the hydrated aluminosilicate added is 0.1 to 30 parts by weight per 100 parts by weight of the metal alkoxide hydrolyzate;
Preferably, the amount is from 1 to 10 parts by weight; less than this will result in insufficient curing, while more than this will cause defects such as poor adhesion and reduced corrosion resistance of the coating film.

The aluminosilicate used in the present invention imparts various functionalities to some or all of the ion-exchangeable ions in the aluminosilicate, such as sodium ions, calcium ions, potassium ions, magnesium ions, and iron ions. It is ion-exchanged with various cations for the purpose of

The types of cations to be ion-exchanged and the functions provided are as follows.

Electronic electromagnetism High insulation: Vanadium ion function 2 Ferroelectricity: Barium, tin ion conductivity 2! ! ! , zirconium, lanthanum ion Optical function: light reflectivity; bismuth, titanium ion Fluorescence: europium, silver ion Thermal function: heat resistance: thorium ion Heat conductivity: lead, platinum ion Biochemical function: antibacterial property: im, zinc, Copper, tin ions Biocompatible niphosphorus ions The amount of cations bonded to the aluminosilicate by ion exchange varies somewhat depending on the function imparted, but is 0.5 to 80%, preferably 5 to 50% in the aluminosilicate. shall be.

In this specification, % refers to % by weight on a dry basis at 110°C.

The method for producing the cation-bonded zeolite used in the present invention will be explained below. For example, the antibacterial zeolite used in the present invention can be prepared by contacting the zeolite with a mixed aqueous solution containing antibacterial metal ions such as silver ions, copper ions, zinc ions, tin ions, etc., prepared in advance, to obtain ion-exchangeable ions in the zeolite. and the above ion are replaced. The contact is
It can be carried out at 10 to 70°C, preferably 40 to 60°C, for 3 to 24 hours, preferably for 10 to 24 hours, by a batch method or a continuous method (for example, a column method).

The pH of the above mixed aqueous solution is 3 to 10. Preferably 5-7
It is appropriate to adjust the This adjustment is preferable because it can prevent the precipitation of daughter oxides and the like on the zeolite surface or in the pores, and each ion in the mixed aqueous solution is usually supplied as a salt.

For example, silver ions include silver nitrate, silver sulfate, perchlorate, silver acetate, diamine silver nitrate, diammine 1117ii acid salt, etc., and copper ions include copper nitrate (■), copper sulfate, steel perchlorate, copper acetate, copper tetracyanate, etc. Potassium acid, etc., zinc ions such as zinc nitrate (■), zinc sulfate, zinc perchlorate, zinc thiocyanate, zinc acetate, etc., and tin ions, tin sulfate, tin nitrate, etc. can be used.

The content of silver ions, etc. in the zeolite can be appropriately controlled by adjusting the concentration of each ion (salt) in the mixed solution. For example, when the antibacterial zeolite contains aluminum ions and ionic ions, The aluminum ion concentration in the mixed aqueous solution was 0.1M71 to 0.1M71.
8M//, silver ion concentration 0.002M/1~0.
15M/j, aluminum ion content 0.2 to 2% and silver ion content 0.1 to 5% as appropriate.
% antibacterial zeolite can be obtained. In addition, when the antibacterial zeolite further contains copper ions and zinc ions, the copper ion concentration in the mixed aqueous solution is 0.1M/1 to
2.3M/1, zinc ion concentration 0.15M/J ~
By setting the amount to 2.8 M/J, antibacterial zeolite having an appropriate copper ion content of 0.1 to 18% and zinc ion content of 0.1 to 18% can be obtained.

In the present invention, in addition to the mixed aqueous solution as described above, ion exchange can also be performed by using an aqueous solution containing each ion individually and bringing each aqueous solution into contact with the zeolite sequentially. The concentration of each ion in each aqueous solution can be determined according to the concentration of each ion in the mixed aqueous solution.

After ion exchange, the zeolite is thoroughly washed with water and then dried. Drying is preferably carried out at 105°C to 115°C under normal pressure or at 70°C to 90°C under reduced pressure (1 to 30 torr).

Ion exchange of ions without suitable water-soluble salts such as lead and bismuth can be carried out using an organic solvent solution such as alcohol or acetone so that hardly soluble basic salts are precipitated.

Similar to the method for preparing aluminosilicates imparting antibacterial properties described above, aluminosilicates imparting various functionalities can be obtained by ion exchange with a corresponding cation solution. The conditions can be carried out in accordance with the method for preparing the antibacterial aluminosilicate described above.

Substances that provide each cation solution include, for example, vanadium ions such as vanadium sulfate and vanadium bromide; barium ions such as barium perchlorate, barium nitrate, and barium acetate; and zirconium ions such as zirconium sulfate, zirconium acetate, and Zirconium nitrate oxide, etc., lanthanum ions include lanthanum sulfate, lanthanum acetate, lanthanum nitrate, etc., bismuth ions include bismuth chloride, bismuth iodide, etc., titanium ions include titanium sulfate, etc., europium ions include europium sulfate, europium acetate, europium nitrate, etc. etc., thorium ions include thorium sulfate, thorium acetate, thorium nitrate, etc.; lead ions include lead perchlorate,
Examples of platinum ions include lead nitrate and lead hexafluorosilicate, platinum chloride, platinum sulfate, and tetraamine platinum chloride; examples of phosphorus ions include phosphorus trichloride, tricyanoline, and the like.

The compositions according to the invention may further contain customary additives such as pigments, surfactants, antifoaming agents, etc.

Methods for applying the coating composition of the present invention to a substrate include printing, spraying, kissing, roller coating, impregnation,
Examples include flowing through a nozzle, bath treatment, foam treatment, etc., but spraying is preferred from the viewpoint of controlling the amount of the resin composition applied and facilitating drying.

The coating amount of the coating composition of the present invention is 0.5 to 50
g/rd, preferably 5 to 20 g/at, from the viewpoint of corrosion resistance.

The heating operation after application can be done at a much lower temperature than in the case of conventional paints, and 10 to 30 minutes at 40 to 60 DEG C. is sufficient. It is particularly suitable for thermoplastic resins because it can be coated at low temperatures.

Substrate materials include thermoplastic resins, thermosetting resins, plastics such as rubber, glass, ceramics, concrete, asbestos, wood, paper, fibers, and metals such as aluminum, copper, iron, and stainless steel. It shows adhesion and is applicable.

The coating composition according to the present invention can also be used as one of the composite materials.

Materials to which the coating composition of the present invention obtained as described above is applied can be used in various fields such as building materials, ships, tanks, piping, etc. For example, materials that impart high insulation properties can be used. , IC substrates, insulating substrates, etc., which provide ferroelectricity, such as electronic circuits, electronic devices, etc., which provide conductivity, such as batteries, gas sensors, thermistors, varistors, semiconductor substrates, etc., and light-reflective materials. Things that give heat resistance include solar heat concentrators, energy-saving window glass, etc. Things that give fluorescence include lighting equipment, television cathode ray tubes, etc. Things that give heat resistance include heat-resistant structures, wall materials, etc. Items that impart antibacterial properties include electrical equipment; items that impart antibacterial properties include cooling tower parts, kitchen utensils, bathroom utensils, food factory machinery, etc. Items that impart biocompatibility include artificial bones, artificial teeth, enzyme fixation, etc. chemical carrier, etc.

〔Effect of the invention〕

The coating composition of the present invention has the general formula R4□M(O
Since it is composed of a metal alkoxide represented by R'')n and a hydrated aluminosilicate, when applied to the surface of plastic products, wood products, metal products, etc., the water contained in the hydrated aluminosilicate gradually evaporates. It can be released to form a uniform oxide coating, and has the effect of providing stable corrosion resistance.

Furthermore, the coating composition of the present invention having the composition as described above has electromagnetic functions such as high insulation, ferroelectricity, and conductivity by bonding various cations to the hydrated aluminosilicate through ion exchange. It also has the effect of imparting many functionalities such as optical functions such as light reflection and fluorescence, thermal functions such as heat resistance and heat conductivity, and biochemical functions such as antibacterial properties and biocompatibility.

〔Example〕

Next, embodiments of the present invention will be described with reference to Examples, but the present invention is not limited to the Examples.

Reference example (preparation of cation-bonded aluminosilicate) Aluminosilicate is commercially available A-type zeolide (NaxO
・Alx03・2.05iOi・χII, O: average particle size 1.1#m), natural clinoptilolite (150~
250 mesh) Amorphous aluminosilicate (Unexamined Japanese Patent Publication No. 61
Prepared by the method of No.-174111: 0.3 μm) No. 3
type was used. aglio, Cu (NOs) as a salt to provide each ion for ion exchange *
・3HzO, Zn (NO3) z ・6HzO+
Zr (Son)z ・4HzO+ La(NOs)z
-7HzOx(NOx)z・6H*0. Ha(NOi
)z were used.

Table 1 shows the type of aluminosilicate used in preparing each sample and the type and concentration of salt contained in the mixed aqueous solution.
Fourteen types of cation-bonded aluminosilicate samples No. 1 to No. 14 were prepared.

For each sample, 1 kg of aluminosilicate powder was heated and dried at 110°C, suspended in water from step 11, and added to
．． A 0.5N nitric acid aqueous solution was added dropwise at a dropping rate of 100 sj/30 minutes, and the pH was adjusted to a predetermined pH value (5 to 7).
Next, a mixed aqueous solution 31 of antibacterial metal salts at a predetermined concentration was added to the slurry for ion exchange. This reaction starts from room temperature at 6
Stir at 0° C. for 10-24 hours to reach equilibrium.

After the ion exchange was completed, the aluminosilicate phase was washed with water at room temperature or hot water until the excess exchanged cations in the aluminosilicate phase disappeared.Next, the sample was heated and dried at 110°C, and the sample was heated to dry at 110°C. Fourteen types of samples were obtained.

Example (Preparation of coating composition) A metal alkoxide and a cation-bonded aluminosilicate obtained in Reference Example with water adsorbed were blended as shown in Table 2, and J
Glass plate and J that comply with IS-G3201
Apply a specified amount to a steel plate that complies with IS-G3141,
It was dried at 40 to 60°C for 10 to 30 minutes (Examples 1 to 14 in Table 2), and as a comparative example, three types of aluminosilicates and no aluminosilicate addition (metal alkoxide only) before ion exchange. Application samples were also created (Comparative Examples 1 to 3 and 4 in Table 2).

Test Example 1 (Coating film corrosion resistance test) A steel plate on which the coating composition prepared in the example had been applied was cut into 50×50III pieces to prepare a test plate. The results of each test are shown in Table 3.

Heat Resistance) After being left at 500°C for 1 hour in an electric furnace, the state of scale generated on the test plate was observed. Judgment was made based on the following criteria.

l: No abnormality was observed and no scale was generated.

2D A slight scale was generated on some parts of the coating film.

3: Scale was generated on the entire surface and the color was yellow.

48 Considerable scale was generated over the entire surface, giving it a brown color.

5: The coating film was damaged.

(Acid resistance) The state of the coating film on the test plate was observed after being immersed in a 10% aqueous sulfuric acid solution at room temperature for 5 hours. Judgment was made based on the following criteria.

l: No abnormality observed at all.

2: Affected in a pinpoint manner.

3: Less than 20% of the coating surface was attacked.

4: 20% or more of the coating surface was attacked.

5: Almost the entire surface of the coating film was attacked.

(Alkali resistance)
After being immersed for a period of time, the state of the coating film on the test board was observed. Judgment was made based on the following criteria.

l: No abnormality observed at all.

2: Slight rastering occurred.

3: Rastering occurred in a wide range.

4: Significant rastering occurred and whitening of the surface was observed.

5;’! The film was damaged and cracked.

(Scratch Resistance) The coating film was strongly rubbed with #000 steel wool, and the degree of scratching was observed. Judgment was made based on the following criteria.

l: No flaws observed at all.

2: Slight scratches occurred.

3: Scratches occurred on the entire surface.

4D Part of the paint film was damaged.

5: The coating film was significantly damaged.

(Solvent Resistance) The surface of the coating film was observed after 48 hours of immersion in a mixture of petroleum benzine and toluene at a weight ratio of 4=1. Judgment was made based on the following criteria.

1: No abnormality observed at all.

2D Some wrinkles appeared.

3D Blisters, cracks, and peeling occurred in some areas.

4; Damage to the coating film occurred.

5: Most of the coating film was damaged.

Test Example 2 (Coating Film Strength Test) A steel plate to which the coating composition prepared in the example was applied was cut into a size of 150 x 70 M and used as a test plate. The results of each test are shown in Table 3.

(Adhesion) Using a cutter, cut 11 parallel lines vertically and horizontally at intervals of 4 IIm on the surface of the coating film to damage 100 squares. A cellophane adhesive tape was attached on top of the tape, and the squares that did not peel off were measured.

(Scratch Resistance) Using a pencil of each hardness, the hardness symbol that caused scratching in two out of five measurements was written in accordance with JIS 5400.

Test Example 3 (Antibacterial Test) The glass plate to which the coating composition prepared in the example was applied was cut into 50 x 50 n pieces, and each was treated with Escherichia coli solution (10' pieces/s1) and Pseudomonas aeruginosa solution (10 S pieces/s1). 1
) was sprinkled on each plate in an amount of 15 ml, and cultured at 37°C for 18 hours.

The bacterial solution was washed away with physiological saline, and the number of Escherichia coli and Pseudomonas aeruginosa present in this solution was measured. The results are shown in Table 4. Generally, if the number of bacteria after 18 hours is two orders of magnitude or more lower than the initial number of bacteria added, it can be said that the product has antibacterial properties.

Test Example 4 (Electroconductivity Test) Two glass plates to which the coating composition prepared in Example was applied were cut into 70 x 30 u pieces and placed at a distance of 2 dragons. Deionized water was flowed down across the two electrodes facing each other, a 3μ DC voltage was applied between the electrodes, and the specific resistance value was measured from the current value. The results are shown in Table 4. Generally, when the resistivity value is 1O-3Ω·1 or less, it can be said that the material has high conductivity.

Test Example 5 (Dielectricity Test) The glass plate to which the coating composition prepared in the example was applied was cut into 70 x 30 m pieces, and this was placed in the measurement cell of a bridge-type dielectric constant measuring device TR-IC manufactured by Ando Electric. , the temperature was raised to 400°C at a heating rate of 0.3°C/min, and the temperature was degassed.
The degree of vacuum was set to be at least X 10-' Torr. 5 for this
Introducing Torr of helium, IKHz at 100℃
The AC dielectric constant of was measured. The results are shown in Table 4. Generally, when the dielectric constant is 50 or more, it can be said to be a ferroelectric material and can be put to practical use in electronic circuits and the like.

Test example 6 (fluorescence test)

Claims (1)

[Claims] 1. (a) General formula R^1_4_-_nM(OR^■)_
A hydrolyzate of a metal alkoxide represented by n (in the formula, M is a metal, R^1, R^■ are hydrocarbon residues having 1 to 5 carbon atoms, and n is a coefficient of 1 to 4); ) A coating composition comprising a hydrated aluminosilicate. 2. The coating composition according to claim 1, wherein the water content of the hydrated aluminosilicate is 5 to 50%. 3. The coating composition according to claim 1, which contains an antibacterial metal ion in the hydrous aluminosilicate. 4. The coating composition according to claim 1, wherein the metal (M) in the metal alkoxide is a metal selected from the group consisting of silicon, zirconium, titanium, and aluminum. 5. Component (a) per 100 parts by weight, component (b) 0.
The coating composition according to claim 1, wherein the amount is 1 to 30 parts by weight.