JPH0718204A - Reaction-curing hard coating material composition - Google Patents

Abstract

PURPOSE:To obtain the composition which can coat the surface of materials, such as plastics, wood, ceramics, glass and metal, to impart high hardness, stain resistance and flame retardancy thereto. CONSTITUTION:The composition is composed mainly of a reaction product of bis[(meth)acryloxymethyl]methanol of formula I and/or tetramethylolmethane (meth)acrylate of formula II with phosphoric anhydride. In the formulas I and II, R is H or CH3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reaction-curable hard coat agent composition having high hardness and excellent stain resistance and flame retardancy.

[0002]

2. Description of the Related Art Conventionally, there has been known a technique of applying a coating agent to the surface of a material such as plastic, wood, ceramics, glass and metal to modify the surface characteristics of the material. Such a hard coating agent imparts properties such as mechanical strength, hardness, weather resistance, flame retardancy, corrosion resistance, water repellency or oil repellency without impairing the excellent properties inherent to the material. It needs to be one. For example, materials such as resins, decorative boards, wood and metals are often used for a long period of time under harsh weather such as hot weather or wind and snow, or in a strong acidic or basic atmosphere. The hard coating agent used for such a material must form a coating capable of imparting properties such as weather resistance, surface hardness, heat resistance, or chemical resistance.

Silicone, acrylic, and urethane polymer compounds are known as hard coat agents conventionally used for these purposes.

[0004]

However, although the conventional hard coating agents of silicone type give a coating excellent in heat resistance and water repellency, they have insufficient flame retardancy and stain resistance, and further have a low adhesiveness. However, there is a problem in that a base treatment must be performed at the time of coating because of poor quality. Further, the acrylic and urethane hard coat agents have a problem that heat resistance, flame retardancy and abrasion resistance are insufficient.

Further, the conventional hard coating agent has a problem that it is partially hydrolyzed by an acid or an alkali and is inferior in acid resistance and alkali resistance, and further the adhesive strength is remarkably lowered by repeating heating and cooling. There was also.

The object of the present invention is to solve the above problems of the prior art and to provide a hard coat agent composition capable of providing a coating excellent in abrasion resistance, weather resistance, heat resistance, chemical resistance and the like. To provide.

[0007]

The reaction-curable hard coating composition of the present invention is represented by the formula (I) bis [(meth) acryloxymethyl] methanol and / or the formula (II). It is characterized in that it contains a reaction product of tetramethylol (meth) acrylate and phosphoric anhydride as a main component.

[0008]

[Chemical 2]

(Here, R represents H or CH _3. )
The reaction product used as the main component in the present invention is one alcohol of bis [(meth) acryloxymethyl] methanol and tetramethylolmethane tri (meth) acrylate, or a mixture of both alcohols and phosphoric anhydride (phosphorus pentoxide). Is a reaction composition reacted with.

The reaction product of alcohol and phosphoric anhydride, which is used as a main component in the present invention, can be produced by a general method for producing a phosphoric acid ester, and can be used in a dry inert non-aqueous solvent or under a solvent-free condition. It can be obtained by reacting ˜3.5 mol of alcohol, preferably 3 mol of alcohol with 1 mol of phosphoric anhydride.

Examples of the inert non-aqueous solvent used in this reaction include benzene, toluene, xylene, chloroform, methylene chloride, cyclohexane, ether, tetrahydrofuran and 1,4-dioxane. The reaction is generally performed at room temperature to 150 ° C. for several hours, preferably at 30 to 70 ° C. for 2 hours.
Stir for 3 hours. Further, if necessary, a polymerization inhibitor such as hydroquinone monomethyl ether may be added to the reaction system.

The hard coat agent composition of the present invention contains a reaction product of such an alcohol and phosphoric anhydride as a main component, but may contain other reaction curable compounds, if necessary. Good. Examples of such a reaction-curable compound include methyl acrylate, hydroxyethyl acrylate, ethylene glycol diacrylate, a mixture of triethylene glycol diacrylate and methacrylates, glycidyl acrylate, 2,2′-
Bis (acryloxyphenyl) propane, 2,2'-bis [4- (3-methacryloxy) -2-hydroxypropoxyphenyl] propane, vinyl acetate, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride , Mono-, di- or tri (methacryloxyethyl) phosphate, dimethylaminoethyl methacrylate and the like.

Such a reaction-curable compound is compounded within a range in which the required characteristics are allowed. For example, when flame retardancy is required, the phosphorus content of the hard coating agent as a whole is from 1 to 1. The reaction-curable compound is contained so as to be 5% by weight.

The reaction-curable hard coat agent composition of the present invention may further contain a filler. By containing the filler, the wear resistance can be further improved. Examples of such fillers include powders and whiskers of mica, silica, talc, alumina, apatite, glass beads, barium silicate, silicon nitride, silicon carbide, potassium titanate, and organic fillers such as polymethylmethacrylate. You can

Among these fillers, silica powder, barium titanate whiskers, and mica are particularly preferable from the viewpoint of wear resistance, friction wear resistance and weather resistance. The addition amount of these fillers is not particularly limited, but is 5 to 200% by weight based on the reaction product of alcohol and phosphoric anhydride.
It is preferably in the range of. If it is less than 5% by weight, the properties may not be sufficiently improved, and if it exceeds 200% by weight, the ratio of the reaction curable composition may decrease and mechanical strength may be insufficient.

In the present invention, the above-mentioned reaction product of alcohol and phosphoric anhydride is generally obtained as a high-viscosity liquid, so that the reaction product can be used as it is, but if necessary, an aqueous or non-aqueous solvent or an organic solvent can be used. It can be used after being dissolved or dispersed in a solvent. For example, by emulsifying or suspending in water or water / alcohol, ketones such as acetone and methyl ethyl ketone, aromatics such as benzene and toluene, halogens such as chloroform and methylene chloride, alcohols such as ethanol and propanol, It can be used by being dissolved or dispersed in ethers such as tetrahydrofuran and dioxane, and alicyclic compounds such as cyclohexane and cyclohexanone.

The reaction-curable hard coat agent composition of the present invention contains various additives such as a curing agent, a polymerization inhibitor, a colorant, an antioxidant, and an ultraviolet absorber which are used in ordinary coating agents. Can be made.

The reaction-curable hard coat agent composition of the present invention can be applied and used in the same manner as an ordinary coating agent. That is, the reaction-curable hard coat agent composition of the present invention is applied to the surface of the material by a dipping method, a spray coating method or the like, and the solvent is removed if necessary.

The reaction-curable hard coat agent composition of the present invention can be cured at room temperature, but considering the characteristics of the coating film obtained, heat curing, photo-curing and electron beam curing are preferable. In this case, a reaction initiator or sensitizer such as benzoyl peroxide, di-t-butyl peroxide, p-methoxybenzophenone, 1-hydroxycyclohexyl phenyl ketone or dibenzoyl may be used in an amount of about 0.05 to 5% by weight. preferable. In the case of heat curing, it is generally cured at a temperature of 100 ° C. or higher, though it depends on the composition of the hard coat agent. In the case of photocuring, ultraviolet rays in the wavelength range of 200 to 550 nm are irradiated for 1 second or longer, and the integrated light amount is 100.
It is preferably 0 to 5000 mJ / cm ² .

[0020]

The film formed by the reaction-curable hard coat agent composition of the present invention has flame retardancy due to the characteristics of the phosphorus atoms contained therein. Further, since it has a plurality of (meth) acrylic groups in one molecule, it forms a film excellent in properties such as heat resistance, water resistance, weather resistance and abrasion resistance.

Furthermore, an antistatic function can be imparted by the effect of the hydroxyl group present in the molecule, and the problem of dust adhesion due to the electrification of the plastic lens or the cathode ray tube can be avoided. Furthermore, the dispersibility of the filler and the adhesion to the substrate are also excellent. Therefore, the surface of the coated material can be stably protected for a long period of time with almost no peeling even when exposed to acid or alkali for a long time.

Furthermore, the coating film formed from the reaction-curable hard coating composition of the present invention is essentially transparent and can be used for coating the surface of a decorative board or the like. Further, since the polymerization shrinkage rate is low, the material is hardly deformed by the curing reaction.

[0023]

【Example】

(Example 1) Bis (methacryloxymethyl) methanol and phosphoric anhydride
Reaction composition with bis (methacryloxymethyl) methanol 4 in a 1 liter flask equipped with a stirrer with water content shut off.
56 g, phosphoric anhydride (phosphorus pentoxide) 95 g, and p-methoxyphenol 0.8 g were charged, and the mixture was shielded from light at 3 ° C at 3 ° C.
The reaction was carried out by stirring for a period of time to quantitatively obtain a slightly yellow reaction composition having a viscosity of about 500 cps. The infrared absorption spectrum of the obtained reaction product is shown in FIG. The analytical values of the hydrogen nuclear magnetic resonance spectrum and the phosphorus nuclear magnetic resonance spectrum are shown below. ¹ H-NMR (CDCL ₃ ): δ (ppm vs. TMS)
1.86 (S, 6H), 4.29 (M, 4H), 5.
25 (T, 1H), 5.54 (S, 2H), 6.04
(S, 2H), 12.30 (S, 1H) ³¹ P-NMR (CDCL ₃ ): δ (ppm vs phosphoric acid)
-0.172 (M, 4P), -13.67 (M, 5)
P) 1-Hydroxycyclohexyl phenyl ketone was added to the obtained reaction composition at a ratio of 1% by weight to prepare a photoreactive curable hard coat agent.

This hard coating agent was applied to a polycarbonate plate having a thickness of 5 mm, and irradiated with a 20 W ultraviolet lamp for 30 minutes in a nitrogen atmosphere to obtain an almost colorless transparent cured coating (thickness: 10 μm).

The surface pencil hardness of the obtained cured coating was 9H. (The surface pencil hardness of the polycarbonate plate is F.) Similarly, when the hard coating agent was applied onto a glass plate and cured to measure the hardness of the coating film, the surface pencil hardness was over 9H.

Further, the sand wear (ΔH) measured according to ASTM D-673 was 23. Since the falling sand wear (ΔH) of the polycarbonate plate is 70,
The effect of applying the hard coat agent is clearly recognized. (Example 2) of tetramethylol methanetriacrylate and phosphoric anhydride
The reaction was performed in the same manner as in Example 1 except that 600 g of tetramethylolmethane triacrylate was used as the alcohol, and a slightly yellow reaction composition having a viscosity of about 20,000 cps was quantitatively obtained. The infrared absorption spectrum of the obtained reaction composition is shown in FIG. The analytical values of the hydrogen nuclear magnetic resonance spectrum and the phosphorus nuclear magnetic resonance spectrum are shown below.

¹ H-NMR (CDCL ₃ ): δ (ppm
Vs. TMS) 4.21 (T, 2H), 4.27 (S,
6H), 5.87 (T, 3H), 6.10 (DD, 3
H), 6.36 (DD, 3H), 11.97 (S, 1
H) ³¹ P-NMR (CDCL ₃ ): δ (ppm vs phosphoric acid)
1.40 (M, 1P), -13.33 (M, 5P) 1-hydroxycyclohexyl phenyl ketone was added to the obtained reaction composition at a ratio of 1% by weight, and this was adjusted to 30% by weight with chloroform. To prepare a photoreactive curable hard coat agent.

The obtained hard coating agent was applied to a polycarbonate plate having a thickness of 5 mm, dried, and then irradiated with a 20 W ultraviolet lamp for 30 minutes in a nitrogen atmosphere to form an almost colorless transparent cured film (thickness 10 μm). Obtained.

The surface pencil hardness of this cured coating was 8H. The surface pencil hardness of the cured film obtained by applying the hard coating agent on the glass plate and curing the same was 9H. When the falling sand wear (ΔH) was measured in the same manner as in Example 1, it was 2
It was 7. (Example 3) Bis (methacryloxymethyl) methanol and tetrame
A mixture of tyrolen methanetriacrylate and phosphoric anhydride
Reaction composition of bis (methacryloxymethyl) methanol 228 g and tetramethylolmethane triacrylate 300 g were used as alcohols, and the reaction was performed in the same manner as in Example 1 except for the above, and a slightly yellow reaction composition having a viscosity of about 10,000 cps. The product was obtained quantitatively. 1% by weight of 3,
3 ', 4,4'-Tetra- (t-butylperoxycarbonyl) benzophenone was added and diluted to 50% by weight with tri (methacryloxyethyl) phosphate to prepare a photoreactive curable hard coat agent. .

Using the obtained hard coat agent, a thickness of 5 m
20 m under a nitrogen atmosphere.
It was irradiated with a W ultraviolet lamp for 30 minutes to obtain an almost colorless transparent cured coating (thickness 10 μm).

The surface pencil hardness of the obtained cured coating was 8H. The pencil hardness of the cured coating applied and cured on the glass plate was 9 or more. Further, the amount of worn sand (ΔH) measured in the same manner as in Example 1 was 25. (Example 4) Evaluation of stain resistance and flame retardancy The cured coatings of Examples 1 to 3 were evaluated for stain resistance with iodine and black magic ink in accordance with JIS K6902. Was also very good. In the flame retardancy test with tobacco, no charring was observed, and very good results were obtained. (Example 5) Evaluation of impact resistance, transparency and oil resistance 20 sheets of polycarbonate plates on which the cured coatings of Examples 1 to 3 were formed were stacked and a steel ball having a diameter of 15 mm was dropped from a height of 2 meters. The impact resistance was evaluated. No crack was observed in any of the test pieces of Examples 1 to 3.

When the transparency was evaluated according to JIS K7105, the visible light transmittance was 90% or more, and the transparency was very good. Further, the test pieces of Examples 1 to 3 were immersed in gasoline for 1 hour, and the oil resistance was evaluated by visually observing the test pieces after the immersion. As a result, no abnormality due to gasoline immersion was observed.

From the above results, by applying the reaction-curable hard coating agent according to the present invention to a polycarbonate plate, it can be used as a window glass for transportation machines and buildings, as well as a windshield for helmets and motorcycles, and transparent protection for various machines. It was confirmed to be suitable as a cover. (Example 6) Application to a wooden table The hard coat agents of Examples 1 to 3 were applied to the surface of a wooden table and irradiated with ultraviolet rays in the same manner as in Examples 1 to 3 to form a cured film. JISK5400 for cured film
No cross-section was observed when a cross-cut test was conducted in accordance with. Further, when the surface of the cured film was strongly rubbed with steel wool to evaluate the scratch resistance, no scratches were found.

When the boiled kettle was placed directly, it was confirmed that no heat marks were left and the heat resistance was good. In addition, no charring was observed in the flame retardancy test with cigarettes, indicating very good heat resistance.

As described above, by applying the hard coating agent according to the present invention to a woodworking product, excellent properties such as scratch resistance and heat resistance can be imparted. (Example 7) Application to unglazed roof tile The hard coat agent compositions of Examples 1 to 3 were applied to the unglazed tile to a thickness of 20 µm, and a distance of 20 cm was applied to 1
A high pressure mercury lamp of 00 W has an integrated light intensity of 5000 mJ / cm ²
Was irradiated to form a cured coating.

The topcoat roof tile thus formed with a cured film showed no contamination even after an outdoor exposure test for 6 months, and no change was observed even after a 5000 hour acidic weather test assuming acid rain. It was

Further, these cured coatings are JIS K540.
No peeling was observed in the cross cut test based on 0.
From the above results, it was confirmed that the hard coat agent composition according to the present invention can be applied to a ceramic product to impart very excellent properties. (Example 8) Evaluation of antistatic performance Polycarbonate plate (PC plate) and polymethylmethacrylate plate (P) treated with the hard coating agent of Examples 1 and 2
The antistatic performance was evaluated using an MMA plate). The results are shown in Table 1. Evaluation is in accordance with MIL standard
manufactured by electro-Tech Systems, Inc.
The static decay meter 406C was used for the charge decay time (until the charge disappeared by charging at 5000 V with + or −).

[0038]

[Table 1]

As is clear from Table 1, the hard coating agent of the present invention has a very large charge decay ability and can impart a good antistatic function.

[0040]

INDUSTRIAL APPLICABILITY As described above, the reaction-curable hard coating composition according to the present invention has a high hardness and can form a coating film excellent in stain resistance and flame retardancy.
In addition, this cured film exhibits very strong adhesion to the surface of materials such as plastic materials, wood, ceramics, glass, paper or metal, and also has good chemical stability such as acid resistance and alkali resistance. Is. Therefore, the hard coating agent of the present invention is a decorative board, plastic, wood,
It can be used as a hard coating agent for coating printed matter, metal, textiles, magnetic materials, ceramics, glass, optical fibers and the like. In particular, antistatic hard coats for plastic glass, plastic lenses, cathode ray tubes, electromagnetic wave cut TV filters, etc., hard coats for inside panels of various types of transport equipment, top coats for main roof tiles and straight roof tiles, tops of high-rise buildings and outer walls of ordinary houses. It can be suitably used as a coat, a top coat for steel towers / piers, a top coat for manholes and gratings, a clear coat for automobile exterior panels, and a hard coat for furniture / woodwork products.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of the reaction composition of alcohol and phosphoric anhydride prepared in Example 1 according to the present invention.

FIG. 2 is an infrared absorption spectrum of a reaction composition of alcohol and phosphoric anhydride prepared in Example 2 according to the present invention.

Claims (1)

[Claims] 1. A reaction product of bis [(meth) acryloxymethyl] methanol represented by formula (I) and / or tetramethylolmethane tri (meth) acrylate represented by formula (II) with phosphoric anhydride. A reaction-curable hard coat agent composition comprising a main component. [Chemical 1] (Here, R represents H or CH _3. )