JP3251721B2 - Reaction curable hard coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art There has been known a technique of applying a coating agent to a surface of a material such as plastic, wood, ceramics, glass and metal to modify the surface characteristics of the material. Such hard coat agents impart properties such as mechanical strength, hardness, weather resistance, flame retardancy, corrosion resistance, water repellency or oil repellency without impairing the excellent properties inherent in the material. Need to be something. For example, materials such as resin, decorative board, wood and metal are often used for a long period of time under severe weather such as hot weather or snowy weather, or in a strong acidic or basic atmosphere. The hard coat agent used for such a material must form a film capable of imparting properties such as weather resistance, surface hardness, heat resistance, and chemical resistance.

[0003] As hard coating agents conventionally used for these applications, silicone-based, acrylic-based, and urethane-based polymer compounds are known.

[0004]

However, the conventional silicone-based hard coat agent gives a film excellent in heat resistance and water repellency, but has insufficient flame retardancy and stain resistance, and further has poor adhesion. However, there is a problem that a base treatment must be performed at the time of coating because of poor quality. In addition, acrylic and urethane hard coat agents have a problem that heat resistance, flame retardancy, and abrasion resistance are insufficient.

Further, the conventional hard coat 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 furthermore a problem that the adhesive strength is remarkably reduced by repeated heating and cooling. There was also.

An object of the present invention is to solve such a conventional problem and to provide a hard coat agent composition capable of providing a film excellent in abrasion resistance, weather resistance, heat resistance, chemical resistance and the like. Is 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). Characterized in that the main component is a reaction product of tetramethylol (meth) acrylate and phosphoric anhydride.

[0008]

Embedded image

(Where R represents H or CH ₃ )
The reactant used as a main component in the present invention is bis [(meth) acryloxymethyl] methanol and one alcohol of tetramethylolmethanetri (meth) acrylate, or a mixture of both alcohols and phosphoric anhydride (phosphorus pentoxide). Is a reaction composition reacted with

The reaction product of the alcohol and phosphoric anhydride used as the main components in the present invention can be produced by a general method for producing a phosphoric acid ester, and can be prepared in a dry inert non-aqueous solvent or without solvent. It can be obtained by reacting .about.3.5 mol of alcohol, preferably 3 mol of alcohol with 1 mol of phosphoric anhydride.

The inert non-aqueous solvent used in this reaction includes benzene, toluene, xylene, chloroform, methylene chloride, cyclohexane, ether, tetrahydrofuran, 1,4-dioxane and the like. The reaction is generally carried out between room temperature and 150 ° C. for several hours, preferably between 30 and 70 ° C. for 2 hours.
Stir for 3 hours. 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 a mixture of methacrylates with methyl acrylate, hydroxyethyl acrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, etc., 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.

[0013] Such a reaction curable compound is blended within a range in which the required properties are acceptable. For example, when flame retardancy is required, the phosphorus content of the entire hard coat agent is 1 to 1. The reaction curable compound is contained so as to be 5% by weight.

[0014] The reaction-curable hard coat agent composition of the present invention may further contain a filler. By including a filler, the abrasion resistance can be further improved. Examples of such a filler include mica, silica, talc, alumina, apatite, glass beads, powders such as barium silicate, silicon nitride, silicon carbide, and potassium titanate, whiskers, and organic fillers such as polymethyl methacrylate. Can be.

Among these fillers, silica powder, barium titanate whiskers, and mica are particularly preferable in terms of abrasion resistance, abrasion 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 the alcohol and phosphoric anhydride.
Is preferably within the range. If the amount is less than 5% by weight, the properties may not be sufficiently improved, and if the amount exceeds 200% by weight, the ratio of the reaction-curable composition may decrease and the mechanical strength may be insufficient.

In the present invention, the reaction product of the above-mentioned alcohol and phosphoric anhydride is generally obtained as a liquid having a high viscosity. Therefore, the reaction product can be used as it is. However, if necessary, an aqueous or non-aqueous solvent or an organic solvent may be used. It can be used by dissolving or dispersing in a solvent. For example, emulsified or suspended in water or water / alcohol, or 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 dissolving or dispersing it in ethers such as tetrahydrofuran and dioxane and alicyclics such as cyclohexane and cyclohexanone.

The reaction-curable hard coat 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 other ordinary coating agents. Can be done.

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

The reaction-curable hard coat composition of the present invention can be cured at room temperature, but heat curing, light curing, and electron beam curing are preferred in view of the properties of the resulting film. In this case, a reaction initiator or a 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, the curing is generally performed at a temperature of 100 ° C. or higher, although it depends on the composition of the hard coat agent. In the case of photo-curing, ultraviolet rays having a wavelength in the range of 200 to 550 nm are irradiated for 1 second or longer, and the integrated light amount is 100
It is preferable to be 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 properties of the contained phosphorus atoms. Further, since one molecule has a plurality of (meth) acrylic groups, a film having excellent properties such as heat resistance, water resistance, weather resistance, and abrasion resistance is formed.

Further, an antistatic function can be provided by the effect of the hydroxyl group present in the molecule, and problems such as adhesion of dust due to charging of a plastic lens or a cathode ray tube can be avoided. Further, the dispersibility of the filler and the adhesion to the substrate are excellent. For this reason, even if it is exposed to an acid or an alkali for a long time, it hardly peels off, and the surface of the coated material can be stably protected for a long time.

Furthermore, the coating formed by the reaction-curable hard coating composition of the present invention is essentially transparent and can be used for coating the surface of decorative boards and the like. Further, since the polymerization shrinkage is low, the material hardly deforms due to the curing reaction.

[0023]

【Example】

(Example 1) Bis (methacryloxymethyl) methanol and phosphoric anhydride
In a 1 liter flask equipped with a stirrer, bis (methacryloxymethyl) methanol 4
56 g, phosphoric anhydride (phosphorus pentoxide) 95 g, and p-methoxyphenol 0.8 g were charged, protected from light,
The mixture was stirred for a period of time to react, and a pale yellow reaction composition having a viscosity of about 500 cps was quantitatively obtained. FIG. 1 shows the infrared absorption spectrum of the obtained reaction product. The analysis 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 5 mm-thick polycarbonate plate, and irradiated with a 20 W ultraviolet lamp for 30 minutes in a nitrogen atmosphere to obtain an almost colorless transparent cured film (thickness: 10 μm).

The surface pencil hardness of the obtained cured film was 9H. (The surface pencil hardness of the polycarbonate plate was F.) The hard coat agent was applied to a glass plate in the same manner, cured, and the hardness of the film was measured. The surface pencil hardness was over 9H.

Further, the sandfall abrasion (ΔH) was measured in accordance with ASTM D-673, and was found to be 23. Since sandfall abrasion (ΔH) of the polycarbonate plate is 70,
The effect of applying the hard coat agent is clearly observed. Example 2 of tetramethylolmethane triacrylate and phosphoric anhydride
The reaction was carried out in the same manner as in Example 1 except that 600 g of tetramethylolmethane triacrylate was used as the alcohol for the reaction composition, and a pale yellow reaction composition having a viscosity of about 20,000 cps was quantitatively obtained. FIG. 2 shows the infrared absorption spectrum of the obtained reaction composition. The analysis 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 at a ratio of 1% by weight to the obtained reaction composition, and this was made up to 30% by weight with chloroform. To prepare a photoreactive curable hard coat agent.

The obtained hard coat agent is applied to a 5 mm-thick polycarbonate plate, dried, and irradiated with a 20 W ultraviolet lamp for 30 minutes under a nitrogen atmosphere to form a nearly colorless transparent cured film (thickness: 10 μm). Obtained.

The surface pencil hardness of this cured film was 8H. Similarly, the surface coating had a hardness of 9H on the cured film obtained by applying and hardening a hard coat agent on a glass plate. Sandfall abrasion (ΔH) was measured in the same manner as in Example 1.
It was 7. Example 3 Bis (methacryloxymethyl) methanol and tetrame
A mixture of tyrolmethane triacrylate and phosphoric anhydride
Using 228 g of bis (methacryloxymethyl) methanol and 300 g of tetramethylol methane triacrylate as alcohols, the reaction was carried out in the same manner as in Example 1, except that the reaction composition was a slightly yellow reaction composition having a viscosity of about 10,000 cps. Was obtained quantitatively. In the obtained reaction composition, 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
m on a polycarbonate plate.
Irradiation with an ultraviolet lamp of W for 30 minutes gave an almost colorless transparent cured film (thickness: 10 μm).

The cured pencil obtained had a surface pencil hardness of 8H. The cured film applied on the glass plate and cured had a pencil hardness of 9 or more. The abrasion loss (ΔH) measured in the same manner as in Example 1 was 25. (Example 4) Evaluation of stain resistance and flame retardancy The cured films 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 using tobacco, no burning was observed, and very good results were obtained. (Example 5) Evaluation of impact resistance, transparency, and oil resistance Twenty polycarbonate sheets 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 cracks were observed in any of the test pieces of Examples 1 to 3.

When the transparency was evaluated in accordance with JIS K7105, the visible light transmittance was 90% or more, showing very good transparency. 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 immersed test pieces. As a result, no abnormalities due to gasoline immersion were observed.

From the above results, by coating the reaction-curable hard coating agent according to the present invention on a polycarbonate plate, it can be used as a window glass for transport equipment and buildings, a windshield for helmets and motorcycles, and a transparent protection for various machines. It was confirmed that it was suitable as a cover. (Example 6) Application to wooden table The hard coat agents of Examples 1 to 3 were applied to the surface of the wooden table, and irradiated with ultraviolet rays in the same manner as in Examples 1 to 3 to form a cured film. JIS K5400 for the cured film
When a cross cut test was performed in accordance with the test, no peeling was observed. In addition, when the surface of the cured film was strongly rubbed with steel wool and the scratch resistance was evaluated, no scratch was found.

The kettle which was boiled was placed directly, but no trace was found, and it was confirmed that the heat resistance was good. In addition, no burning was observed in the flame retardancy test using tobacco, and very good heat resistance was exhibited.

As described above, by applying the hard coat agent according to the present invention to a woodwork product, excellent properties such as scratch resistance and heat resistance can be imparted. (Example 7) Application to unglazed roof tiles The hard coat agent compositions of Examples 1 to 3 were applied on unglazed roof tiles to a thickness of 20 µm, and 1 mm from a distance of 20 cm.
A high-pressure mercury lamp of 00W with an integrated light quantity of 5000 mJ / cm ²
Irradiation was performed to form a cured film.

The top-coated roof tile having the cured film thus formed showed no contamination even after a 6-month outdoor exposure test, and no change was observed in a 5000-hour acid weather test assuming acid rain. Was.

These cured films are made of JIS K540.
No peeling was observed in the grid 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 give very excellent properties. (Example 8) Evaluation of antistatic performance A polycarbonate plate (PC plate) and a polymethyl methacrylate plate (P) treated with the hard coat agent of Examples 1 and 2
(MMA plate) to evaluate the antistatic performance. Table 1 shows the results. Evaluation is based on MIL standard
Electro-Tech Systems, Inc
The charge was attenuated by Static Decay Meter 406C (until the charge was applied at 5000 V with + or-and the charge disappeared).

[0038]

[Table 1]

As is evident from Table 1, the hard coat agent of the present invention has a very large charge attenuating ability and can provide a good antistatic function.

[0040]

As described above, the reaction-curable hard coat agent composition according to the present invention has high hardness and can form a film excellent in stain resistance and flame retardancy.
In addition, this cured film shows very strong adhesion to the surface of materials such as plastic materials, wood, ceramics, glass, paper and metal, and also has good chemical stability such as acid resistance and alkali resistance. It is. Therefore, the hard coat agent of the present invention can be used for decorative board, plastic, wood,
It can be used as a hard coat agent for coating printed matter, metal, textile, magnetic material, ceramics, glass, optical fiber, and the like. In particular, antistatic hard coats such as plastic glass, plastic lenses, cathode ray tubes, and electromagnetic wave cut TV filters, hard coats on the inside panels of various transports, top coats on this tile and straight tiles, top coats on high-rise buildings and general residential exterior walls It can be suitably used for a coat, a top coat of a tower / pier, a top coat of a manhole and a grating, a clear coat for an automobile exterior plate, and a hard coat of furniture / woodwork products.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of a 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 an alcohol and phosphoric anhydride prepared in Example 2 according to the present invention.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C09D 4/00-4/06 CA (STN)

Claims (1)

(57) [Claims] 1. A reaction product of bis [(meth) acryloxymethyl] methanol represented by the formula (I) and / or tetramethylolmethanetri (meth) acrylate represented by the formula (II) and phosphoric anhydride. A reaction-curable hard coat agent composition comprising a main component. Embedded image (Where R represents H or CH ₃ )