JPS6051512B2 - Paint composition with excellent functionality - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention uses active energy ray irradiation in an air atmosphere to
The present invention relates to a coating composition that has excellent abrasion resistance, antifogging properties, and antistatic properties, and is capable of forming a crosslinked cured film that can be dyed.

Synthetic resin molded products made from polymethyl methacrylate resin, polycarbonate resin, polyallyl diglycol carbonate resin, etc. are not only lighter and more impact resistant than glass products, but also inexpensive and easy to mold. It has various advantages such as organic plate glass, lighting equipment covers, optical lenses, eyeglass lenses, reflectors, mirrors, and other optical applications, signboards, displays, etc. Applications are being developed in many fields such as decorative applications, name plates, dust cover cases, and automobile parts.

However, these synthetic resin molded products lack abrasion resistance on the surface, so parts may break during transportation. During installation or use, the surface may be damaged due to contact with other objects, impact, or attraction, resulting in lower product yields and loss of aesthetic appearance.

The present applicant has already discovered that a polyfunctional (meth)acrylate monomer is crosslinked and cured by active energy ray irradiation, and has excellent weight properties, and that it can improve the abrasion resistance of the surface of synthetic resin molded articles. He discovered that it was effective as a forming material and made many proposals (Special Publication No. 48-42211).
No. 49-12886, No. 49-22951, No. 49-148, No. 49-22952, Japanese Patent Application No. 49-407? ).

However, although the synthetic resin molded products manufactured by the previous method have excellent wear resistance and smoothness, they become cloudy when exposed to moisture, and the coating formed on the synthetic resin molded products hardens due to crosslinking. Since it is a film, it is easily charged and attracts dust, and it is also difficult to dye it.

Therefore, the inventors of the present invention have conducted further studies to improve the above-mentioned problems, and have found that polyethylene glycol (meth)
By combining acrylate with a phosphate ester monomer having a specific structure and an ethanolamine compound, antifogging properties, antistatic properties, and dyeability can be improved while maintaining wear resistance and smoothness. They discovered this and completed the present invention.

That is, the present invention is based on the following general formula (where n is 0 or an integer of 1 to 4, at least three of X are CH2=CR-COO, and the remaining are 10H groups).

R is hydrogen or a methyl group. ) and 95% by weight of a polyfunctional monomer A3O of mono- or polypentaerythritol poly(meth)acrylate having three or more (meth)acryloyloxy groups in one molecule and the following general formula (in the formula, R1 is hydrogen or a methyl group, R2 is an alkoxy group or (meth)acryloyloxy group having 1 to 5 carbon atoms, and n is an integer of 5 to 30.) Polyethylene glycol (meth)acrylate monomer represented by (#) 3~
A monomer CO having 4% weight and 2 or less (meth)acryloyloxy groups in 1 molecule and 3% weight and the following general formula (wherein R3 is hydrogen or a methyl group, R4 is hydrogen or CH2- and -℃(CH2)n group, R5 is water
11 or a methyl group, and m and n are integers of 1 to 5.

) and the following general formula (wherein R6 and R7 are hydrogen and have 1 to 1 carbon atoms)
15 alkyl group or CH2CH2OH group.

) Ethanolamine compounds e1 to W weight %
5 to 9 parts by volume of a monomer mixture A, 95 to 1 part by volume of at least one organic solvent B mixed with the monomer mixture A to form a homogeneous solution, and a photosensitizer CO to 1 part by weight (based on a total of 100 parts by weight of the monomer mixture A and organic solvent B), and by irradiating it with active energy rays in air, it improves wear resistance, surface smoothness, and cloudiness,
The present invention also provides a coating composition that has excellent antistatic properties and can form a crosslinked cured film that can be dyed. General formula used in the present invention (wherein n is 0 or an integer of 1 to 4, at least three of X are CH2=CR-COO, and the rest are 1OH groups).

R represents hydrogen or a methyl group. Polyfunctional monomer a of mono- or polypentaerythritol poly(meth)acrylate shown in ) has very good polymerization activity when irradiated with active energy rays, and is crosslinked and cured to have high resistance. It forms a cross-linked cured polymer that exhibits abrasion properties. In the present invention, the purpose can be fully achieved by using the polyfunctional monomer a represented by the above general formula (1), but especially pentaerythritol tri(meth)
Polymerization activity of acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. when exposed to active energy rays in air , and ease of handling due to low viscosity.

The polyfunctional monomer a represented by the general formula (1) may be used alone or in combination of two or more. The proportion of polyfunctional monomer a used in monomer mixture A is 30 to 95% by weight, preferably 35 to 94% by weight.

If the amount of polyfunctional monomer a is less than 3% by weight in monomer mixture A, a cured film with sufficient wear resistance cannot be obtained,
Moreover, if the amount exceeds 95% by weight, the smoothness of the coating will be poor, which is not preferable. Furthermore, in the present invention, even if a polyfunctional monomer has three or more (meth)acryloyloxy groups in one molecule, a polyfunctional monomer that does not satisfy the general formula (1), such as a Methylol propyl
Polyfunctional (meth)acrylates such as tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and pentaglycerol tri(meth)acrylate have poor polymerization activity when irradiated with active energy rays in the air, making it difficult to form a coating film.・It is not used because it cannot perform crosslinking and curing. Formula (■) used in the present invention
The polyethylene glycol (meth)acrylate monomer b represented by has a ring-opening polymerization degree n of ethylene oxide of 51
-30 (meth)acrylic acid mono- or diester of polyethylene glycol.

When n is less than 4, hydrophilicity is low and the effect of the present invention on antifogging properties cannot be obtained, and when n exceeds 30, solubility in organic solvents decreases, resulting in poor hardness and poor smoothness of the cured line. Therefore, it is undesirable. A particularly preferred range is for n to be 9 to 23. Regarding the ester structure, either mono- or diester of (meth)acrylic acid may be used, but diester is more preferable from the viewpoint of developing hardness. The proportion of monomer b used is 3 to 4% in monomer mixture A;
The amount is preferably 10 to 3% by weight, and if it is less than 3% by weight, the antifogging property will not be improved, and if it exceeds 4% by weight, the hardness will decrease, which is not preferable. In the present invention, the inclusion of monomer b is an essential condition from the viewpoint of improving antifogging properties. Moreover, monomer c [
Monomer c (hereinafter simply referred to as monomer c) is used after coating a molded article with a coating composition to provide smoothness to the coated surface and flexibility to the cured film. . Specific examples of monomer c include neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. methacrylate, 1,3-butylene di(meth)acrylate,
1,4-butanediol di(meth)acrylate, 1,
6-hexanediol di(meth)acrylate, 1,3
-Propylene glycol di(meth)acrylate, butyl(meth)acrylate, isobutyl(meth)acrylate, t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, 1,4-butylene glycol mono (
meth)acrylate, ethoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, 2-
Examples include hydroxy-3-chloropropyl (meth)acrylate, dipropylene glycol di(meth)acrylate, and the like.

Among these monomers, diethylene glycol di(meth)acrylate, triethylene diglycol di(meth)
acrylate, tetraethylene glycol dimethacrylate, 2-hydroxyethylene (meth)acrylate,
2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (
meth)acrylate, ethoxyethyl(meth)acrylate, ethyl carbitol(meth)acrylate, butoxyethyl(meth)acrylate, 1,4-butylene glycol mono(meth)acrylate, dipropylene glycol di(meth)acrylate etc. Monomers having a hydroxyl group and/or a cyclic ether bond and/or a chain ether bond between the side chains or two (meth)acryloyloxy monomers have particularly excellent polymerization activity in air. Preferably used. These monomers c
may be used alone or in combination of two or more within the composition range. monomer c
The usage ratio of is 0 to 3% by weight in mixture A. On the other hand, if the amount of monomer c exceeds 3%, it is not preferable because a crosslinked cured coating having sufficient wear resistance cannot be obtained. The phosphoric acid ester monomer d used in the present invention has at least one (meth)acryloyloxy group in the molecule as shown by (■), and specific examples include:
Examples include (meth)acryloxyethyl phosphate, di(meth)acryloxyethyl phosphate, (meth)acryloxypropyl phosphate, and (meth)acryloxybutyl phosphate.

Other halogenated vinyl phosphates, alkyl-substituted vinyl phosphates, and other substances that do not have a (meth)acryloyloxy group may inhibit air curing, or may not improve antifogging properties, antistatic properties, or dyeing properties. Appropriate. In the composition of the present invention, even if it has a (meth)acryloyloxy group, it is necessary to contain at least one 0H group in the phosphoric acid group, and if there is no 0H group, ethanolamine-based This is not preferable because the effect of combined use with other compounds is reduced. The ethanolamine compound e used in the present invention has at least one CH2C as shown by the formula (■).
Alkylamine having H2OH group and CH2CH
Alkylamines that do not contain 2OH groups are not preferred because they show little effect on improving antifogging properties and antistatic properties. The number of carbon atoms in the N-substituted alkyl group is suitably 1 to 15, and 16 or more carbon atoms are not preferred because the solubility in solvents decreases. In carrying out the present invention, it is essential that the above-mentioned phosphoric acid ester monomer and ethanolamine compound be blended together; even if they are blended alone, the desired effect cannot be obtained, and the anti-fogging Only poor properties can be obtained in terms of properties, antistatic properties, and dyeability.

Phosphate ester monomers and ethanolamine compounds undergo an exothermic reaction when mixed to form a complex that significantly improves hydrophilicity, resulting in antifogging, antistatic, and dyeing properties. This point is one of the major features of the present invention. In addition, if it is simply to impart antifogging properties, antistatic properties, and dyeability, conventionally known methods such as blending a surfactant or a hydrophilic compound with a dyeing seat may be applied; All of these methods cannot be put to practical use because they cause a drastic deterioration in wear resistance and appearance. However, when the phosphoric acid ester monomer and the ethanolamine compound of the present invention are combined, a crosslinked cured film can be obtained by irradiation with active energy rays in air without any deterioration in wear resistance or appearance. The usage ratio of phosphate ester monomer is
The weight amount in mixture A is from 1 to 15% by weight, preferably from 3 to 15%.

If it is less than 1% by weight, sufficient antifogging properties, antistatic properties and dyeing properties cannot be obtained, and if it exceeds 2% by weight, clouding occurs in the cured film and transparency is reduced, which is not preferable.

The proportion of ethanolamine compound used is monomer mixture A.
The content is 1 to 1% by weight, preferably 2 to 6% by weight.

If it is less than 1% by weight, sufficient antifogging properties, antistatic properties and dyeing properties cannot be obtained, and if it exceeds 1% by weight, the surface smoothness and hardness of the cured film will deteriorate, which is not preferable.

The blending ratio of the phosphoric acid ester monomer d and the ethanolamine compound e is not particularly limited as long as each is within the above usage amount range, but a weight ratio of D, e = 0.5/1 to 5/1 is particularly preferred. This is a preferable range.

The organic solvent B used in combination with the monomer mixture A constituting the coating composition of the present invention improves coating workability when coating the coating composition on the surface of a synthetic resin molded article, improves the ability to form a uniform coated film, and It is used to impart an extremely favorable effect on storage stability and to dramatically increase the adhesion of the crosslinked cured coating to the substrate. In the present invention, the organic solvent used is mixed with monopolyfunctional (meth)acrylate monomer mixture A to form a homogeneous solution.

2 The boiling point at normal pressure is 50°C or higher and 200°C or lower.

3.The viscosity at room temperature is 10 centipoise or less. 4
It is used in a proportion of 95 to 10 parts by weight (total 100 parts by weight) based on 5 to 9 parts of polyfunctional (meth)acrylate monomer mixture A.

It is necessary to satisfy the following conditions.

First, the first condition is to form a homogeneous solution with the polyfunctional (meth)acrylate monomer mixture A, for example, n
- Saturated hydrocarbon organic solvents such as hexane, n-heptane, and cyclohexane cannot be used because they do not form a homogeneous solution. The second condition of boiling point at normal pressure of 50°C or more and 200°C or less is important in order to form a crosslinked cured film with excellent uniform film formation properties or surface smoothness when applied to the surface of a synthetic resin molded product. and is a necessary requirement. If the boiling point at normal pressure is less than 50°C, after the coating composition is applied, the substrate surface is cooled by the latent heat of the organic solvent that evaporates from the coating film, and moisture in the air condenses there, causing the coating film to deteriorate. In addition, if the temperature exceeds 200°C, the organic solvent evaporates from the coating film very slowly, causing problems in workability, and the residual organic solvent may be removed during the active energy ray irradiation process. This is undesirable because the uniformity and surface smoothness of the cross-linked cured film may be lost due to the lack of balance between volatilization and the formation of a cross-linked cured film through polymerization, or the organic solvent may coat the cross-linked cured film and cause the film to whiten. . Therefore, the boiling point of the organic solvent used must be 50°C or more and 200°C or less at normal pressure, and more preferably 60 to 150°C. Also, the viscosity of the organic solvent used is 1
It is necessary that it is 0 centipoise or less, and if it exceeds 10 centipoise j, it is not preferable because the viscosity of the coating composition increases and the coating properties and crosslinked cured film performance deteriorate.

The amount of organic solvent used is preferably in the range of 95 to 1 part by weight (total 100 parts by weight) per 5 to 9 parts of the monomer mixture A, and if it is less than 1 part by weight, the paint composition Due to the high viscosity of the material, coating workability is poor, making it difficult to control the thickness of the applied film, reducing the ability to form a uniform film, and furthermore, the adhesion of the cross-linked cured film to the substrate may be affected under harsh conditions. Then it decreases.

On the other hand, if it exceeds 95 parts by weight, it is difficult to control the thickness of the crosslinked cured film, resulting in loss of surface smoothness and poor abrasion resistance, which is not preferred. Depending on the article on which a cross-linked cured film is formed, the cross-linked cured film is required to have extremely high surface smoothness, flexibility, and thinness of the film.

For this purpose, the viscosity of the paint composition is adjusted to improve coating workability.
In practice, it is extremely important to improve the uniformity of the applied film and to facilitate the control of the film thickness. In such cases, the viscosity of the coating composition should be controlled by adjusting the blending ratio of each component monomer in the monomer mixture and the amount of organic solvent used, and the method of forming the coating film should be adjusted according to the purpose. You need to choose. The type of organic solvent used must satisfy the conditions mentioned above, specifically alcohols such as ethanol, isopropanol, normal propanol, isobutyl alcohol, normal butyl alcohol,
Aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane, acid esters such as ethyl acetate, n-butyl acetate, and ethyl propionate, N, N'' Dimethylformamide, etc. These organic solvents may be used alone, or two or more types may be mixed as long as the boiling point and component ratio of the mixture meet the requirements mentioned above. Polymerizable monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, and styrene may be used as long as they have a specific purpose and meet the same conditions and have the same effects as organic solvents. It is also possible to use the organic solvent as a type of organic solvent.

Depending on the type of synthetic resin that is used as the base material, these organic solvents may cloud the material used for transparent purposes, elute dyes and pigments from the colored base material, and cause discoloration. Since the organic solvent itself may be prone to cracking, it is desirable to select the type of organic solvent to be used depending on the type of substrate or purpose on which a crosslinked cured film is to be formed. In the present invention, in order to apply the coating composition to the surface of a synthetic resin molded article and form a crosslinked cured film, it is necessary to irradiate the coating composition with active energy rays such as ultraviolet rays, electron beams, or radiation. Among these, the method using ultraviolet irradiation is the most preferred from a practical standpoint. When ultraviolet rays are used as energy rays for crosslinking and curing coatings, it is necessary to add to the coating composition a photosensitizer C that can initiate a polymerization reaction upon irradiation with ultraviolet rays.

Specific examples of such photosensitizers include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetone,
butyroin, toluoin, benzyl, benzophenone,
Carbonyl compounds such as P-chlorobenzophenone and P-methoxybenzophenone, sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide, azo compounds such as azobisisobutyronitrile and azobis-24-dimethylvaleronitrile, benzoyl Examples include peroxide compounds such as peroxide and ditertiary butyl peroxide.
These photosensitizers may be used alone or in combination of two or more. The amount of these photosensitizers added to the coating composition is in the range of 0 to 1 part by weight, preferably 0.01 to 1 part by weight, based on a total of 100 parts by weight of mixture A and organic solvent B. be.

Addition of too large a quantity is not preferable since it may cause coloring of the crosslinked cured film or a decrease in weather resistance. The coating composition used in the present invention may also contain a surface smoothing agent,
Additives such as surfactants, ultraviolet absorbers, and storage stabilizers may be added as appropriate.

Next, a wear-resistant synthetic resin molded article using the above-mentioned coating composition is manufactured by applying the coating composition to the surface of the synthetic resin molding and then irradiating it with active energy rays. Ru.

Synthetic resin molded products used to produce synthetic resin molded products with excellent abrasion resistance, surface smoothness, antifogging properties, and antistatic properties using the coating composition of the present invention include thermoplastic resins, thermoplastic resins, Various synthetic resin molded products regardless of curable resin, such as polymethyl methacrylate resin, polycarbonate resin, polyallyl glycol carbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin (AS
resin), polyvinyl chloride resin, acetate resin, ABS
Sheet-like molded products such as organic glass and reflective mirrors manufactured from resins, polyester resins, etc., film-like molded products,
Specific examples include rod-shaped molded products, various lens molded products, and various injection molded products such as lighting equipment covers.

Among these molded products, molded products manufactured from polymethyl methacrylate resin, polycarbonate resin, polyallyl diglycol carbonate resin, etc. are used to take advantage of their properties such as optical properties, heat resistance, and impact resistance. This is particularly preferred since it is often the case.

The various molded products described above can be used as they are, but if necessary, they can be used after being subjected to pretreatments such as cleaning, etching, corona discharge, active energy ray irradiation, dyeing, and printing.

In addition, methods such as brush coating, flow coating, spray coating, spin coating, or dip coating are used to apply the above-mentioned coating composition to synthetic resin molded products, but the coating process is simple and there is no loss of coating composition. Less workability,
Alternatively, a dip coating method is preferable in terms of productivity.

The amount of coating composition applied to the surface of the synthetic resin molded article varies depending on the amount of monomer mixture A contained in the coating composition or the purpose, but It is necessary to apply the crosslinked cured coating so that the film thickness is in the range of 1 to 30 μm.

The amount of coating composition corresponding to this is approximately . Around 15-3
The coating film may be made to have a coating thickness of 00 μm. If the thickness of the cross-linked cured film formed on the surface of the synthetic resin molded product is less than 1μ, the abrasion resistance will be poor, and if it exceeds 30μ, the cured film will have poor flexibility. This is not preferable because cracks are likely to occur, which may reduce the strength of the molded product itself.

In order to crosslink and cure the applied film, ultraviolet rays emitted from a light source such as a xenon lamp, low pressure mercury lamp, high pressure mercury lamp, or ultra-high 8 pressure mercury lamp or ultraviolet rays of 20 to 2,000 yen are usually used.
Electron beams, α rays, and β extracted from the KV electron beam accelerator
It is necessary to irradiate active energy rays such as rays and gamma rays.

The atmosphere for irradiating active energy rays is nitrogen gas,
Although it is of course possible to use an atmosphere of an inert gas such as carbon dioxide or an atmosphere with a reduced oxygen concentration, the coating composition according to the present invention can be crosslinked and cured with excellent wear resistance and other properties even under a normal air atmosphere. It is possible to form a film.

The temperature of the irradiation atmosphere may be room temperature, or may be an atmosphere heated to such an extent that no harmful deformation occurs to the base synthetic resin molded article. The synthetic resin molded product having a crosslinked cured film on the surface produced using the coating composition of the present invention has excellent surface smoothness and aesthetic appearance, and has extremely excellent surface hardness, abrasion resistance, and scratch resistance. be.

Furthermore, the hardened film formed on the surface has excellent anti-fogging and antistatic properties, and does not generate fog even when exposed to humidity, nor does it attract dust or dust at all even when rubbed. Furthermore, cross-linked cured coatings that do not contain phosphate ester monomers and ethanolamine compounds are difficult to dye regardless of the type of dye, but the cured coating of the present invention can be dyed with most types of dyes. It is. Among these, dyeing with basic dyes having amine salts or quaternary ammonium groups, or nitro-, azo-, anthraquinone-, or aminoketone-based disperse dyes is preferred; in the latter case, cationic,
Anionic, nonionic, or amphoteric surfactants can be used as dispersants, and chromiumbenzene-based, methylnaphthalene-based, 0-phenylphenol-based, aromatic ether-based, alkyl salicylate-based compounds, etc. can be used as carriers. . Furthermore, the crosslinked cured film of the present invention has excellent adhesion to substrates, and is extremely useful for applications such as organic window glasses, lighting equipment cover reflectors, eyeglass lenses, sunglass lenses, and optical lenses.

The contents of the present invention will be explained in more detail below with reference to Examples.

Note that the measurement and evaluation in the Examples was performed in the following manner. (
1) Abrasion resistance a Surface hardness...JISK565l-1
Pencil hardness b scratch test according to 966...
・Abrasion test with #000 steel wool 0... Even if lightly rubbed, the surface will hardly be scratched.
No scratches.

Δ...If you rub it lightly, the surface will be slightly scratched.
×...Even if you rub it lightly, the surface will be seriously scratched.
(same level as the base resin) (2) Cross-cut cellophane tape peel test on adhesive crosslinked cured film.

That is, 100 cuts of 1 Tr0ft were made by cutting 11 lines in the length and width of the film, each reaching the base material at intervals of 1 wn, and then cellophane tape was pasted on the cut line and rapidly peeled off. Repeat this cellophane tape operation three times at the same location. 0...No peeling of the cross-linked cured film even after repeating 3 times Δ...Number of peeling after repeating 3 times 1 to 5 Faults ×...Number of peeling after repeating 3 times 51 ~10 Smoothness measurement of the fence (3) surface 0...The smoothness of the surface of the coating is very good and mirror-like.
It can be said that it is a face.

Δ...The surface smoothness of the film is good, but it is young.
There is a drought.

×: The surface is disordered and the smoothness is poor.

(4) Antistatic property a Cigarette ash adhesion test 0...Rinse the surface of the cured film 20 times with a cotton cloth.
Approximately 1 CrI from fresh cigarette ash after rubbing
No ash attached at all even when brought close to 1.

Δ: Slight adhesion due to the same operation as above. ×: Significant adhesion occurs during the same operation as above.

b Measurement of charging half-life After holding the sample for 24 hours under constant temperature and humidity at a temperature of 20°C and a relative humidity of 60%, a voltage of 10 KV was applied for 10 seconds using an Honest meter (manufactured by Shishido Shokai) to measure the half-life. .

(5) Anti-fogging property 0...Temperature 20℃, relative humidity 60% constant temperature and humidity
Even if you hold a sample between 2 servings below and blow air into it for 1 time, no clouding will occur.

Δ...Slight cloudiness occurs due to the same operation as above.
Living.

×...Due to the same operation as above, fogging will occur significantly.
Living.

Example 1 A curing liquid having the composition shown in Table 1 was prepared, and a methacrylic resin plate (manufactured by Mitsubishi Rayon,
0.5C by soaking (product name: Acrylite)! RL/Se
A pulled film was formed at a speed of c.

After leaving it as it is, the board coated with the paint composition was exposed to a high-pressure mercury lamp (Iwasaki Electric, 2KWH0-L2L) in the air.
) was irradiated on both sides of the plate from a distance of 20α for 1 to 2 minutes. The results obtained are shown in Table-1. As shown in Experiment No. 1, the composition of the present invention forms a good crosslinked cured film by irradiation in the air, and has not only abrasion resistance, smoothness, and adhesion, but also antifogging properties, antistatic properties, It also has uniformly excellent performance in terms of dyeability.

In comparison, systems lacking either polyethylene glycol (meth)acrylate, phosphoric acid ester monomer, or ethanolamine compound, as in Experiments 2 to 4, had poor wear resistance, smoothness, and adhesion. is good, but it is not possible to obtain one that satisfies all of the antifogging properties, antistatic properties, and dyeing properties. Furthermore, as shown in Experiment No. 5, systems using trifunctional acrylates other than those of the present invention do not crosslink and cure even when exposed to ultraviolet rays in air.

Example 2 A methacrylic resin plate having a thickness of 2 globes was immersed in a curing liquid having the composition shown in Table 2, and the plate was pulled up at a speed of 0.5 cm/Sec to form a coating.

After leaving it as it is for one minute, it was exposed to ultraviolet rays from a high-pressure mercury lamp in an air atmosphere from a distance of 20CTn on each side of the board.
It was irradiated for 5 seconds. The obtained results are shown in Table 2, and they show uniformly good performance. Example 3 Curing solutions were prepared with different types and amounts of polyethylene glycol ester as shown in Table 3, and the method of Example 1 was repeated to form cured films and evaluate the performance.

As is clear from Table 3, if the degree of ring-opening polymerization of polyoxyethylene is too small (n = 4), the antifogging property will be poor, and if it is too large (n = 32), the antifogging property will be good, but the hardness, smoothness and It can be seen that this is not preferable because the adhesion decreases.

Furthermore, if the amount of polyethylene glycol ester added is too small, the antifogging properties will be poor, and if it is too large, the smoothness, hardness and adhesion will be reduced.

It should be noted that the antistatic property and dyeability are uniformly good regardless of the type or amount of polyethylene glycol ester added, and it is clear that only the antifogging property is greatly affected.

Example 4 As shown in Table 4, methacryloxyethyl phosphate (MEP) and N-lauryl diethanolamine (RE
Curing liquids were prepared with varying amounts of A), crosslinked cured films were prepared according to Example 1, and the performance was evaluated.

The results are shown in Table 4. A system lacking either MEP or REA provides poor antifogging and antistatic properties.

Even if they are used in combination, if either ITO or REA is blended in a ratio outside the scope of the present invention, some kind of performance deterioration occurs and a satisfactory product cannot be obtained.
That is, if it is too small, both the anti-fog and anti-static properties will be insufficient.
If the amount is too large, the appearance, hardness and adhesion of the cured film will deteriorate. As for dyeability, it is possible to dye by adding MEP or REA, but from the viewpoint of concentration or uniformity, it is preferable to use them together within the scope of the present invention.

Example 5 A cured film was prepared by repeating the method of Example 1, except that the composition of Experiment No. 1 of Example 1 was changed, and the types of phosphate ester monomer and alkylamine were changed, and the performance was evaluated.

The results are shown in Table-5. Even if a phosphate ester monomer without a (meth)acryloxy group or an alkylamine without a CH2CH2OH group is combined, the effects of the present invention cannot be obtained, and only products with inferior antifogging and antistatic properties are obtained. I can't get it.
Furthermore, when N-lauryl diethanolamine, which has an alkyl amine having a CH2CH2OH group and whose alkyl group has 15 or more carbon atoms, is used, the solubility deteriorates, resulting in a decrease in the smoothness and transparency of the cured film, and the antistatic property is also poor. It was also difficult to achieve sufficient and uniform staining. Example 6 Methacryloxyethyl phosphate (MEP) and N-lauryl diethanolamine (RE
A hardening liquid was prepared by changing the amount of A), and the method of Example 1 was repeated to form a cured film.Table 6 shows the results of comparing the dyeability of basic dye and disperse dye.

In systems lacking one or both of MEP and REA, antifogging properties,
Not only is the antistatic property inferior, but also the dyeing property is not satisfactory.

On the other hand, the composition of the present invention shows uniformly excellent performance, and it is clear that it is uniformly dyed in deep colors with no significant difference with either basic dyes or disperse dyes.

Example 7 3rn! A cured film was formed on an n-thick polycarbonate resin plate (manufactured by Mitsubishi Gas Chemical, trade name: Iupilon) using the subdural liquid of Experiment No. 1 in the same manner as in Example 1, and its performance was investigated.

The cured film was smooth, had a thickness of 3.5 μm, and had good adhesion when scratched by the pencil hardness test and steel wool test. Regarding the antistatic property, cigarette ash did not adhere to it and the half-life was 1.1 seconds, which was good. In addition, it was possible to dye a dark color uniformly, and there was no fogging caused by the exhalation test, and the antifogging property was excellent. Example 8 Diameter 8C made of polyallyl diglycol carbonate
! TL and thickness 2? The performance of the cured product was examined in the same manner as in Example 7 except that a lens (CR-39 lens) was used.

The cured film was smooth and had a good appearance, the pencil hardness showed no scratches in the 7H1 steel wool test, and the adhesion was good. Also, the half-life is 0. In the second beating, no cigarette ash was attached, a dark and uniform dyeing was possible, and the anti-fogging property was also good. Example 9 Polymethyl methacrylate lens (diameter 8α, thickness 2
T! The method of Example 8 was repeated using Rm).

The cured film of the obtained product was also good and had almost the same performance as Example 8. Example 10 21 parts of dipentaerythritol pentaacrylate, 1.8 parts of pentapentaerythritol dodeca acrylate, 3.8 parts of tetrahydrofurfuryl acrylate, poly. Ethylene glycol dimethacrylate (n=23) 3
．． 8 parts, methacryloxyethyl phosphene. Part 6,
A cured film was formed on the surface of a methacrylic resin board in the same manner as in Example 1 using a composition consisting of 1.4 parts of N-lauryl diethanolamine, 54.5 parts of isopropanol, 9.1 parts of toluene, and 1.8 parts of benzoin ethyl ether. The performance was evaluated by forming a

The resulting sample had a pencil hardness of 7H and was not scratched in the steel wool test.

Claims (1)

[Claims] 1. The following general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (in the formula, n
is 0 or an integer from 1 to 4, at least 3 of X are CH
_2=CR-COO- group and the rest are -OH groups. R represents hydrogen or a methyl group. ) Polyfunctional monomer a of mono- or polypentaerythritol poly(meth)acrylate having three or more (meth)acryloyloxy groups in one molecule represented by 30 to 95% by weight and the following general formula ▲ Numerical formula, chemical formula , tables, etc.▼(II) (In the formula, R_
1 is hydrogen or a methyl group, R_2 is an alkoxy group or (meth)acryloyloxy group having 1 to 5 carbon atoms, and n is an integer of 5 to 30. ) polyethylene glycol (meth)acrylate monomer b 3 to 40% by weight and 2 or less (
Monomer c0-30 having meth)acryloyloxy group
Weight% and the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (III) (In the formula, R_3 is hydrogen or methyl group,
R_4 is hydrogen or a ▼ group, R_5 is hydrogen or a methyl group, and m and n are integers from 1 to 5. ) phosphoric acid ester monomer d1 to 20% by weight
and the following general formula NR_6R_7(CH_2CH_2OH
) (IV) (In the formula, R_6 and R_7 are hydrogen, carbon number 1-
15 alkyl group or CH_2CH_2OH group. ) and at least one organic solvent B95 which is mixed with the monomer mixture A to form a homogeneous solution. ~10 parts by weight and photosensitizer C0-1
0 parts by weight (total of monomer mixture A and organic solvent B: 1
00 parts by weight), and by irradiating it with active energy rays in the air, it forms a crosslinked cured film that has excellent abrasion resistance, smoothness, antistatic properties, and antifogging properties, and is dyeable. A coating composition with excellent functionality that is characterized by its ability to absorb moisture. 2. Phosphate monomer d of general formula (III) is selected from the group consisting of acryloxyethyl phosphate, methacryloxyethyl phosphate, and dimethacryoxyethyl phosphate. A highly functional coating composition according to claim 1. 3. The highly functional coating composition according to claim 1, wherein the ethanolamine compound of general formula (IV) is diethanolamine having an alkyl group having 1 to 15 carbon atoms.