JPS621425B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a coating material composition capable of forming a crosslinked cured coating having excellent abrasion resistance, surface smoothness, dyeability, and antistatic performance with excellent durability by irradiation with active energy rays. Synthetic resin molded products such as polymethyl methacrylate resin, polycarbonate resin, and polyallyl diglycol carbonate resin are not only lighter and more impact resistant than glass products, but also inexpensive and easy to mold. It has the advantages of organic plate glass, lighting equipment covers, optical lenses, eyeglass lenses, reflectors, mirrors, and other optical applications; signboards, display displays, and other decorative applications; name plates, dust cover cases, Application development is progressing in many fields such as automobile parts. However, these synthetic resin molded products lack surface wear resistance, so they are susceptible to contact with other objects, impact, and pulling during transport, when installing parts, or during use. As a result, the surface is damaged, reducing product yield and deteriorating the aesthetic appearance. In particular, molded products are used for cameras, optical lenses such as magnifying glasses, optical lenses such as fashion glasses, sunglasses, corrective lenses, or window glass, decorative cases and covers, watch lenses, reflectors, and mirrors. In such cases, the damage that occurs to the surface may significantly reduce its commercial value, or
Since it becomes unusable in a short period of time, there is a strong demand for improving the abrasion resistance of the surface. The present applicant has already discovered that a polyfunctional (meth)acrylate monomer has excellent crosslinking and curing polymerizability upon irradiation with active energy rays, and that it can improve the abrasion resistance of the surface of synthetic resin molded products by forming a crosslinked cured film. He discovered that it was effective as a forming material and made many proposals (Special Publications No. 48-42211, No. 49-12886).
No. 49-22951, No. 49-14859, No. 49-
Publication No. 22952, Japanese Patent Application No. 52-18485, No. 52-19038
No. 53-4079). However, on the other hand, it has also been found that there are the following problems. In other words, since the coating formed on the surface of the molded product is a crosslinked cured coating, it is difficult for the dye to diffuse and cannot be dyed, and the product value is reduced because static electricity is generated due to friction and dust tends to adhere. As a result, the range of applications was limited and this became a major obstacle in practical use. Conventionally, a method has been proposed in which a compound having a large number of dyeing sites is added to a coating material composition for the purpose of improving dyeability, but the addition of these compounds reduces abrasion resistance and is therefore not practical. In addition, as a method for preventing the generation of static electricity, a method of blending an antistatic agent and a method of copolymerizing a monomer having antistatic ability are known. The former method is easy to manufacture, but only the inhibitor present on the surface is effective; therefore, a high concentration is required to obtain sufficient inhibitory ability, resulting in a decrease in wear resistance and appearance. It will happen. In addition, since the inhibitor present on the surface easily falls off due to washing or friction, and the prevention ability decreases, devises are made so that the inhibitor present in the matrix gradually oozes out, but this is due to the stickiness of the surface. Not only does it become opaque, but its resistance to washing and the like is so-called temporary and not permanent. The latter, ie, the copolymer type, exhibits no effect other than the monomers in the surface layer, so a large amount of monomers must be added, resulting in a decrease in wear resistance and appearance. In view of the current situation, the present inventors have conducted extensive research and have found that the above-mentioned drawbacks can be solved at once by blending a sulfonic acid monomer with a specific structure and an ethanolamine compound. Heading The invention has been completed. That is, the present invention provides three or more (meta) molecules in one molecule.
Polyfunctional monomer (a) with acryloyloxy group 50
~98% by weight and the general formula below (In the formula, R ₁ is hydrogen or a methyl group, R ₂ is an alkoxy group having 1 to 5 carbon atoms or a (meth)acryloyloxy group, and n is an integer of 5 to 30.) Quantity (b) 0 to 40% by weight and the following general formula (In the formula, R ₃ is hydrogen or a methyl group, Y is a -COOH group or -COO group, and l, m, n and r are integers of 0 to 5.) 1 to 30% by weight of mer (c) and the following general formula NR ₄ R ₅ (CH ₂ CH ₂ OH) () (wherein R ₄ and R ₅ are hydrogen, an alkyl group having 1 to 15 carbon atoms, or - 5 to 90 parts by weight of a monomer mixture (A) consisting of 1 to 20% by weight of an ethanolamine compound (d) represented by CH ₂ CH ₂ OH group, and the mixture (A)
95 to 10 parts by weight of at least one organic solvent (B) mixed with to form a homogeneous solution and 0 to 10 parts by weight of a photosensitizer (C) (the monomer mixture (A) and the organic solvent ( Total with B)
(based on 100 parts by weight), and has the functionality of forming a cross-linked cured film with excellent abrasion resistance, surface smoothness, dyeability, and permanent antistatic properties by irradiation with active energy rays. The present invention provides an excellent coating material composition. The polyfunctional monomer (a) having three or more (meth)acryloyloxy groups in one molecule used in the present invention refers to a trihydric or higher polyhydric alcohol or a derivative thereof, (meth)acrylic acid or Crosslinkable monomers obtained by reaction with halides or esters of these acids, examples of polyhydric alcohols include trimethylolpropane, pentaglycerol, glycerin, diglycerin, pentaerythritol, Specific examples include pentaerythritol. These polyfunctional monomers are the main components that form a crosslinked and cured film when irradiated with active energy rays, but when irradiated in the air, the crosslinking and curing reaction is suppressed by the oxygen in the air. Some materials do not exhibit sufficient wear resistance, and in this case, it is necessary to irradiate under an inert gas atmosphere such as nitrogen gas or carbon dioxide gas. Since this is disadvantageous in practice due to the complexity of the working process, it is preferable to use a monomer that can form a crosslinked cured film having sufficient abrasion resistance by irradiation in air. A polyfunctional monomer that satisfies this condition has the following general formula: (In the formula, X ₁₁ , X ₁₂ , X ₁₃ , X ₂₂ , X ₂₃ ...Xn ₂ ,
At least three of Xn ₃ and X ₁₄ are CH ₂ = CR−COO
- group, and the rest are -OH groups. n is an integer from 1 to 5. R represents hydrogen or a methyl group. ) Mono- or polypentaerythritol poly(meth)acrylates represented by: It has very good polymerization activity upon irradiation with active energy rays, and is crosslinked and cured to form a highly crosslinked and cured polymer exhibiting high wear resistance. In the present invention, the purpose can be sufficiently achieved by using a polyfunctional monomer represented by the above general formula (), but in particular, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate,
Dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like are particularly preferred in terms of polymerization activity when irradiated with active energy rays in air and ease of handling based on low viscosity. The polyfunctional monomers represented by the general formula () may be used alone or in combination of two or more. The proportion of polyfunctional monomer (a) used is as follows: monomer mixture (A)
The content is 50 to 98% by weight, preferably 60 to 90% by weight.
The amount of polyfunctional monomer (a) is 50% by weight in the monomer mixture (A)
If the amount is less than 98 parts by weight, a cured film with sufficient wear resistance cannot be obtained, and if the amount exceeds 98 parts by weight, the smoothness of the film will be poor. The polyfunctional monomer (a) having three or more (meth)acryloyloxy groups in one molecule used in the present invention generally has a high viscosity, and in some cases, the surface smoothness of the crosslinked cured film may be affected. This may have an adverse effect on film thickness control. In such cases, a low-viscosity monomer (f) having two or less (meth)acryloyloxy groups in one molecule can be used in combination with the polyfunctional monomer (a). Specific examples of this monomer (f) 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 ) 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 cerbitol (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, dipropylene glycol di(meth)acrylate, and the like. Among these monomers, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol dimethacrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, glycidyl(meth)acrylate, ) acrylate, tetrahydrofurfuryl (meth)acrylate, ethoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate,
Butoxyethyl (meth)acrylate, 1,4-
butylene glycol mono(meth)acrylate,
Products that have a hydroxyl group and/or a cyclic ether bond and/or a chain ether bond between the monomer side chain or two (meth)acryloyloxy groups, such as dipropylene glycol di(meth)acrylate, are exposed to air. It is particularly preferred because it has excellent polymerization activity. Also, the boiling point of monomer (f) at normal pressure is
A suitable material has a viscosity of 20 centipoise or less at 150°C or higher and 20°C, and it is also possible to use a mixture of two or more types. The usage ratio is monomer mixture (A)
The content is preferably 30% by weight or less. If it exceeds 30% by weight, the abrasion resistance of the cured film decreases, which is not preferable. Monomer (b) of formula () used in the present invention
is a (meth)acrylic acid mono- or diester of polyethylene glycol having a degree of ring-opening polymerization n of ethylene oxide of 5 to 30. Although this is not an essential component in carrying out the present invention, it is preferable to use it in order to synergistically make the improvement effects of dyeability, permanent antistatic properties, etc. more remarkable. where n
If n is less than 4, the hydrophilicity is low and a synergistic effect on improving dyeability or antistatic property cannot be obtained, and if n exceeds 30, hardness decreases, which is not preferable. The proportion of monomer (b) used is 40% in the monomer mixture (A).
It is preferable that the amount is less than 40% by weight, and if it exceeds 40% by weight, the hardness will decrease and the wear resistance will be poor, so it is not preferable. The sulfonic acid monomer (c) of formula () used in the present invention is a sulfoalkyl ester of an unsaturated monocarboxylic acid having a double bond or an acid amide thereof. Ethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, sulfobutyl acrylate, sulfobutyl methacrylate, sulfoethyl vinyl acetate, sulfopropyl vinyl acetate, sulfopropyl vinyl propionate,
Examples include 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, and 3-acrylamido-3-methylbutanesulfonic acid. in general
Compounds having an SO ₃ H group are known to be effective in imparting hydrophilicity, but because of their strong hydrophilicity, they are highly soluble in water, but hardly soluble in organic solvents. Therefore, when applied to a reaction system that is mixed with an organic solvent as in the present invention,
Conventionally, it has been difficult to put it into practical use because it causes phase separation and becomes non-uniform. This is the same even when no organic solvent is used; it is almost incompatible with organic monomers, and although it is soluble in specific hydrophilic organic monomers, its solubility is extremely low and only a trace amount can be blended, so it is not enough. No effect will be obtained. Therefore, conventionally
The reality is that compounds with SO ₃ H groups can only be applied to systems using water as a solvent or systems using special organic solvents such as N,N-dimethylformamide or dimethyl sulfoxide as a medium. . However, when such a solvent system is applied to plastic, it has poor wettability and repulsion occurs, making it difficult to form a uniform coating film. Therefore, by using the sulfonic acid monomer represented by the general formula () in combination with a specific ethanolamine compound represented by the general formula (), the solubility in organic solvents can be greatly improved. The inventors of the present invention have discovered that a uniform cured film can be formed and that it has a remarkable effect on improving dyeing properties and antistatic properties. The effect of the present invention cannot be obtained with a sulfonic acid compound having a structure other than that shown in the above formula (). For example, in a compound in which Y is a phenyl group or a phenol group in the formula (), the ethanolamine of the formula () is not obtained. There is almost no improvement in solubility even when these compounds are used together. It should be noted that when using an alkali metal salt such as Na or K as a derivative of the sulfonic acid compound of the formula (), it is necessary to keep in mind that although the salt has a high hydrophilicity, the effect of improving solubility is small. ()
The proportion of the sulfonic acid monomer (c) of the formula in the monomer mixture (A) is 1 to 30% by weight, particularly preferably 5 to 20% by weight.
If the amount is less than 1% by weight, dyeing properties and antistatic properties will not be improved, and if it exceeds 30% by weight, the transparency and abrasion resistance of the cured film will decrease, which is not preferable. The most important features of the effects of the present invention obtained by using the sulfonic acid monomer (c) of formula () of the present invention are, firstly, dyeability without deteriorating wear resistance or appearance; The second point is that it provides permanent antistatic properties that do not deteriorate in performance due to washing or friction. Such an effect is extremely specific and can be obtained by the combined use of the sulfonic acid monomer of the formula () and the ethanolamine compound of the formula (), and increases the commercial value of the coating material composition of the present invention. This is a significant improvement. Taking 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as an example, which fits formula (), AMPS
Even when using diacetone acrylamide in which the SO ₃ H group is replaced with a COCH ₃ group, the dyeability is improved to some extent, but the hardness is greatly reduced and no effect on antistatic properties is observed. Also, like AMPS, vinylbenzenesulfonic acid has a vinyl group and an SO ₃ H group, and although it improves dyeability and antistatic properties to some extent, it has poor solubility and its usage is limited, so it must be added in small amounts. Due to this, the cured film becomes cloudy and the hardness decreases significantly. Furthermore, the slightly improved antistatic properties are easily lost by washing with water and are not permanent. The ethanolamine compound used in the present invention is an alkylamine having at least one -CH 2 CH 2 OH group in one molecule, as shown in the formula (), and is an alkylamine having at least one -CH ₂ CH ₂ OH group in one molecule, and is capable of dissolving sulfonic acid monomers. Alkylamines that do not have a CH ₂ CH ₂ OH group are not preferred because they have a small effect on improving solubility. Further, the number of carbon atoms in the N-substituted alkyl group is suitably 1 to 15, and if it exceeds 15, it is not preferable because the hardness decreases. Specific examples include ethanolamine, β-ethylhexylethanolamine, diethanolamine, N-butyldiethanolamine, N-hexyldiethanolamine, N-
-lauryldiethanolamine, N-cetyldiethanolamine, triethanolamine, and the like. As for the usage ratio, monomer mixture (A)
The appropriate amount is 1 to 20% by weight, preferably 5 to 15% by weight. If it is less than 1% by weight, the solubility of the sulfonic acid monomer will not improve, and if it exceeds 20% by weight, the transparency and hardness of the cured film will deteriorate. This is not preferable because it reduces the The blending ratio of the sulfonic acid monomer (c) and the ethanolamine compound (d) is not necessarily limited, but the weight ratio
A range of (c)/(d)=0.5/1 to 3/1 is particularly preferred. Monomer mixture constituting the coating composition of the present invention
The organic solvent (B) used in combination with (A) has extremely favorable effects on coating workability, uniform coating film formation, and storage stability when coating the coating composition on the surface of synthetic resin molded products. It is also used to increase the adhesion of crosslinked cured coatings to substrates. In the present invention, the organic solvent used is 1. A mixture of polyfunctional (meth)acrylate monomers.
(A) to form a homogeneous solution. 2 The boiling point at normal pressure is 50°C or higher and 200°C or lower. 3. Viscosity at room temperature is 10 centipoise or less. 4 Polyfunctional (meth)acrylate monomer mixture
95 to 10 parts by weight for 5 to 90 parts by weight of (A) (total
100 parts by weight). 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).
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 uniform film-forming property or a crosslinked cured film with excellent surface smoothness when applied to the surface of a synthetic resin molded product. be. If the boiling point at normal pressure is less than 50°C, after the coating composition is applied, the surface of the substrate is cooled by the latent heat of the organic solvent that evaporates from the coating, and moisture in the air condenses there, causing the coating to deteriorate. The surface smoothness of the membrane is lost and
On the other hand, if the temperature exceeds 200℃, the organic solvent evaporates from the coating film very slowly, causing problems in workability, and the residual organic solvent evaporates and polymerizes during the active energy ray irradiation process, resulting in the formation of a cross-linked cured coating. This is undesirable because the uniformity and surface smoothness of the cross-linked cured film may be lost due to unbalanced formation, or the organic solvent may remain in the cross-linked cured film and the film may become white. 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. In addition, the viscosity of the organic solvent used must also be 10 centipoise or less; if it exceeds 10 centipoise, the viscosity of the coating material composition will increase and the coating properties and crosslinked cured film performance will decrease, which is not preferable. The amount of organic solvent used is from 5 to 5 for the monomer mixture (A) mentioned above.
A range of 95 to 10 parts by weight (total 100 parts by weight) for 90 parts by weight is good; if it is less than 10 parts by weight, the viscosity of the coating material composition is high, resulting in poor coating workability.
It becomes difficult to control the thickness of the applied film,
Under severe conditions, uniform film formation may be reduced, and the adhesion of the crosslinked cured film to the substrate may also be reduced. 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. To this end, it is extremely important in practice to adjust the viscosity of the coating material composition to improve coating workability and uniformity of the coated film, and to facilitate control of film thickness. In such cases, the viscosity of the coating material 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 for forming the applied film should be adjusted. You need to choose accordingly. 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, and aromatic substances such as benzene, toluene, xylene, and ethylbenzene. group hydrocarbons, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane, ethyl acetate, acetic acid n
-butyl, esters such as ethyl propionate, and N,N dimethyl formamide. These organic solvents may be used alone,
Moreover, two or more types may be used in combination as long as the boiling point and component ratio of the mixture are within the range that satisfies the above-mentioned requirements. In addition, polymerizable monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, and styrene can be used as a type of organic solvent if they have a specific purpose and meet the same conditions and have the same effects as organic solvents. You can also. Depending on the type of synthetic resin that is used as the base material, these organic solvents may cause haze in those used for transparent purposes, may discolor the dyes and pigments in the colored base material, or may cause discoloration on the base material itself. Since cracks may easily occur, it is desirable to select the type of organic solvent to be used depending on the type of substrate on which a crosslinked cured film is to be formed or the purpose. In order to apply the coating composition of the present invention to the surface of a synthetic resin molded article and form a crosslinked cured film, it is necessary to irradiate the surface 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 applied films, it is necessary to add to the coating material composition a photosensitizer 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, acetoin, butyroin, toluoin, benzyl, benzophenone, p-chlorobenzophenone, p-methoxybenzophenone. Carbonyl compounds such as non, sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide, azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile, benzoyl peroxide, Examples include peroxide compounds such as 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 0 to 10 parts by weight, preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the monomer mixture (A) and organic solvent (B). is within the range of 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. Further, additives such as a surfactant, an ultraviolet absorber, or a storage stabilizer may be appropriately added to the coating material composition used in the present invention, if necessary. Next, the above-mentioned coating material composition was used to improve wear resistance,
In order to produce synthetic resin molded products with excellent surface smoothness, dyeability, and antistatic properties, a coating composition is applied to the surface of the synthetic resin molded product and then irradiated with active energy rays. be done. As base materials for synthetic resin molded products used in the production of synthetic resin molded products having the above characteristics, various synthetic resin molded products, regardless of thermoplastic resin or thermosetting resin, such as polymethyl methacrylate resin, polycarbonate resin, etc. Sheet-shaped molded products such as organic glasses and mirrors manufactured from polyallyl diglycol carbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin (AS resin), polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, etc. , film-shaped molded products,
Specific examples include rod-shaped molded products and various injection molded products such as lighting equipment and lenses.
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 preferable because it is often used and there is a strong demand for improved wear resistance. The various molded products used in the present invention described above can be used as they are, but if necessary, pre-treatments such as cleaning, etching, corona discharge, active energy ray irradiation, dyeing, and printing may be used. can. Furthermore, methods such as brush coating, flow coating, spray coating, spin coating, or dip coating are employed as methods for applying the above-mentioned coating composition to the synthetic resin molded article. The amount of the coating composition applied to the surface of the synthetic resin molded article varies depending on the amount of the monomer mixture (A) contained in the coating composition and the purpose. It is necessary to apply the coating so that the thickness of the crosslinked cured film formed is in the range of 1 to 30 μm. The coating amount of the coating material composition corresponding to this may be adjusted to give a coating film of approximately 1.5 to 300 microns. If the thickness of the cross-linked cured film formed on the surface of the synthetic resin molded product is less than 1μ, the wear resistance will be poor;
If it exceeds 30μ, the cured film will have poor flexibility.
This is not preferable because cracks are more likely to occur and the strength of the molded product itself may be reduced. 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 pressure mercury lamp, or electron beams, α rays, β rays, usually extracted from a 20 to 2000 KV electron beam accelerator, It is necessary to irradiate active energy rays such as gamma rays. From the point of view of practicality or workability, ultraviolet light is the most preferable irradiation source. The atmosphere in which active energy rays are irradiated is preferably an inert gas atmosphere such as nitrogen gas or carbon dioxide gas, but in a system using a polyfunctional monomer of formula (), irradiation may be performed in air. The coating material composition of the present invention and the synthetic resin molded article having a cured film on the surface obtained using the coating material composition are as follows:
It has excellent abrasion resistance and permanent antistatic properties, and has a good appearance such as surface smoothness. Furthermore, although the film formed on the surface is a cross-linked cured film, it is easy to dye, and can be dyed with basic dyes having amine salts or quaternary ammonium groups, nitro-based, azo-based, anthraquinone-based, and aminoketone-based dyes. Dyeing with disperse dyes such as these is particularly suitable. When using disperse dyes, various surfactants such as cationic, anionic, nonionic, and amphoteric surfactants are used as dispersants.
Also, chlorobenzene type, methylnaphthalene type, o
- Phenylphenol-based, aromatic ether-based, alkyl salicylate-based, and other compounds can be used as the carrier. The cured film of the present invention also has excellent adhesion to substrates, and is extremely useful for applications such as organic glasses, lighting equipment covers, mirrors, spectacle lenses, and optical lenses. The contents of the present invention will be explained in more detail below with reference to Examples. In addition, the measurement evaluation in the examples was performed by the following method. (1) Abrasion resistance a.Surface hardness...Pencil hardness according to JISK5651-1966 b.Abrasion test...Abrasion test with #000 steel wool○...Almost no scratches on the surface even when lightly rubbed△... 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) Adhesion Cross-cut cellophane tape peel test on cross-linked cured film. That is, make 100 1 mm ² cuts by inserting 11 film cutting lines vertically and horizontally into the film that reach the base material at 1 mm intervals, then stick cellophane tape on top of it and peel it off rapidly. Repeat this cellophane tape operation 3 times in the same place.
Repeat. ○...No peeling marks in the cross-linked cured film even after repeating 3 times △...Number of peeling marks after repeating 3 times 1-50 ×...Number of peeling marks after repeating 3 times 51-100
(3) Measurement of surface smoothness ○...The surface smoothness of the coating is very good and can be said to be a mirror surface. Δ...The surface of the coating has good smoothness, but there is some disturbance. ×...The surface is disordered and the smoothness is poor. (4) Antistatic property a. Cigarette ash adhesion test ○... After rubbing the surface of the cured film with a cotton cloth 20 times, bring it close to about 1 cm from fresh cigarette ash and there was no ash adhesion. △...Slight adhesion due to the same operation as above. ×...Significant adhesion occurs during the same operation as above. b Measurement of charging half-life 24 hours at a constant temperature and humidity of 20℃ and 60% relative humidity.
After holding the sample for a time, a voltage of 10 KV was applied for 10 seconds using an honest meter (manufactured by Shishido Shokai) to measure the half-life. Example 1 A coating curing liquid having the composition shown in Table 1 was prepared, and a 2 mm thick methacrylic resin plate (Mitsubishi Rayon, Acrylite) was immersed in it.
The plate was pulled up at a speed of 0.5 cm/sec to form a coating. After standing for 10 minutes, both sides of the plate were irradiated with ultraviolet rays from a high-pressure mercury lamp (2KWHO-L21 manufactured by Iwasaki Electric) for 15 seconds from a distance of 20 cm in the atmosphere shown in Table 1. The results of performance evaluation are shown in Table 1.

【table】

[Table] Example 2 A coating curing liquid was prepared using the sulfonic acid monomers shown in Table 2, and a cured film was created by irradiating it with ultraviolet rays in the air according to Example 1. Performance was evaluated. The results are shown in Table-2. As is clear from Table 2, the sulfonic acid monomer of the present invention represented by formula () shows uniformly excellent performance, has good dyeing properties and antistatic properties, and can be controlled by washing or friction. Almost no decrease in conductivity was observed. On the other hand, when vinylbenzenesulfonic acid, which is a sulfonic acid other than the present invention, is used, it has poor solubility, so it is necessary to incorporate a large amount of N,N dimethylformamide, which results in repellency and poor smoothness. , and the decrease in hardness is also large. Furthermore, the dyeability and antistatic properties are also insufficient, and in particular, although the initial performance is slightly improved, the antistatic properties completely disappear after washing. For comparison, Table 2 shows the results of a study using hydrophilic monomers, which have traditionally been considered effective in improving dyeability and chargeability. However, it was not possible to obtain a composition exhibiting uniformly excellent performance like the composition of the present invention.

【table】

[Table] Example 3 Curing liquids for coating with different types of alkylamine as shown in Table 3 were prepared, and cured films were made according to Example 2, and their performance was evaluated. The results are shown in Table-3. The ethanolamine compounds of the present invention as shown in formula () have uniformly excellent performance, but those using alkylamines outside the scope of the present invention have some inferior performance. That is,
Triethylamine, which does not have a CH ₂ CH ₂ OH group, has poor smoothness and transparency of the cured film, and uneven dyeing is also observed. In addition, when the number of carbon atoms in the N-substituted alkyl group is too large, such as hexadecyldiethanolamine, the hardness is greatly reduced. Example 4 2-acrylamide-2- as shown in Table-4
A cured film was formed according to Example 2 by changing the blending ratio of methylpropanesulfonic acid (AMPS) and N-lauryldiethanolamine (REA).
The performance was measured and the obtained results are shown in Table 4.

【table】

【table】

【table】

[Table] Example 5 Experiment numbers 2, 3, 4, 6 obtained in Example-4
A dyeing test with a disperse dye was conducted using the cured products of No. 7 and No. 7. When tested under the following dyeing conditions, both the cured products of experiment numbers 2 and 3 were dyed darkly and uniformly, but the cured product 4, which is outside the scope of the present invention, was dyed unevenly, and also hardened. Items 6 and 7 were dyed somewhat uniformly, but the dye density was low and they were only dyed to a pale blue color that was almost transparent. Dyeing conditions: Dianix Blue BG-FS (disperse dye manufactured by Mitsubishi Kasei Co., Ltd.) 5 parts by weight Disper TL (dispersant manufactured by Meisei Chemical Co., Ltd.) 3 〃 Methyl salicylate 1 〃 Deionized water 100 〃 Temperature 90℃ Time 1 hr Example 6 A cured film was formed on a 3 mm thick polycarbonate resin plate (manufactured by Mitsubishi Gas Chemical Co., Ltd., Iupilon) using the curing liquid of Experiment No. 4 in the same manner as in Example-2, and its performance was investigated. The film was smooth, had a thickness of 3.4μ, had a pencil hardness of 6H, and showed good adhesion with no scratches in the steel wool test. The half-life of A is 0.5 seconds,
Dark and uniform staining was possible in 0.6 seconds for B and 0.6 seconds for C. Example 7 The performance of the cured product was examined in the same manner as in Example 6 except that a lens (CR39 lens) with a diameter of 8 cm and a thickness of 2 mm made of polyaryl diglycol carbonate was used. The coating is smooth and has a good appearance.
Pencil hardness was 7H and adhesion was good with no scratches in the steel wool test. The half-lives of A, B, and C were 1.1 seconds, 0.9 seconds, and 1.0 seconds, respectively, and uniform dark staining was possible. Example 8 Lens made of polymethyl methacrylate (diameter 8
When the performance of the cured film was examined by repeating the method of Example 7 using a lens with a diameter of 2 mm (cm, thickness: 2 mm), the performance of the cured film equivalent to that of Example 7 was obtained.

Claims (1)

[Claims] 1. 50 to 98% by weight of a polyfunctional monomer (a) having three or more (meth)acryloyloxy groups in one molecule and the following general formula (In the formula, R ₁ is hydrogen or a methyl group, R ₂ is an alkoxy group having 1 to 5 carbon atoms or a (meth)acryloyloxy group, and n is an integer of 5 to 30.) Quantity (b) 0 to 40% by weight and the following general formula (In the formula, R ₃ is hydrogen or a methyl group, Y is a -CONH group or a -COO group, and l, m, n and r are integers of 0 to 5.) 1 to 30% by weight of mer (c) and the following general formula NR ₄ R ₅ (CH ₂ CH ₂ OH) () (wherein R ₄ and R ₅ are hydrogen, an alkyl group having 1 to 15 carbon atoms, or - 5 to 90 parts by weight of a monomer mixture (A) consisting of 1 to 20% by weight of an ethanolamine compound (d) represented by CH ₂ CH ₂ OH group, and the mixture (A)
95 to 10 parts by weight of at least one organic solvent (B) mixed with to form a homogeneous solution and 0 to 10 parts by weight of a photosensitizer (C) (the monomer mixture (A) and the organic solvent ( Total with B)
(based on 100 parts by weight), and has the functionality to form a crosslinked cured film with excellent wear resistance, surface smoothness, and dyeability, and permanent antistatic properties by irradiation with active energy rays. Excellent dressing composition. 2 The polyfunctional monomer (a) having three or more (meth)acryloyloxy groups in one molecule has the following general formula (In the formula, X ₁₁ , X ₁₂ , X ₁₃ , X ₂₂ , X ₂₃ ...Xn ₂ ,
At least three of Xn ₃ and X ₁₄ are CH ₂ = CR−COO
- group, the rest are -OH groups, and n is 1 to 5
is an integer of , and R is hydrogen or a methyl group. )
The excellent functionality according to claim 1, characterized in that it is a mono- or polypentaerythritol poly(meth)acrylate having three or more (meth)acryloyloxy groups in one molecule represented by dressing composition. 3. The highly functional coating material composition according to claim 1, wherein the ethanolamine compound of general formula () is diethanolamine having an alkyl group having 1 to 15 carbon atoms.