JPS6224464B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a coating material composition that can form a crosslinked cured film with excellent abrasion resistance, surface smoothness, flexibility, heat resistance, solvent resistance, durability, and adhesion to a substrate by irradiation with active energy rays. relating to things. Synthetic resin molded products made from polymethyl methacrylate resin, polycarbonate resin, polyallyl glycol carbonate resin, etc. are not only lighter and more impact resistant than glass products, but also cheaper and easier 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, display displays, and other decorative applications, name plates, and dust covers. Application development is progressing in many fields such as cases and 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. The present applicants have also discovered that (meth)acrylate monomers with more polytubular properties have excellent crosslinking and curing polymerizability upon irradiation with active energy rays, and that this crosslinking and curing can improve the abrasion resistance of the surface of synthetic resin molded products. He discovered that it was effective as a film-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. 53-4079). However, the polyfunctional monomers used in the above-mentioned patents generally have high viscosity, and when a coating composition containing them is applied to a resin molded article, it is difficult to obtain an excellent surface smoothness. Particularly in the case of optical applications, this has caused a significant decrease in the commercial value. In view of these circumstances, the present inventors have conducted extensive research and found that the above-mentioned drawbacks can be solved at once by adding and using a surfactant with a specific structure, and at the same time, the interface The present invention was completed by discovering that the combined use of an activator has other unexpected effects, such as preventing whitening of the film and defoaming the foam. That is, the present invention is based on the following general formula (In the formula, X ₁₁ , X ₁₂ , X ₁₃ , X ₂₂ , X ₂₃ ......, X _o2 , X _o
3 , at least three of X ₁₄ are CH ₂ = CR−COO−
The rest are -OH groups. n is an integer from 1 to 5. R represents hydrogen or a methyl group. ) 30 to 95% by weight of polyfunctional monomer (a) of mono- or polypentaerythritol poly(meth)acrylate having three or more (meth)acryloyloxy groups in one molecule, and Monomer (b) having 1 to 2 (meth)acryloyloxy groups in 70 to
0 to 10 parts by weight of a photosensitizer per 100 parts by weight of a monomer mixture consisting of 5% by weight, and the following general formula: (In the formula, X is

[Formula], where m and n represent positive numbers of 1, 2, 3, etc., and x and y represent numbers of 0, 1, 2, 3, and so on, and the formula 0.1≦xn+yn/2m≦ Take a value that satisfies 10. ) Matama (In the formula, Y is

[Formula] or

[Formula], where m and n are positive numbers of 1, 2, 3, etc., x and y are numbers of 0, 1, 2, 3, and so on, and the formula 0.1≦
Take a value that satisfies xn+yn/2m+n≦10. ) of at least one silicone-based surfactant represented by 0.0001
This relates to a coating material composition in which ~2.0 parts by weight is added. The feature of the present invention is that a specific trifunctional or higher functional (meth)acrylate monomer and a specific one or two (meth)acrylate monomers are used.
A monomer having an acryloyloxy group and a specific silicone surfactant are blended in a predetermined ratio,
A coating material composition that can form a transparent crosslinked cured film with excellent abrasion resistance, surface smoothness, flexibility, water resistance, heat resistance, chemical resistance, and adhesion to a substrate when irradiated with active energy rays. The most important feature is that by adding a small amount of a specific silicone surfactant, the smoothness of the cross-linked cured film can be improved. The objective is to always maintain stable consistency and uniformity. The poly(meth)acrylate of mono- or polypentaerythritol represented by the general formula () used in the present invention has very good polymerization activity when irradiated with active energy rays, and can be crosslinked and cured to a high degree. It forms a highly cross-linked cured polymer that exhibits wear resistance. In the present invention, a polyfunctional monomer represented by the above general formula ()
By using (a), the purpose can be fully achieved, but in particular, pentaerythritol tri(meth)acrylate (meaning pentaerythritol triacrylate and pentaerythritol trimethacrylate, hereinafter the same), pentaerythritol tetra(meth)acrylate acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate,
Dipentaerythritol hexa(meth)acrylate and the like are particularly preferred from the viewpoint of polymerization activity by irradiation with active energy rays in air and ease of handling based on low viscosity. The general formula ()
The polyfunctional monomer (a) represented by (a) may be used alone or in combination of two or more. The proportion of polyfunctional monomer (a) used is as follows: monomer mixture (A)
It is 30 to 95 parts by weight, preferably 35 to 94 parts by weight per 100 parts by weight. The amount of polyfunctional monomer (a) in the monomer mixture
If the amount in (A) is less than 30 parts by weight, a cured film with sufficient wear resistance cannot be obtained, and if the amount exceeds 95 parts by weight, the smoothness of the film will be poor, which is not preferable. In addition, in the present invention, even if it is a polyfunctional monomer having three or more (meth)acryloyloxy groups in one molecule, a polyfunctional monomer that does not satisfy the general formula (), such as trimethylol Polyfunctional (meth)acrylates such as propane 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, resulting in poor coating film formation. This is not preferred because sufficient crosslinking and curing cannot be achieved. Further, when a polyfunctional monomer that does not satisfy the above general formula () is used, it is not preferable because the effect of the silicone surfactant of the present invention on the smoothness and uniformity of the film is reduced. A monomer having 1 to 2 (meth)acryloyloxy groups in one molecule used in combination with the polyfunctional monomer (a) represented by the general formula () has flexibility and adhesion to the crosslinked cured film. Specific examples 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. Ethylene glycol dimethacrylate, 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 , dipropylene glycol di(meth)acrylate, 2.2-
Bis(4-acryloyloxyphenyl)propane, 2,2-bis(4-methacryloyloxyphenyl)propane, 2,2-bis(4-acryloyloxyethoxyphenyl)propane, 2,2
-bis(4-methacryloyloxyethoxyphenyl)propane, 2,2-bis(4-acryloyloxydiethoxyphenyl)propane, 2,2
-bis(4-methacryloyloxydiethoxyphenyl)propane, 2,2-bis(4-acryloyloxypropoxyphenyl)propane, 2.
2-bis(4-methacryloyloxypropoxyphenyl)propane, 2,2-bis[4-acryloyloxy(2-hydroxypropoxy)phenyl]propane, 2,2-bis[4-methacryloyloxy(2-hydroxypropoxy)] Phenyl]propane, 2,2-bis[4-acryloyloxy(2-hydroxypropoxyethoxy)phenyl]propane, 2,2-bis[4-methacryloyloxy(2-hydroxypropoxyethoxy)phenyl]propane, 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-hydroxy -3-chloropropyl (meth)acrylate, etc. In the present invention, among the monomers having 1 to 2 (meth)acryloyloxy groups in one molecule, the following general formula is used: (In the formula, R ₁ is hydrogen or a methyl group, X ₁ , X ₂ ,...
_. For example, 2,2-bis(4-acryloyloxyphenyl)propane, 2,2-
Bis(4-methacryloyloxyethoxypropoxyphenyl)propane, 2,2-bis[4-acryloyloxy(2-hydroxypropoxy)
Phenyl]propane and its boiling point at normal pressure is 150℃
Monomers having physical properties of the above and a viscosity of 20 cps or less at 20°C, and further having a hydroxyl group or an ether group in the group bonded to the (meth)acryloyloxy group, such as 2-hydroxyethyl acrylate, glycidyl acrylate, Diethylene glycol dimethacrylate, 2-hydroxypropyl acrylate, and the like are particularly preferred because they impart flexibility, adhesion, and smoothness to the crosslinked cured film, and have excellent crosslinking and curing properties when irradiated with active energy rays in air. These monomers (b) can be used alone or in combination of two or more within the composition range. The proportion of monomer (b) used is
The amount is 5 to 70% by weight based on 100 weight of the monomer mixture (A).
If the amount of monomer (b) is less than 5% by weight in the monomer mixture (A), the flexibility, adhesion, and smoothness of the crosslinked cured film will be poor; If it exceeds 70% by weight, it is not preferable because a crosslinked cured coating with sufficient wear resistance cannot be obtained. The specific silicone surfactant represented by the general formula () or () used in the present invention has a molecular structure consisting of polydimethylsiloxane units, a part of which is modified with a polyoxyalkylene group. It is. As for the degree of modification, at least one oxyalkylene group - for each unit of methylsiloxane group CH ₃ (SiO) -
OCH ₂ CH ₂ − or

[Formula] etc. are preferably bonded within a range of 0.1 to 10.0 units. Further, it may contain less than 0.1 unit of ester group, mercapto group, hydroxyl group, amino group, etc. per unit of siloxane group. If the degree of modification by oxyalkylene groups per unit of methylsiloxane group is less than 0.1, the smoothness of the coating will be worse than if no silicone surfactant is added; If it exceeds the range, the smoothness of the coating will deteriorate, which is not preferable. The amount of silicone surfactant added is the total amount of monomer mixture or monomer mixture and organic solvent.
The amount is preferably in the range of 0.0001 to 20 parts by weight per 100 parts by weight, and if it is less than 0.0001 parts by weight, the effect of addition will be small, while if it exceeds 20 parts by weight, the smoothness of the film will be poor, which is not preferred. Furthermore, the excellent effects of adding these silicone surfactants include the effect of preventing whitening of the film and the effect of defoaming. In other words, in the case of resins with poor solvent resistance such as AS resin, polycarbonate resin, ABS resin, etc., if a large amount of a good solvent for these resins such as toluene, benzene, acetone, methyl ethyl ketone, etc. is used as a diluent, UV rays The crosslinked film may turn white after irradiation. However, even in such a case, if a small amount of a silicone surfactant as described above is added and used in combination, whitening of the coating can be prevented and a transparent crosslinked coating can be obtained. In addition, it has been reported that fluorine-based surfactants are effective in improving the smoothness of the film surface, but although these have some effect on improving the smoothness of the film, they are difficult to mix. Alternatively, it has the effect of stabilizing bubbles generated during the coating process, and hardly disappears even after a long period of time. Therefore, when a paint containing a fluorine-based surfactant is applied to a plastic molded product, the air bubbles formed in the film are difficult to eliminate, and when the paint film is cured, these air bubbles form as spots on the film. As a result, the uniformity of the coating is extremely poor. On the other hand, the silicone surfactant discovered in the present invention has excellent defoaming properties, and almost no bubbles are formed in the coating film, or even if bubbles are formed in the coating film, they disappear immediately. I end up. Furthermore, when a plastic molded article is coated by dipping in a coating solution containing bubbles, the bubbles do not adhere to the base material. On the other hand, fluorine-based surfactants have the disadvantage that air bubbles adhere to the substrate. The above are the essential constituent parts of the coating material composition used in the present invention, but if necessary, within the range where these constituent conditions are satisfied, the crosslinked cured film formed will have antistatic properties and antifogging properties. Alternatively, for the purpose of imparting other functions, at least one other monofunctional vinyl monomer that is copolymerizable with these monomer mixtures and has polymerization activity with active energy rays may be used in combination. In the present invention, the coating material composition containing a monomer mixture as a main component can be used alone, but the coating workability when applying the coating material composition to the surface of a synthetic resin molded article, and the formation of a uniform coating film. Organic solvents can also be used in order to have a very favorable effect on the properties or storage stability, and to increase the adhesion of the crosslinked cured coating to the substrate. In the present invention, the organic solvent used is (1) mixed with a polyfunctional (meth)acrylate monomer mixture to form a homogeneous solution. (2) The boiling point at normal pressure is 50℃ or higher and 200℃ or lower. (3) Viscosity at room temperature is 10 centipoise or less. (4) 95 to 10 parts by weight per 5 to 90 parts by weight of the polyfunctional (meth)acrylate monomer mixture (total 100 parts by weight)
(parts by weight). It is necessary to satisfy the following conditions. The first condition is to form a homogeneous solution with a polyfunctional (meth)acrylate monomer mixture, 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 uniform film-forming property or a crosslinked cured film with excellent 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 applying the coating material composition, the surface of the substrate is cooled by the latent heat of the organic solvent that evaporates from the coating film.
Moisture in the air condenses there and the surface smoothness of the paint film is lost, and if the temperature exceeds 200°C, the organic solvent from the paint film evaporates very slowly, causing problems with workability. During the active energy ray irradiation process, the balance between the volatilization and escape of the remaining organic solvent and the formation of a cross-linked cured film through polymerization is not maintained, resulting in a loss of uniformity and surface smoothness of the cross-linked cured film, or a loss of surface smoothness in the cross-linked cured film. This is not preferable because the organic solvent remains and the coating becomes white. Therefore, the boiling point of the organic solvent used must be between 50°C and 200°C at normal pressure, more preferably between 60 and 150°C.
It is within the range of . The viscosity of the organic solvent used must also be 10 centipoise or less at room temperature; if it exceeds 10 centipoise, it will have little effect on coating workability or film smoothness. The amount of organic solvent used is 5 to 90% of the monomer mixture described above.
95 to 10 parts by weight (total 100 parts by weight)
If the amount is less than 10 parts by weight, the viscosity of the coating material composition may be so high that coating workability by dipping may not be sufficient, or it may be difficult to control the thickness of the applied film, or it may be difficult to form a uniform film. may decrease. 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. 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
-Acid esters such as butyl and ethyl propionate. One type of these organic solvents may be used alone, or two or more types may be used in combination as long as the boiling point and component ratio of the mixture are within a 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 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, causing discoloration, or may damage 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 the present invention, in order to apply the coating material composition to the surface of a synthetic resin molded article and form a crosslinked cured film, it is necessary to irradiate it with active energy rays such as ultraviolet rays, electron beams, or radiation. Among these, the method using ultraviolet irradiation with a wavelength of 2000 to 8000 Å is the most preferred crosslinking and curing method 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, and 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 monomer mixture is in the range of 0 to 10 parts by weight per 100 parts by weight of the monomer mixture or the monomer mixture and the organic solvent. Addition is not preferable because it causes coloring of the crosslinked cured film and a decrease in weather resistance. Furthermore, additives such as antistatic agents, ultraviolet absorbers, and storage stabilizers may be added to the coating material composition used in the present invention, if necessary. 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. be done. In the present invention, synthetic resin molded products used in the production of wear-resistant synthetic resin molded products include various synthetic resin molded products, regardless of thermoplastic resin or thermosetting resin, such as polymethyl methacrylate resin, polycarbonate resin, polycarbonate resin, etc. Sheet-shaped molded products such as plate glass and mirrors, film-shaped products manufactured from allyl diglycol carbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin (AS resin), polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, etc. Specific examples include molded products, 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 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 contained in the coating composition or the purpose.
It is necessary to apply the crosslinked cured film formed on the surface of the synthetic resin molded product so that the film thickness 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. As mentioned above, there are various methods for applying the coating material composition, but among them, the dip coating method is limited to some extent depending on the shape of the synthetic resin molded product. It has advantages such as a simple working process, less loss of coating material composition, excellent workability and productivity, and excellent reproducibility. 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, Active energy rays such as radiation such as gamma rays must be irradiated. From the viewpoint of practicality or workability, ultraviolet light with a wavelength of 2000 to 8000 Å is most preferable as the radiation source. Although the atmosphere for irradiating active energy rays may be an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or an atmosphere with a reduced oxygen concentration, the coating material composition according to the present invention can be irradiated under a normal air atmosphere. However, it is possible to form a crosslinked cured film with excellent wear resistance and other properties.
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 coating material composition of the present invention and the synthetic resin molded product having a crosslinked cured coating on the surface produced using the same have excellent surface smoothness and aesthetic appearance, and extremely excellent surface hardness, abrasion resistance, and scratch resistance. It is something that Furthermore, the cross-linked cured coating formed on the surface is a transparent, flexible, and uniform coating that has extremely good adhesion to the substrate, and does not cause peeling or cracking even under harsh conditions or environments. There is no
It is extremely useful in applications such as organic window glasses, light fixture covers, reflectors, mirrors, eyeglass lenses, sunglass lenses, and optical lenses. The content of the present invention will be explained in more detail with reference to Examples below, in which parts are by weight. In addition, the measurement evaluation in the example was performed by the following method. (1) Abrasion resistance (a) Surface hardness...Pencil hardness according to JISK 5651-1966 (b) Scratch test...Scratch test with #000 steel wool 〇...Even when lightly rubbed, there are almost no scratches on the surface. Does not stick △...The surface will be slightly scratched if rubbed lightly ×...The surface will be severely scratched even if rubbed lightly (same level as the base resin) (2) Adhesion Cross-cut cellophane tape to cross-linked cured film Peeling test. 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. 〇……No peeling marks of the cross-linked cured film even after repeating 3 times △……Number of peeling marks after repeating 3 times 1 to 50 ×……Number of peeling marks after repeating 3 times 51 to 100
(3) Measurement of surface smoothness ◎...The smoothness of the surface of the coating is very good and can be said to be a mirror surface. 〇...The smoothness of the surface of the coating is good, but there are subtle disturbances and it cannot be said to be a mirror surface. ×...The surface is disordered and the smoothness is poor (4) Method for testing the smoothness stability of the coating before UV curing The smoothness is determined according to (3). Test A: After blowing hot air at 60° C. at a speed of 2 m/sec for 5 minutes perpendicularly to the surface of the substrate on which the coating before UV curing has been formed, judgment is made according to method (3). Examples 1-2 and Comparative Examples 1-2 A methacrylic resin plate with a thickness of 4 mm was mixed with 10 parts of dipentaerythritol hexaacrylate, 20 parts of dipentaerythritol pentaacrylate, 4 parts of dipentaerythritol tetramethacrylate, and 2 parts of 2-hydroxypropyl acrylate. , 4 parts of 2-hydroxyethyl acrylate, 40 parts of iso-propyl alcohol, 20 parts of methyl ethyl ketone, and 0.2 parts of the silicone surfactant shown in Table 1 at a speed of 0.5 cm/sec. After forming a pulled film and leaving it for 5 minutes, it was exposed to air using a 2KW high-pressure mercury lamp from a distance of 15cm on both sides of the resin plate.
The resin plate was irradiated for 10 seconds and had a film thickness of 4 μm.
Table 1 shows the test results of the adhesion, surface hardness, and surface smoothness of the obtained resin plate. As can be seen from Table 1, if the silicone surfactant of the present invention is not used, a film with good surface smoothness cannot be obtained.

[Table] Example 3 and Comparative Example 3 30 parts of pentaerythritol tri(meth)acrylate, 30 parts of dipentaerythritol pentaacrylate, 20 parts of 2,2-bis(4-acryloyloxydiethoxyphenyl)propane, 2-hydroxy A mixture consisting of 20 parts of ethyl acrylate and 5 parts of benzoin ethyl ether was prepared. To this was added 0.1 part of a silicone surfactant (a) consisting of a polyoxyalkylene modified product of polydimethylsiloxane, and a 10μ
It was coated using a percoater to a thickness of , and irradiated for 8 seconds with a 5KW high-pressure mercury lamp from a distance of 20cm in an air atmosphere. In addition, samples were prepared in the same manner as above and compared in the case where the silicone surfactant (a) was not added. As is clear from Table 2, the surface smoothness of the present invention in which silicone surfactant (a) was added is superior.

[Table] 〓｜ 〓 〓 〓

Claims (1)

[Claims] First-order general formula (In the formula, X ₁₁ , X ₁₂ , X ₁₃ , X ₂₂ , X ₂₃ ......X _o2 , X _o
3 , at least three of X ₁₄ are CH ₂ = CR−COO−
The rest are -OH groups. Moreover, n is an integer of 1-5. R represents hydrogen or a methyl group. )
30 to 95% by weight of polyfunctional monomer (a) of poly(meth)acrylate of mono- or polypentaerythritol having three or more (meth)acryloyloxy groups in one molecule represented by Monomer (b) having 1 to 2 (meth)acryloyloxy groups
0 to 10 parts by weight of a photosensitizer per 100 parts by weight of a monomer mixture consisting of 70 to 5% by weight, and the following general formula: (In the formula,
Take a value that satisfies the formula 0.1≦xn+yn/2m≦10. ) or (In the formula, Y is [Formula] or [Formula], m and n are positive numbers of 1, 2, 3......, and x and y are numbers of 0, 1, 2, 3... represents the formula 0.1≦
Take a value that satisfies xn+yn/2m+n≦10. ) of at least one silicone-based surfactant represented by 0.0001
A coating material composition capable of forming a cross-linked cured film with excellent wear resistance and surface smoothness upon irradiation with active energy rays, with the addition of ~2.0 parts by weight. 2nd order general formula (In the formula, X ₁₁ , X ₁₂ , X ₁₃ , X ₂₂ , X ₂₃ , ......, X _o
At least three of ₂ , X _o3 , and X ₁₄ are CH ₂ = C
(R) -COO- group and the rest are -OH groups. n is 1
It is an integer of ~5. R represents hydrogen or a methyl group. ) 30 to 95% by weight of polyfunctional monomer (a) of mono- or polypentaerythritol poly(meth)acrylate having three or more (meth)acryloyloxy groups in one molecule, and 5 to 90 parts by weight of a monomer mixture consisting of 70 to 5% by weight of a monomer (b) having 1 to 2 (meth)acryloyloxy groups is mixed with the monomer mixture to form a homogeneous at least one organic solvent forming a solution95~
10 parts by weight and 0 parts by weight of photosensitizer for a total of 100 parts by weight.
~10 parts by weight and the following general formula (In the formula, X is [Formula], m and n are positive numbers of 1, 2, 3, etc.,
Further, x and y represent numbers of 0, 1, 2, 3, . . . and take values that satisfy the formula 0.1≦xn+yn/2m≦10. ) or (In the formula, Y is [Formula] or [Formula], m and n are positive numbers of 1, 2, 3......, and x and y are numbers of 0, 1, 2, 3... represents the formula 0.1≦
Take a value that satisfies xn+yn/2m+n≦10. ) of at least one silicone-based surfactant represented by 0.0001
A coating material composition capable of forming a crosslinked cured film with excellent abrasion resistance and surface smoothness upon irradiation with active energy rays by adding ~2.0 parts by weight.