JP6519946B2 - UV curable coating composition and cured film thereof - Google Patents

Description

The present invention has excellent thin-film, high-speed curability, slipperiness, anti-soiling properties that can be used for applications of rewritable cards such as IC cards, for building materials, for packaging of food packaging, for optical products. The present invention relates to a UV curable coating composition having excellent properties and a cured film thereof.

In recent years, IC cards have been used in various fields including financial fields such as credit cards and cash cards, traffic fields such as automatic ticket gates for stations and automatic tolls on expressways, and fields of identification such as membership cards and registration documents. An information recognition medium on which an IC chip such as an IC tag or an IC sheet is mounted is used. In particular, expectations for noncontact information recognition technology (referred to as RFID (Radio Frequency Identification)) using radio technology by radio waves are increasing, and an RFID card, RFID tag, RFID sheet, etc. using this technology The use of information recognition media is also being expanded.

An ultraviolet curable resin has been proposed for use as a protective layer on the surface of these IC cards, IC sheets and other rewritable cards (Patent Documents 1 to 3). However, wrinkles scraped by the thermal head may adhere to the thermal head, which may cause problems such as insufficient formation and erasing of an image. Therefore, a curable silicone resin or a silicone modified resin is used for the formed protective layer, slipperiness is given, and adhesion prevention of head wrinkles was examined (patent documents 4-7).

However, the curable silicone resin and the silicone modified resin require several hours to several days to form a cured film, and there is little cost merit.

Moreover, although the silicone resin composition which had ultraviolet curability was proposed in the past (patent documents 8 and 9), curability was inadequate in order to cure | harden at high speed.

In addition, attempts have been made to use the ultraviolet curable resin composition as a thin film by reducing the amount used for cost reduction. However, if it is several μm or more, it can be cured, but in the case of a thin film cured film less than 1 μm, there is a problem that it is strongly affected by polymerization inhibition by oxygen and it is difficult to form a cured film at high speed curing.
Unexamined-Japanese-Patent No. 06-8626 Japanese Patent Application Publication No. 06-344672 Unexamined-Japanese-Patent No. 08-11433 Unexamined-Japanese-Patent No. 2005-212362 JP 2005-53124 A Unexamined-Japanese-Patent No. 05-38881 JP, 2013-121677, A Japanese Patent Application Publication No. 2006-045504 Japanese Patent Application Publication No. 2003-192751

The present invention is a UV curable coating composition which is excellent in slipperiness and capable of thin film curing and high speed curing which are superior to ordinary UV curable resins, and which is also excellent in stain resistance and cellophane tape removability It aims at providing the cured film.

The inventors of the present invention have found that a specific polysiloxane-containing polyisocyanate derivative [A], a specific (meth) acrylate compound [B] and a specific photopolymerization initiator [A] as constituent components of a UV-curable coating composition. By having C1] and / or [C2] and making them into a specific composition ratio, it discovers that the said subject is solvable and completed this invention.

That is, in the present invention, a polysiloxane compound (a1) having a hydroxyl group at one end, a polyisocyanate compound (a2) having an average of three or more isocyanate groups, and a hydroxyl group containing an average of three or more (meth) acryloyl groups Polysiloxane-containing polyisocyanate derivative [A] formed by reacting (meth) acrylate compound (a3), acrylate compound having an average of 3 to 20 acryloyl groups per molecule and having no urethane bond [B] And a photopolymerization initiator-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one [C1] and / or 2 -Ultraviolet containing -methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [C2] A curable coating composition (present invention 1).

Invention 2 includes the acrylate compound [B] of the invention 1 as pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri The ultraviolet curable coating composition according to claim 1, which is one or more selected from the group consisting of pentaerythritol hepta (meth) acrylate and tripentaerythritol octa (meth) acrylate.

Invention 3 of the present invention 1 or 2 according to Invention 1 or 2 [A]: [B]: [C1] and / or [C2] = 0.1 to 5.0% by weight: 75 to 95% by weight: 4.9 to 20 It is a UV curable coating composition which is% by weight.

The fourth invention is a cured film formed from the ultraviolet curable coating composition according to any one of the first to third inventions.

According to the present invention, it is possible to obtain a cured film having excellent thin film and high-speed curability and excellent in slipperiness. Such a cured film is useful as a UV curable coating composition in applications of rewritable cards such as IC cards. Moreover, since it has stain resistance and cellophane tape peelability, it is also useful as a surface coating agent for construction materials, food packaging packages, optical products, and the like.

Hereinafter, the present invention will be described in detail. The present invention relates to a polysiloxane compound (a1) (hereinafter referred to as "component (a1)") having a hydroxyl group at one end, a polyisocyanate compound (a2) (hereinafter referred to as "(a2), having three or more isocyanate groups. A polysiloxane-containing polyisocyanate-based derivative obtained by reacting a hydroxyl group-containing (meth) acrylate compound (a3) (hereinafter referred to as "component (a)") having three or more (meth) acryloyl groups [A] (hereinafter referred to as "component (A)"), an acrylate compound having an average of 3 to 20 acryloyl groups per molecule and having no urethane bond [B] (hereinafter referred to as "component (B)" And photopolymerization initiators-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl- Lopan-1-one [C1] (hereinafter referred to as “component (C1)”) and / or 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [C2] (hereinafter referred to as It is an ultraviolet curable coating composition containing "(C2) component".

The component [A] is obtained by reacting the components (a1), (a2) and (a3).

The component (a1) is a compound having a hydroxyl group and an organopolysiloxane unit in the following general formulas (1) and (2) in one molecule. By using this component, it is possible to impart slipperiness, stain resistance and cellophane tape peelability to the cured film.

(In the general formula (1), R ¹ and R ² may be the same or different and each represents a hydrogen atom, or any of a methyl group, an ethyl group, a propyl group, and a butyl group. An integer of 300, m is an integer of 1 to 50, and n is an integer of 1 to 50.)

(In the general formula (2), R ¹ and R ² may be the same or different and each represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group. L is 1 to 300) M is an integer of 1 to 50, n is an integer of 1 to 50, R ³ is at least 2 or more of-(CH ₂ ) _r -OH, and the others are a hydrogen atom, a methyl group and-(CH ₂ It may be any of _q- OH, _q is an integer of 1 to 50, and r is an integer of 1 to 50.)

The above l is preferably 5 to 120, more preferably 9 to 60 in terms of slipperiness and curability. The above m is preferably 1 to 20, more preferably 1 to 10 from the viewpoint of curability. The above n is preferably 1 to 20, more preferably 1 to 10 from the viewpoint of curability. The above q is preferably 1 to 20, more preferably 1 to 10 from the viewpoint of curability. The above r is preferably 1 to 20, more preferably 1 to 10 from the viewpoint of curability.

The number average molecular weight of the component (a1) is not particularly limited, but is preferably 100 to 20,000. Here, the number average molecular weight is a value converted from a hydroxyl value (number average molecular weight = 56110 ÷ hydroxy value (mg KOH / g) × number of hydroxyl groups per molecule). By making the number average molecular weight 100 or more, it is possible to make the cured film excellent in slipperiness, stain resistance and cellophane tape releasability, and by making it 20,000 or less, the cured film is easily solidified. be able to.

The quantification of the above hydroxyl value can be measured, for example, in accordance with JIS K 1557.

Specific examples of the component (a1) include X-22-170DX (Shin-Etsu Silicone Co., Ltd.), X-22-4015 (Shin-Etsu Silicone Co., Ltd.), Cyraplane FM-0411 (JNC (share) ), Cyraplane FM-0421 (JNC Co., Ltd.), Cyraplane FM-0425 (JNC Co., Ltd.), Cyraplane FM-DA11 (JNC Co., Ltd.), Cyraplane FM -DA21 (made by JNC Co., Ltd.), Cylaplane FM-DA26 (made by JNC Co., Ltd.), etc. goods, etc. are mentioned.

The component (a2) is not particularly limited as long as it is a polyisocyanate compound having three or more on average, and examples thereof include polyisocyanates such as aromatic, aliphatic and alicyclic. By having three or more isocyanate groups, unreacted low molecular weight components such as the reaction products of only (a2) and (a1) and the reactions of only (a2) and (a3) can be reduced, and curing is achieved. The membrane bleed is reduced. Furthermore, it is preferable that isocyanate equivalent (g / eq) is 200 or less. This leads to a decrease in bleed. For example, tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethyl xylylene diisocyanate , Isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, phenylene diisocyanate, lysine diisocyanate, lysine triisocyanate, polyisocyanate such as naphthalene diisocyanate, or a polymer compound of these polyisocyanates, biuret type polyisocyanate Over DOO, water-dispersible polyisocyanate (e.g., Nippon Polyurethane Industry Co., Ltd. "Aquanate 100", "Aquanate 110", "Aquanate 200", "AQUANATE 210", etc.) and the like.

The determination of the above-mentioned isocyanate equivalent can be measured, for example, in accordance with JIS K 7301.

The component (a3) is not particularly limited, but preferably has a hydroxyl value of 250 mg KOH / g or less. Thereby, the concentration of acryloyl group in one molecule can be increased. For example, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate Etc. These can be used alone or in combination of two or more. By using these components, the thin film curability of a cured film can be provided. If only two or less acryloyl groups are present, the curability is insufficient and the thin film curability is lowered.

As a method of synthesizing the component (A), a known method may be adopted. For example, the components (a1), (a2) and (a3) may be used as a solventless or nonalcoholic organic solvent such as toluene. In a solvent, triethylenediamine, 1,8-diazabicyclo- [5,4,0] -undecene-7, stannous octoate, lead dioctylate, bismuth dioctylate, bismuth trioctylate, bismuth trineodecanoate, dibutyltin dilaurate, The reaction may be carried out usually at a reaction temperature of about 60 to 90 ° C. in the presence of a catalyst selected from dioctyltin laurate and the like.

With respect to the use ratio of the component (a1), the component (a2) and the component (a3), the molar ratio of the hydroxyl group of the component (a1) / the isocyanate group of the component (a2) / the hydroxyl group of the component (a3) is 1-2. It is preferably 25/1 to 1.25 / 1-2.25.

The average number of acryloyl groups per molecule of the component [A] is preferably 5 to 20 in order to make the thin film curability and the fast curability excellent. More preferably, it is 5-10.

The component [B] is not particularly limited as long as it is an acrylate compound having an average of 3 to 20 acryloyl groups per molecule and having no urethane bond. By containing an average of 3 to 20 acryloyl groups per molecule, it is possible to obtain excellent curability even for a thin film that is susceptible to inhibition of curing by oxygen. The acrylate compound which has a urethane bond does not show the effect of this invention by the photopolymerization reactivity being inferior compared with a [B] component. It is preferably an acrylate compound having an average acryloyl number of 5 to 20 per molecule, from the viewpoint that the thin film curing and high-speed curing properties become better. More preferably, it is an acrylate compound having an average acryloyl number of 5 to 10 per molecule. More preferable specific [B] components are pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta ( It is one or more acrylate compounds selected from the group of (meth) acrylates and tripentaerythritol octa (meth) acrylates.

As the photopolymerization initiators [C1] and [C2] used in the present invention, the photopolymerization initiator hydroxy 1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2 is used. It is necessary to contain -methyl-propan-1-one [C1] and / or 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [C2]. Specific examples of [C1] include Irgacure 907 by BASF, and LUNACURE 907 by DKSH Japan. Examples of [C2] include Irgacure 127 manufactured by BASF. By using these, the curability can be improved, and a thin film, a cured film that can be cured even at high speed can be obtained.

The UV-curable resin composition of the present invention further comprises triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone as an auxiliary agent for a photopolymerization initiator. -Dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4- It is also possible to use diethylthioxanthone, 2,4-diisopropylthioxanthone, etc. in combination.

The UV curable coating composition of the present invention can be produced by mixing the [A] component, the [B] component, the [C1] component and / or the [C2] component in a desired ratio. There is no particular limitation on the mixing method and the addition order of each component.

The ultraviolet curable coating composition containing the component [A], the component [B], the component [C1] and / or the component [C2] has a composition ratio of [A]: [B]: [C1] and It is preferable that it is / or [C2] = 0.1-5.0 weight%: 75-90 weight%: 4.9-20 weight%. Thereby, a cured film which can be cured even with a thin film can be obtained. More preferably, the [C1] and / or [C2] component is 10% by weight or more.

Thus, the polysiloxane-containing polyisocyanate derivative [A] of the present invention, a (meth) acrylate compound [B] having three or more (meth) acryloyl groups, and a photopolymerization initiator [C1] and / or [C2] are included. An ultraviolet curable coating composition is obtained.

This composition can be blended with an organic solvent, if necessary, and used after adjusting its viscosity. Such organic solvents include, for example, ethyl acetate, butyl acetate, toluene, xylene, methanol, ethanol, propanol, butanol, acetone, methyl isobutyl ketone, cellosolves such as methyl ethyl ketone, cyclohexanone and ethyl cellosolve, and propylene such as propylene glycol monomethyl ether Glycol ethers, diacetone alcohol and the like can be mentioned. These may be used alone or in combination of two or more.

As a method of curing by ultraviolet irradiation, using a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrode lamp, an LED lamp etc. The irradiation may be about 50 to 100 mJ / cm ² . After irradiation with ultraviolet light, heating may be performed as necessary to complete curing.

Moreover, the coating agent composition of this invention can also be mix | blended with various additives, such as a leveling agent, an antifoamer, a slip agent, and a photosensitizer, as needed.

As a method of forming a coating layer (cured film) on the article surface using the coating composition of the present invention, the coating composition is applied to the article surface by a known method and dried, and then the active energy ray is applied. It is carried out by curing by irradiation. Examples of the coating method of the coating composition include bar coater coating, mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, and the like. The application amount is not particularly limited, but usually, the weight after drying is in the range of 0.1 to 20 g / m ² .

There is no particular limitation on an article (substrate) on which a coating layer can be formed using the coating composition of the present invention, and, for example, plastics (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine) Resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin etc.), metal, wood, paper, glass, slate etc. are mentioned.

A cured film formed from the ultraviolet curable coating composition of the present invention is also one of the present invention. Thereby, since the film thickness of the cured film of this invention can be made into less than 1 micrometer, it becomes possible to reduce cost. According to the present invention, such a cured thin film can be formed by high-speed curing.

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In the examples, all parts and percentages are by weight unless otherwise specified.

Synthesis Example 1 Synthesis of Polysiloxane-Containing Polyisocyanate Derivative [A-1]
In a reaction vessel equipped with a stirrer, a cooling pipe, a dropping funnel and a nitrogen introducing pipe, 100 parts of isocyanurate of hexamethylene diisocyanate, 0.3 parts of tin octylate, polysiloxane compound (a1) (general formula (1) R ¹ = butyl group, R ² = methyl group, l = 10, m = 3, n = 2) 182 parts, 347 parts of dipentaerythritol pentaacrylate, 629 parts of ethyl acetate part are charged, and it takes about 1 hour, The temperature in the system was raised to about 70 ° C. Subsequently, the reaction system was maintained at the same temperature for 3 hours, and after confirming that the isocyanate group disappeared, the reaction system was cooled to obtain an ultraviolet-curable urethane acrylate oligomer [A-1].

Synthesis Example 2 Synthesis of Polysiloxane-Containing Polyisocyanate Derivative [A-2]
Example 1 100 parts of isocyanurate of isophorone diisocyanate, 0.2 parts of tin octylate, 0.2 part of tin octylate, and a polysiloxane compound (a1) (general formula (1) R ¹ ) in a reaction vessel equipped with a stirrer, a cooling pipe, a dropping funnel and a nitrogen introducing pipe. = Butyl group, R ² = methyl group, l = 10, m = 3, n = 2) 157 parts, 300 parts of dipentaerythritol pentaacrylate, 557 parts of ethyl acetate part are charged, and the system is taken for about 1 hour. The temperature inside was raised to about 70 degrees. Next, the reaction system was maintained at the same temperature for 3 hours, and after confirming that the isocyanate group disappeared, the reaction system was cooled to obtain an ultraviolet ray curable urethane acrylate oligomer [A-2].

Synthesis Example 3 Synthesis of Polysiloxane-Containing Polyisocyanate Derivative [A-3]
In a reaction vessel equipped with a stirrer, a cooling pipe, a dropping funnel and a nitrogen introducing pipe, 100 parts of isocyanurate of hexamethylene diisocyanate, 0.1 parts of tin octylate, polysiloxane compound (a1) (general formula (1) R ¹ = butyl group, R ² = methyl group, l = 10, m = 3, n = 2) 157 parts, 40 parts of 2-hydroxyethyl acrylate (one acryloyl group), 297 parts of ethyl acetate, The temperature in the system was raised to about 70 ° C. over about one hour. Next, the reaction system was maintained at the same temperature for 3 hours, and after confirming that the isocyanate group disappeared, the reaction system was cooled to obtain an ultraviolet-curable urethane acrylate oligomer [A-3].

Synthesis Example 4 Synthesis of Urethane (Meth) Acrylate Compound
Charge 77.1 parts of hexamethylene diisocyanate trimer, 0.10 parts of dibutyltin dilaurate, and 500 parts of methyl ethyl ketone in a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port at 60 ° C or less 422.9 parts of dipentaerythritol pentaacrylate and 0.4 parts of 2,6-di-tert-butylcresol are dropped in about 1 hour, the reaction is continued at 60 ° C., and the reaction is completed when the isocyanate group disappears Thus, a urethane (meth) acrylate compound was obtained.

(Preparation of coating solution)
The coating composition was prepared using each of the UV curable coating compositions obtained by the above synthesis.

Example 1
2 parts of the polysiloxane-containing polyisocyanate derivative obtained in Synthesis Example 1 93 parts of dipentaerythritol pentaacrylate, hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl 5 parts of 2-methyl-propan-1-one [C1] was blended, diluted with methyl ethyl ketone to a nonvolatile content of 25%, and uniformly mixed.

(Example 2)
In 2 parts of the polysiloxane-containing polyisocyanate derivative obtained in Synthesis Example 1, 93 parts of dipentaerythritol pentaacrylate, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one [C2] Five parts were blended, diluted with methyl ethyl ketone to a nonvolatile content of 25%, and uniformly mixed.

(Example 3)
In 2 parts of the polysiloxane-containing polyisocyanate derivative obtained in Synthesis Example 2, 93 parts of dipentaerythritol pentaacrylate, -hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] Five parts of phenyl} -2-methyl-propan-1-one [C1] were blended, diluted with methyl ethyl ketone to a nonvolatile content of 25%, and uniformly mixed.

(Example 4)
In 2 parts of the polysiloxane-containing polyisocyanate derivative obtained in Synthesis Example 2, 93 parts of dipentaerythritol pentaacrylate, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [C2] Five parts were blended, diluted with methyl ethyl ketone to a nonvolatile content of 25%, and uniformly mixed.

(Comparative example 1)
To 95 parts of dipentaerythritol pentaacrylate, 5 parts of hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one [C1] Were diluted with methyl ethyl ketone so that the non-volatile content was 25%, and mixed uniformly.

(Comparative example 2)
In 95 parts of the polysiloxane-containing polyisocyanate derivative obtained in Synthesis Example 1, -hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl- Five parts of propan-1-one [C1] was blended, diluted with methyl ethyl ketone to a nonvolatile content of 25%, and uniformly mixed.

(Comparative example 3)
93 parts of dipentaerythritol pentaacrylate and 5 parts of DAROCURE 1173 (Ciba Specialty Chemicals Co., Ltd.) are blended with 2 parts of the polysiloxane-containing polyisocyanate derivative obtained in Synthesis Example 1, and the nonvolatile content is 25%. The mixture was diluted with methyl ethyl ketone and uniformly mixed.

(Comparative example 4)
93 parts of dipentaerythritol pentaacrylate and 5 parts of Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.) are blended with 2 parts of the polysiloxane-containing polyisocyanate derivative obtained in Synthesis Example 1, and the nonvolatile content becomes 25%. The mixture was diluted with methyl ethyl ketone and uniformly mixed.

(Comparative example 5)
To 2 parts of the polysiloxane-containing polyisocyanate derivative obtained in Synthesis Example 3 93 parts of dipentaerythritol pentaacrylate, hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl 5 parts of 2-methyl-propan-1-one [C1] was blended, diluted with methyl ethyl ketone to a nonvolatile content of 25%, and uniformly mixed.

(Comparative example 6)
Into 2 parts of the polysiloxane-containing polyisocyanate derivative obtained in Synthesis Example 1, 93 parts of 1,6-hexanediol diacrylate, hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl)- Five parts of benzyl] phenyl} -2-methyl-propan-1-one [C1] were blended, diluted with methyl ethyl ketone to a nonvolatile content of 25%, and uniformly mixed.

(Comparative example 7)
93 parts of the urethane (meth) acrylate compound obtained in Synthesis Example 4 to 2 parts of the polysiloxane-containing polyisocyanate compound derivative obtained in Synthesis Example 1, and hydroxy-1- {4- [4- (2-hydroxy-2) 5 parts of -Methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one [C1] was blended, diluted with methyl ethyl ketone to a nonvolatile content of 25%, and uniformly mixed.

(Evaluation of cured film)
A substrate surface cured film was formed by the following method using the paint obtained above, and the evaluation test was performed. The results are shown in Table 1. Coat with a bar coater # 2 (film thickness 0.5 μm) on a polyethylene terephthalate film with a thickness of 100 μm, dry for 1 minute in a circulating dryer at 80 ° C., and then high pressure mercury lamp 120 W / cm (1 lamp), A cured film was formed at an irradiation distance of 25 cm and a belt speed of 43 m / min with a cumulative irradiation amount of 30 mJ / cm 2.

<Appearance>
The appearance of the cured film was visually evaluated for the leveling property (smoothness), the presence or absence of defects on the skin, and pinholes.
== smooth and free from problems such as skin and pinholes
X = not smooth, there is a defect such as skin of yuzu, pinhole.

<Curable>
A cotton swab impregnated with methyl ethyl ketone was rubbed against the cured film to make 50 cycles, and the presence or absence of a cured film change was visually confirmed.
○ = No change in the cured film compared to before the test.
X = whitening is observed in the cured film.
×× = The cured film is peeled off.

<Slipperiness>
The static friction coefficient was measured according to JIS-K-7125.

<Stain resistance>
Using an oil-based magic ink (Hi-Mckee Black Zebra Co., Ltd.), the oil-based magic ink was applied linearly to the cured coating, dried for 5 minutes, wiped with a Kimwipe, and the wiping property was evaluated.
○ = no wiping mark
X = not wipeable

<Cellophane tape peelability>
Using a cellophane tape (manufactured by L-PACK LP-24, manufactured by Nichiban Co., Ltd.), the cellophane tape was attached to the cured coating film, allowed to stand for 5 minutes, peeled off, and peelability was evaluated.
○ = easy peeling
× = Peeling is heavy and difficult to peel

*: It could not be measured because the cured film component was not cured.

The symbols in Table 1 are as follows.
DPPA: dipentaerythritol pentaacrylate HDDA: 1,6-hexanediol diacrylate D.I. 1173: Darocure 1173 (manufactured by Ciba Specialty Chemicals Co., Ltd.)
Irg. 184: Irgacure 184 (Ciba Specialty Chemicals Co., Ltd. product)

Claims (2)

General formula (1)
(In the general formula (1), R ¹ and R ² may be the same or different and each represents a hydrogen atom, or any of a methyl group, an ethyl group, a propyl group, and a butyl group. An integer of 300, m is an integer of 1 to 50, and n is an integer of 1 to 50.)
The polysiloxane compound (a1) having a hydroxyl group at one end represented by the above, an isocyanurate of hexamethylene diisocyanate and an isocyanurate of isophorone diisocyanate is an average of three or more isocyanate groups which are one or more selected from the group Polyisocyanate compounds (a2) and pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, ethylene oxide modified at least one selected from the group of pentaerythritol tri (meth) acrylate (meth) hydroxyl group-containing having an average acryloyl groups 3 to 20 (meth) acrylate Polysiloxane-containing polyisocyanate derivative obtained by reacting rate based compound (a3) [A], pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Urethane bond having an average of 3 to 20 acryloyl groups per molecule, which is one or more selected from the group of hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate and tripentaerythritol octa (meth) acrylate; [A], [B], and [A], [A], and [A], an acrylate compound [B] that does not have a component, and a photopolymerization initiator, 2 -methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [C2] 100 times the sum of [C2] % And the when [A]: [B]: [C2] = 0.1~5.0 wt%: 75 to 95% by weight: UV-curable coating composition containing at from 4.9 to 20 wt% . A cured film formed from the ultraviolet curable coating composition according to claim 1 .