JP2016216623A - Ultraviolet curable coating agent composition and cured film thereof - Google Patents

Abstract

PURPOSE: To provide an ultraviolet curable coating agent composition having excellent thin film high speed curability and excellent in slipperiness and a cured film using the same.SOLUTION: There are provided an ultraviolet curable coating agent composition containing [A] a polysiloxane-containing polyisocyanate-based derivative by reacting a polysiloxane compound containing a hydroxyl group at a single terminal (a1), a polyisocyanate compound which is a trimer compound or a polymer compound (a2) and a hydroxyl group-containing (meth)acrylate compound having 3 or more (meth)acryloyl groups (a3), [B] a (meth)acrylate compound having 3 or more (meth)acryloyl groups, [C1] a photoinitiator-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1-one and/or [C2] 2-methyl-1-(4-methyl thiophenyl)-2-morpholinopropane-1-one and a cured film thereof.SELECTED DRAWING: None

Description

The present invention can be used for rewritable cards such as IC cards, building materials, food packaging packages, and optical products. It has excellent thin film and high-speed curability, and is slippery and antifouling. The present invention relates to an ultraviolet 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, transportation fields such as automatic ticket gates and automatic toll collection on highways, and identification fields such as membership cards and registration cards. Information recognition media on which IC chips such as IC tags and IC sheets are mounted are used. In particular, there is an increasing expectation for non-contact information recognition technology (referred to as RFID (Radio Frequency Identification)) using radio technology using radio waves, and RFID cards, RFID tags, RFID sheets, etc. using this technology. The use of other information recognition media is also expanding.

An ultraviolet curable resin has been proposed for use as a protective layer on the surface of rewritable cards such as IC cards and IC sheets (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 image formation and erasure. Therefore, a curable silicone resin or a silicone-modified resin is used for the formed protective layer to impart slipperiness to prevent head wrinkle adhesion (Patent Documents 4 to 7).

However, a curable silicone resin or a silicone-modified resin requires several hours to several days to produce a cured film, and has little cost merit.

Moreover, although the silicone resin composition with ultraviolet curing property was proposed in the past (patent documents 8 and 9), the curability was insufficient for curing at high speed.

Furthermore, an attempt has been made to use the ultraviolet curable resin composition in a thin film by reducing the amount used for cost reduction. However, it can be cured if it is usually several μm or more, but in the case of a thin film of less than 1 μm, there is a problem that it is difficult to form a cured film by high-speed curing because it is strongly affected by the inhibition of polymerization by oxygen.
Japanese Patent Laid-Open No. 06-8626 Japanese Patent Application Laid-Open No. 06-344672 Japanese Patent Laid-Open No. 08-11433 JP-A-2005-212362 JP 2005-53124 A JP 05-38881 A JP 2013-121777 A JP 2006-0455504 A JP 2003-192751 A

The present invention is an ultraviolet curable coating composition that is excellent in slipperiness and capable of thin film curing and high-speed curing superior to ordinary ultraviolet curable resins, and also has good stain resistance and cellophane tape peelability. It aims at providing the cured film.

The present inventor used a specific polysiloxane-containing polyisocyanate derivative [A], a specific (meth) acrylate compound [B], and a specific photopolymerization initiator as constituents of the ultraviolet curable coating composition. It has been found that the above problems can be solved by having C1] and / or [C2] and making them have a specific composition ratio, and the present invention has been completed.

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

In the present invention 2, the acrylate compound [B] of the present invention 1 is 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 at least one selected from the group consisting of pentaerythritol hepta (meth) acrylate and tripentaerythritol octa (meth) acrylate.

Invention 3 is the invention 1 or 2, wherein [A]: [B]: [C1] and / or [C2] = 0.1 to 5.0% by weight: 75 to 95% by weight: 4.9 to 20 It is an ultraviolet curable coating composition that is wt%.

This invention 4 is a cured film formed from the ultraviolet curable coating agent composition in any one of this invention 1-3.

According to the present invention, a cured film having an excellent thin film / high-speed curability and excellent slipperiness can be obtained. Such a cured film is useful as an ultraviolet curable coating composition for use in a rewritable card such as an IC card. In addition, since it has stain resistance and cellophane tape peelability, it is also useful as a surface coating agent for building materials, food packaging packages, optical products and the like.

The present invention is described in detail below. The present invention relates to a polysiloxane compound (a1) containing a hydroxyl group at one end (hereinafter referred to as “component (a1)”), a polyisocyanate compound (a2) having three or more isocyanate groups (hereinafter referred to as “(a2)”. ) Component ”and a polysiloxane-containing polyisocyanate derivative obtained by reacting a hydroxyl group-containing (meth) acrylate compound (a3) (hereinafter referred to as“ component (a3) ”) having three or more (meth) acryloyl groups. [A] (hereinafter referred to as “component (A)”) An acrylate compound [B] (hereinafter referred to as “component (B)”) having an average of 3 to 20 acryloyl groups per molecule and having no urethane bond. ) And photoinitiator-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 “component (C2)”).

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

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

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

(In 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. integer, m is an integer of 1 to 50, n is from 1 to 50 integer, ^{R 3} is at least 2 or more - _{(CH 2)} a r -OH, others a hydrogen atom, and methyl group - (CH _{2 Q} may be any one of -OH, _q is an integer of 1 to 50, and r is an integer of 1 to 50.)

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

Although it does not specifically limit as a number average molecular weight of the said (a1) component, It is preferable that it is 100-20,000. Here, the number average molecular weight is a converted value from the hydroxyl value (number average molecular weight = 56110 ÷ hydroxyl value (mgKOH / g) × number of hydroxyl groups per molecule). By setting the number average molecular weight to 100 or more, the cured film can have excellent slipping property, stain resistance and cellophane tape peelability, and by setting the number average molecular weight to 20,000 or less, the cured film is easily solidified. be able to.

The quantification of the hydroxyl value can be measured, for example, according to JIS K 1557.

Specific examples of the component (a1) include X-22-170DX (manufactured by Shin-Etsu Silicone Co., Ltd.), X-22-4015 (manufactured by Shin-Etsu Silicone Co., Ltd.), Silaplane FM-0411 (JNC Co., Ltd.) ), Silaplane FM-0421 (manufactured by JNC), Silaplane FM-0425 (manufactured by JNC), Silaplane FM-DA11 (manufactured by JNC), Silaplane FM -Products such as DA21 (manufactured by JNC Corporation), Silaplane FM-DA26 (manufactured by JNC Corporation), and the like.

As said (a2) component, if it is a polyisocyanate type compound which has 3 or more on average, it will not specifically limit, For example, polyisocyanate of an aromatic type, an aliphatic type, an alicyclic type etc. is mentioned. By having three or more isocyanate groups, it is possible to reduce unreacted low molecular weight components such as the reaction product of only (a2) and (a1) and the reaction product of only (a2) and (a3), and curing. Reduced membrane bleed. Furthermore, the isocyanate equivalent (g / eq) is preferably 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, tetramethylxylylene diisocyanate Polyisocyanates such as isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, phenylene diisocyanate, lysine diisocyanate, lysine triisocyanate, naphthalene diisocyanate, etc., or multimeric compounds of these polyisocyanates, burette 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 quantification of the isocyanate equivalent can be measured according to, for example, JIS K 7301.

The component (a3) is not particularly limited, but a hydroxyl value of 250 mgKOH / g or less is preferable. Thereby, the concentration of acryloyl groups 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 the cured film can be imparted. When only two or less acryloyl groups are present, the curability is insufficient and the thin film curability is lowered.

As a method for synthesizing the component (A), a known method may be employed. In a solvent, triethylenediamine, 1,8-diazabicyclo- [5,4,0] -undecene-7, stannous octylate, lead dioctylate, bismuth dioctylate, bismuth trioctylate, bismuth trineodecanoate, dibutyltin dilaurate, In the presence of a catalyst selected from dioctyltin laurate and the like, the reaction is usually carried out at a reaction temperature of about 60 to 90 ° C.

As 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 to 2. It is preferably 25/1 to 1.25 / 1 to 2.25.

The average number of acryloyl groups per molecule of the above-mentioned [A] component is preferably 5 to 20 from the viewpoint of improving thin film curability and fast curability. More preferably, it is 5-10.

The [B] component 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, excellent curability can be obtained even for thin films that are susceptible to curing inhibition by oxygen. The acrylate compound having a urethane bond does not exhibit the effects of the present invention because the photopolymerization reactivity is inferior to that of the [B] component. Preferably, it is an acrylate compound having an average acryloyl number of 5 to 20 per molecule in terms of better thin film curing and high-speed curability. 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) acrylate and tripentaerythritol octa (meth) acrylate.

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

The ultraviolet curable resin composition of the present invention further comprises triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2 as an auxiliary of the photopolymerization initiator. -Dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4- Diethylthioxanthone, 2,4-diisopropylthioxanthone and the like can be used in combination.

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

The ultraviolet curable coating composition containing the [A] component, the [B] component, the [C1] component and / or the [C2] component has a composition ratio of [A]: [B]: [C1] and [C2] = 0.1 to 5.0% by weight: 75 to 90% by weight: 4.9 to 20% by weight is preferable. Thereby, a cured film that can be cured even by 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 contained. An ultraviolet curable coating agent composition is obtained.

This composition can be used by blending an organic solvent and adjusting the viscosity as necessary. Examples of the organic solvent include ethyl acetate, butyl acetate, toluene, xylene, methanol, ethanol, propanol, butanol, acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, cellosolve such as ethyl cellosolve, and propylene such as propylene glycol monomethyl ether. Examples include glycol ethers and diacetone alcohol. 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 that emits light in a wavelength range of 150 to 450 nm, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless lamp, an LED lamp, etc. What is necessary is just to irradiate about 50-100 mJ / cm < ² >. After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.

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

As a method for forming a coating layer (cured film) on the article surface using the coating agent 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 performed 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, and screen printing. The coating amount is not particularly limited, but is usually in a range where the weight after drying is 0.1 to 20 g / m ² .

The article (base material) on which the coating layer can be formed using the coating agent composition of the present invention is not particularly limited. For example, plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine) Resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene-based resin, etc.), metal, wood, paper, glass, slate and the like.

The cured film formed from the ultraviolet curable coating composition of the present invention is also one aspect 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 thin film cured film can be formed by high-speed curing.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In each example, all parts and% are based on 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 tube, a dropping funnel and a nitrogen introducing tube, 100 parts of isocyanurate of hexamethylene diisocyanate, 0.3 part 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, dipentaerythritol pentaacrylate 347 parts, ethyl acetate part 629 parts, The temperature in the system was raised to about 70 degrees. Next, at the same temperature, the reaction system was maintained for 3 hours, and after confirming that the isocyanate group had 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])
In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, 100 parts of an isocyanurate body of isophorone diisocyanate, 0.2 part 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, dipentaerythritol pentaacrylate 300 parts, ethyl acetate part 557 parts, and about 1 hour The temperature inside was raised to about 70 degrees. Next, at the same temperature, the reaction system was held for 3 hours, and after confirming that the isocyanate group had disappeared, the reaction system was cooled to obtain an ultraviolet 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 tube, a dropping funnel and a nitrogen introducing tube, 100 parts of isocyanurate of hexamethylene diisocyanate, 0.1 part 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, 2-hydroxyethyl acrylate (one acryloyl group) 40 parts, ethyl acetate 297 parts, The temperature in the system was raised to about 70 degrees over about 1 hour. Next, at the same temperature, the reaction system was maintained for 3 hours, and after confirming that the isocyanate group had 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)
A four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet is charged with 77.1 parts of hexamethylene diisocyanate trimer, 0.10 parts of dibutyltin dilaurate, and 500 parts of methyl ethyl ketone at 60 ° C. or less. 422.9 parts of dipentaerythritol pentaacrylate and 0.4 part of 2,6-di-tert-butylcresol were added dropwise in about 1 hour, the reaction was continued at 60 ° C., and the reaction was completed when the isocyanate group disappeared. As a result, a urethane (meth) acrylate compound was obtained.

(Preparation of coating solution)
Each ultraviolet curable coating composition obtained by the above synthesis was used as a paint to prepare a coating solution.

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

(Example 2)
To 2 parts of the polysiloxane-containing polyisocyanate derivative obtained in Synthesis Example 1, 93 parts of dipentaerythritol pentaacrylate, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [C2] 5 parts was blended, diluted with methyl ethyl ketone so that the nonvolatile content was 25%, and mixed uniformly.

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

Example 4
To 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] 5 parts was blended, diluted with methyl ethyl ketone so that the nonvolatile content was 25%, and mixed uniformly.

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

(Comparative Example 2)
To 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- 5 parts of propan-1-one [C1] was blended, diluted with methyl ethyl ketone so that the nonvolatile content was 25%, and mixed uniformly.

(Comparative Example 3)
The polysiloxane-containing polyisocyanate derivative obtained in Synthesis Example 1 is blended with 85 parts of dipentaerythritol pentaacrylate and 5 parts of Darocur 1173 (Ciba Specialty Chemicals Co., Ltd.), resulting in a nonvolatile content of 25%. Diluted with methyl ethyl ketone and mixed uniformly.

(Comparative Example 4)
The polysiloxane-containing polyisocyanate derivative obtained in Synthesis Example 1 is mixed with 85 parts of dipentaerythritol pentaacrylate and 5 parts of Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.), resulting in a nonvolatile content of 25%. Diluted with methyl ethyl ketone and mixed uniformly.

(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- [2- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl } 5 parts of 2-methyl-propan-1-one [C1] was blended, diluted with methyl ethyl ketone so that the nonvolatile content was 25%, and mixed uniformly.

(Comparative Example 6)
To 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)- [Benzyl] phenyl} -2-methyl-propan-1-one [C1] (5 parts) was blended, diluted with methyl ethyl ketone so that the nonvolatile content was 25%, and mixed uniformly.

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

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

<Appearance>
The appearance of the cured film was visually evaluated for the presence or absence of defects in leveling (smoothness), yuzu skin, and pinholes.
○ = Smooth and free from defects such as yuzu skin and pinholes.
× = Not smooth, with defects such as yuzu skin and pinholes.

<Curing property>
A cotton swab soaked with methyl ethyl ketone was rubbed against the cured film 50 times, and the presence or absence of change in the cured film was visually confirmed.
○ = There is no change in the cured film compared to before the test.
X = Whitening is observed in the cured film.
Xx = The cured film is peeled off.

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

<Contamination resistance>
Using oil-based magic ink (Hi-Mckee Black Zebra Co., Ltd.), the oil-based magic ink was applied linearly to the cured coating film, dried for 5 minutes, then wiped with Kimwipe, and the wiping property was evaluated.
○ = No wiping trace
× = Can not be wiped off

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

*: Since the cured film component was not cured, it could not be measured.

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

Claims (4)

Polysiloxane compound (a1) containing a hydroxyl group at one end, polyisocyanate compound (a2) having an average of three or more isocyanate groups, and hydroxyl group-containing (meth) acrylate compound having an average of 3 to 20 (meth) acryloyl groups A polysiloxane-containing polyisocyanate derivative [A] obtained by reacting (a3), an acrylate compound [B] having an average of 3 to 20 acryloyl groups per molecule and having no urethane bond, and a photopolymerization initiator -Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one [C1] and / or 2-methyl-1- ( UV-curable coating containing 4-methylthiophenyl) -2-morpholinopropan-1-one [C2] Composition. The acrylate compound [B] is pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and 2. The ultraviolet curable coating composition according to claim 1, wherein the composition is one or more selected from the group of tripentaerythritol octa (meth) acrylate. The ultraviolet curable coating composition of Claim 1 is [A]: [B]: [C1] and / or [C2] = 0.1-5.0 weight%: 75-95 weight%: 4.9. The ultraviolet curable coating composition according to claim 2, wherein the composition is -20% by weight. The cured film formed from the ultraviolet curable coating agent composition in any one of Claims 1-3.