JP7367316B2 - Highly hydrophobic active energy ray-curable composition and resin molded product - Google Patents

Description

The present invention relates to a curable composition that can be cured by irradiation with active energy rays, and that can form a cured product with high water slipping properties on the surface of a base material such as a resin molded article. The present invention also relates to a resin molded article in which a cured product of the curable composition is formed.

Resin molded products made from polymethyl methacrylate resin, polymethacrylimide resin, polycarbonate resin, polystyrene resin, acrylonitrile styrene resin, etc. are not only lightweight and have excellent impact resistance, but also have good transparency. These resins are used as materials for various automotive lamp lenses, glazings, exteriors, instrument covers, and other members.

In recent years, in vehicles such as automobiles, millimeter wave radar devices have been placed behind the emblem or front grill on the front of the vehicle in order to measure obstacles in front and the distance between vehicles.
However, since millimeter waves are highly attenuated by water, it is required that water droplets do not adhere to surfaces such as the front emblem and front grill of millimeter wave radar devices.
For example, Patent Document 1 describes that a polycarbonate resin copolymerized with dimethylpolysiloxane is used for the surface of a cover of a millimeter wave radar device.

JP2016-80479

However, the method described in Patent Document 1 has a problem in that the performance deteriorates over time and the initial performance cannot be maintained.

The purpose of the present invention is to solve these problems, and to provide an active energy ray-curable composition that can maintain water sliding properties for a long period of time, and a resin molded article containing the cured product. .

The gist of the present invention is an active energy ray-curable composition containing a copolymer A having an ionic group and a polysiloxane structure, a urethane (meth)acrylate B, and a polyfunctional (meth)acrylate C.

According to the present invention, it is possible to provide an active energy ray-curable composition capable of forming a cured product with excellent water sliding properties and appearance for a long period of time, and a resin molded article having the cured product.

Embodiments of the present invention will be described in detail below. Note that (meth)acryloyl means a generic term for methacryloyl and acryloyl. Similarly, (meth)acrylate means a generic term for methacrylate and acrylate.

The active energy ray-curable composition of the present invention includes a copolymer A having an ionic group and a polysiloxane structure, a urethane (meth)acrylate B, and a polyfunctional (meth)acrylate C.

<Copolymer A having an ionic group and a polysiloxane structure>
The active energy ray-curable composition contains a copolymer A having an ionic group and a polysiloxane structure in order to improve the water sliding properties of the surface of the cured product.
The main chain of the copolymer A has a polysiloxane structure.
Examples of the ionic group include cation species such as ammonium cation, phosphonium cation, imidazolium cation, and pyrrolidinium cation.
Among these, ammonium cations and phosphonium cations are preferred from the viewpoint of stability of the ionic group.

Examples of the copolymer having a polysiloxane structure and an ionic group include X-40-2450, X-40-2750, and X-48-9000 manufactured by Shin-Etsu Chemical Co., Ltd.

The amount of copolymer A in the composition is 0.1 parts by mass or more based on 100 parts by mass of the total amount of radically polymerizable compounds, which is the total amount of urethane (meth)acrylate B and polyfunctional (meth)acrylate C. It is preferably 10 parts by mass or less, more preferably 0.3 parts by mass or more and 5 parts by mass or less. The greater the amount of copolymer A blended, the better the water sliding properties are, and the smaller the amount of copolymer A blended, the better the transparency of the coating film.

<Urethane (meth)acrylate B>
The active energy ray-curable composition contains, as a radically polymerizable compound, urethane (meth)acrylate B synthesized from a polyol, a diisocyanate, and a mono(meth)acrylate containing a hydroxyl group. By using urethane (meth)acrylate B, the toughness and weather resistance of the cured product of the composition can be improved.

The polyol used in the synthesis of the urethane (meth)acrylate B is not particularly limited, but specific examples thereof include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, sorbitol, mannitol, and glycerin. Alkyl polyols such as and polyether polyols thereof; polyester polyols synthesized from polyhydric alcohols and polybasic acids, polyester polyols such as polycaprolactone polyols, polycarbonate polyols synthesized from transesterification of polyhydric alcohols and carbonate esters, etc. can be mentioned. Among these, polyester polyols and polycarbonate polyols are preferred from the viewpoint of weather resistance, and polycarbonate polyols are more preferred.

Specific examples of the mono(meth)acrylate containing a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy Examples include hydroxyalkyl (meth)acrylates such as butyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate. From the viewpoint of excellent balance between toughness and hardness, hydroxyalkyl (meth)acrylates having a hydroxyalkyl group having 4 or less carbon atoms are preferred, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4 -Hydroxybutyl acrylate is more preferred.

Specific examples of the polyisocyanate compound include isophorone diisocyanate, 2,2'-methylenebis(cyclohexyl)isocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3-bis(isocyanate). Examples include polyisocyanate monomers such as methyl) cyclohexane. From the viewpoint of weather resistance of the cured product, isophorone diisocyanate and 1,3-bis(isocyanatomethyl)cyclohexane are preferred.

The reaction between polyisocyanate, various diols, and (meth)acrylates containing hydroxyl groups is carried out in the presence of a tin-based catalyst such as n-butyltin dilaurate so that the isocyanate groups and hydroxyl groups are approximately equivalent. A method of heating at 60 to 80° C. for several hours can be adopted. Since the reactant generally has a high viscosity, it is preferable to dilute it with an organic solvent or other monomer during or after the reaction.

The amount of urethane (meth)acrylate B in the active energy ray-curable composition is preferably 10 parts by mass or more and 43 parts by mass or less, and 15 parts by mass or more and 29 parts by mass, based on 100 parts by mass of the total amount of the radically polymerizable compound. Part or less is more preferable. The higher the amount of urethane (meth)acrylate B, the better the weather resistance of the cured product and the curability of the curable composition in an air atmosphere, and the lower the amount of urethane (meth)acrylate B, the better the cured product. Improves wear resistance.

<Polyfunctional (meth)acrylate C>
The active energy ray-curable composition preferably contains polyfunctional (meth)acrylate C in order to further improve the surface hardness of the cured product and the adhesion to the substrate. The polyfunctional (meth)acrylate C is not particularly limited as long as it is a polyfunctional ethylenically unsaturated compound other than the urethane (meth)acrylate B, but aromatic A compound having two or more (meth)acryloyl groups that does not contain is preferred. Examples of the compound include di(meth)acrylate, trifunctional or higher polyfunctional (meth)acrylate, polyurethane poly(meth)acrylate, polyester poly(meth)acrylate, and the like.

Examples of the di(meth)acrylate include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and neopentyl glycol. Di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol (repeat unit n = 2 to 15) di(meth)acrylate, polypropylene glycol (repeat unit n = 2 to 15) di(meth)acrylate, polybutylene Glycol (repeat unit n = 2 to 15) di(meth)acrylate, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl) ) propane, trimethylolpropane di(meth)acrylate, tricyclodecane dimethanol diacrylate, and the like.

Examples of the trifunctional or higher polyfunctional (meth)acrylate include trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate modified with caprolactone, pentaerythritol tri(meth)acrylate, and caprolactone modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate modified with caprolactone, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate modified with caprolactone meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate modified with caprolactone, dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate modified with caprolactone, etc. can be mentioned.

Examples of the polyester poly(meth)acrylate include polyester poly(meth)acrylate such as polyester(meth)acrylate obtained by reacting trimethylolethane with succinic acid and (meth)acrylic acid.

Other specific examples of the polyfunctional (meth)acrylate C include polybasic acids such as phthalic acid, succinic acid, hexahydrophthalic acid, tetrahydrophthalic acid, terephthalic acid, azelaic acid, and adipic acid, ethylene glycol, and hexane. Examples include polyester (meth)acrylate obtained by reacting a polyhydric alcohol such as diol, polyethylene glycol, polytetramethylene glycol, trimethylolethane, and trimethylolpropane with (meth)acrylic acid or a derivative thereof. These may be used alone or in combination of two or more.

Among these, from the viewpoint of improving the surface protection performance of the cured product, polyfunctional (meth)acrylate C is preferably a trifunctional or higher functional (meth)acrylate, and trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, Dipentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate modified with caprolactone, dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate modified with caprolactone, pentaerythritol tri( Preferred are meth)acrylate, pentaerythritol tri(meth)acrylate modified with caprolactone, pentaerythritol tetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate modified with caprolactone. From the viewpoint of achieving both weather resistance and scratch resistance of the cured product, examples of polyfunctional (meth)acrylate C include dipentaerythritol hexa(meth)acrylate modified with caprolactone and trimethylolpropane tri(modified with caprolactone). Preference is given to meth)acrylates and mixtures thereof.

The blending amount of polyfunctional (meth)acrylate C in the active energy ray-curable composition is preferably 20 parts by mass or more and 90 parts by mass or less, and 30 parts by mass or more and 80 parts by mass or less, based on 100 parts by mass of the total amount of radically polymerizable compounds. Parts by mass or less are more preferable. By setting the blending amount of polyfunctional (meth)acrylate C to 20 parts by mass or more and 90 parts by mass or less, it is possible to achieve both wear resistance and weather resistance when the cured product is made.

The double bond equivalent of the radically polymerizable compounds of the active energy ray-curable composition means the total double bond concentration of all the radically polymerizable compounds contained in the composition, and is expressed by the following formula: It can be calculated by adding together the calculated values in proportion to the blend.

Double bond equivalent (mmol/g) of the active energy ray-curable composition = Σ {(number of acryloyl groups of each radically polymerizable compound) x 1000 x (mass fraction of each radically polymerizable compound in the composition)/ (Molecular weight of each radically polymerizable compound)}

The double bond equivalent of the radically polymerizable compound of the active energy ray-curable composition of the present invention is 3 mmol/g or more and 8 mmol/g or less. If it is more than the above lower limit, curing shrinkage will increase, resulting in poor adhesion to the substrate. Moreover, if it is less than the above upper limit, the crosslinking density becomes small and the scratch resistance becomes insufficient.

From the viewpoint of curing shrinkage and scratch resistance, the double bond equivalent of the radically polymerizable compound of the composition is preferably 5 mmol/g or more and 7 mmol/g or less.

<Photopolymerization initiator>
The active energy ray-curable composition of the present invention preferably contains a photopolymerization initiator from the viewpoint of curability. Any photopolymerization initiator can be used as long as it generates radicals when exposed to ultraviolet rays and polymerizes polymerizable monomers and oligomers, and may be appropriately selected in consideration of compatibility in the composition. Not done.

Specific examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, 2, 2-dimethoxy-2-phenylacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4-bis(dimethylaminobenzophenone), 2 -Carbonyl compounds such as hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one; tetra Sulfur compounds such as methylthiuram disulfide; azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile; peroxide compounds such as benzoyl peroxide and di-tert-butyl peroxide; 2,4,6- Examples include acylphosphine oxide compounds such as trimethylbenzoyldiphenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

Among them, benzophenone, methylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1, 2-diphenylethan-1-one and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferred. These may be used alone or in combination of two or more.

The amount of the photopolymerization initiator in the composition is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 5 parts by mass or less, based on 100 parts by mass of the total amount of radically polymerizable compounds. preferable. The larger the amount of the photopolymerization initiator is, the more the curability of the composition is improved, and the smaller the amount of the photopolymerization initiator is, the better the transparency and weather resistance of the cured product of the composition are.

<Ultraviolet absorber>
The active energy ray-curable composition preferably contains an ultraviolet absorber from the viewpoint of weather resistance of the cured product. The ultraviolet absorber is not particularly limited as long as it dissolves uniformly in the composition and the weather resistance of the cured product is good, but the UV absorber has high solubility in the composition and has good weather resistance of the cured product. From a certain point, it is a compound derived from any one of the triazine type, benzophenone type, benzotriazole type, phenyl salicylate type, and phenyl benzoate type, and has a maximum absorption wavelength in the range of 240 nm or more and 380 nm or less. Ultraviolet absorbers are preferred. In particular, benzophenone-based ultraviolet absorbers are more preferred since they can be contained in large amounts in the composition. Furthermore, triazine-based and benzotriazole-based ultraviolet absorbers are more preferred since they can prevent yellowing of base materials such as polycarbonate.

The content of the ultraviolet absorber in the composition is not particularly limited, but the ultraviolet absorber is The content is preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably 3 parts by mass or more and 15 parts by mass or less. If the content of the ultraviolet absorber is within the above range, the curability of the composition and the abrasion resistance of the cured product of the composition will be good. Moreover, the weather resistance (yellowing resistance) of the cured product of the composition is improved.

<Hindered amine light stabilizer>
The active energy ray-curable composition preferably contains a hindered amine light stabilizer in order to prevent deterioration of the substrate to which the composition is applied due to ultraviolet rays.

As the hindered amine light stabilizer, known ones can be used. Examples of hindered amine light stabilizers include 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol, and β,β,β,β-tetramethyl-3 , 9-(2,4,8,10-tetraoxaspiro[5,5])undecane) condensate with diethanol, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6- Condensate of pentamethyl-4-piperidinol and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5])undecane)diethanol, 1,1 - Condensate of dimethylethyl hydroperoxide and octane (for example, trade name: Tinuvin 123, manufactured by BASF), 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6) -tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine and the like are preferred. Further, a hindered amine light stabilizer having a (meth)acryloyl group in the molecule can also be used. Examples of the hindered amine light stabilizer having a (meth)acryloyl group in the molecule include {2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine) -4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine and 2-acryloyloxyethyl isocyanate. The reactant can be produced, for example, by the method described in JP-A No. 2008-56906. Among these, 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino ]-6-(2-hydroxyethylamine)-1,3,5-triazine, a hindered amine light stabilizer having a (meth)acryloyl group in the molecule, is preferred.

The content of the hindered amine light stabilizer in the composition is not particularly limited, but the content of the hindered amine light stabilizer in the composition is not particularly limited. The content of the light stabilizer is preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 0.5 parts by mass or more and 3 parts by mass or less. If the content of the hindered amine light stabilizer is within the above range, the cured product will have good weather resistance (crack resistance) and abrasion resistance.

The active energy ray-curable composition preferably contains an inorganic filler from the viewpoint of improving surface hardness, heat resistance, and electrical conductivity. The inorganic filler may include metal oxides such as silica, alumina, titanium oxide, or composite oxides thereof, from the viewpoint of shape stability, heat resistance, flame retardance, insulation properties, etc. of the cured product of the composition; Preferred are surface-treated metal oxides or surface-treated composite oxides obtained by surface-coating metal oxides or composite oxides with a silane coupling agent, etc., and hydroxides such as aluminum hydroxide, magnesium hydroxide, potassium hydroxide, and the like. In addition, from the viewpoint of improving conductivity, examples of the inorganic filler include metal particles such as gold, silver, copper, nickel, and alloys thereof, conductive particles such as carbon, carbon nanotubes, carbon nanohorns, and fullerenes, as well as glass, ceramics, Particles made of plastic, metal oxide, etc. whose core surface is coated with metal, ITO (indium tin oxide), etc. are preferable. These may be used alone or in combination of two or more. The conductive particles preferably have an aspect ratio of 5 or more from the viewpoint of conductivity. Note that the aspect ratio is a value calculated from (longer axis)/(breadth axis). The particle diameter of the inorganic filler is optically preferably 1 μm or less in terms of area average particle diameter. The amount of inorganic filler added to the active energy ray-curable composition can be adjusted as appropriate depending on the use of the composition, required mechanical strength, fluidity, etc. A known method can be used for blending the inorganic filler.

The active energy ray-curable composition preferably contains an organic solvent from the viewpoint of adjusting the viscosity to a value depending on the coating method. Examples of the organic solvent include alcoholic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, cyclohexyl alcohol, and diacetone alcohol; methyl cellosolve, cellosolve, butyl cellosolve, and methyl. Ether solvents such as carbitol, carbitol, butyl carbitol, diethyl carbitol, propylene glycol monomethyl ether; "Swazol 1000" (trade name, manufactured by Maruzen Petrochemical Co., Ltd.), "Supersol 100" (trade name, Nippon Petrochemical Co., Ltd.), "Supersol 150" (trade name, Nippon Petrochemical Co., Ltd.), aromatic solvents such as benzene, toluene, and xylene; cyclic hydrocarbon solvents such as cyclohexane; Examples include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, and propylene glycol acetate. These may be used alone or in combination of two or more. The organic solvent used is preferably selected appropriately depending on the type of substrate. For example, when polycarbonate is used as the base material, it is preferable to use an alcohol solvent such as isobutanol and an ester solvent such as n-butyl acetate as the organic solvent alone or in combination of two or more.

From the viewpoint of coating workability, the content of the organic solvent in the composition is preferably 30% by mass or more and 80% by mass or less. When spray painting the composition, Ford Cup No. It is preferable to add the organic solvent so that the viscosity is 15 seconds or more and 30 seconds or less at 20° C. using a 4-viscosity meter.

The active energy ray-curable composition may optionally contain a polymerization inhibitor, an anti-yellowing agent, an infrared absorber, a bluing agent, a pigment, a leveling agent, an antifoaming agent, a thickener, and a sedimentation agent as other components. It may also contain various additives such as an inhibitor, an antistatic agent, and an antifogging agent.

The active energy ray-curable composition can be produced by uniformly mixing the above-mentioned components using a known stirrer.

After the active energy ray-curable composition is applied onto a substrate, it can be crosslinked by irradiation with active energy rays to form a cured product. The amount of the composition applied to the substrate is preferably such that the thickness of the cured product is 1 μm or more and 50 μm or less, more preferably 3 μm or more and 40 μm or less. Methods for applying the composition to the substrate include bar coater coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, microgravure coating, brush coating, spray coating, and shower coating. Examples include flow coating method, dip coating method, curtain coating method, offset printing method, flexo printing method, screen printing method, potting and the like. Moreover, in order to adjust the viscosity, the composition may be applied after being heated.

The active energy ray is preferably an ultraviolet ray, and more preferably an ultraviolet ray with a wavelength of 340 nm or more and 380 nm or less. As the ultraviolet light source, a high pressure mercury lamp, a metal halide lamp, etc. can be used. The amount of ultraviolet irradiation can be, for example, 1000 mJ/cm ² or more and 5000 mJ/cm ² or less using ultraviolet rays with a wavelength of 340 nm or more and 380 nm or less. The active energy rays may be irradiated in air or in an inert gas such as nitrogen or argon.

After applying the active energy ray-curable composition onto the substrate, heat treatment may be performed before irradiating the active energy ray. The heat treatment can be performed by irradiation with a near-infrared lamp, circulation of hot air, or the like. When performing heat treatment, the surface temperature of the substrate in the furnace (hereinafter referred to as heating temperature) should be 40°C or more and 90°C or less, and the heating time should be 60 seconds or more and 180 seconds, in order to maintain adhesion for a long time outdoors. It is preferable that it is below. More preferably, the heating temperature is 50° C. or more and 70° C. or less, and the heating time is 90 seconds or more and 120 seconds or less. When the heating temperature is 40° C. or higher, organic solvents and the like inside the coating film can be sufficiently removed, and hardness, water resistance, and weather resistance are improved. In addition, when the heating temperature is 90° C. or less, the appearance becomes good and the weather resistance improves. When the heating time is 60 seconds or more, organic solvents and the like inside the coating film can be sufficiently removed, and hardness, water resistance, and weather resistance are improved. In addition, when the heating time is 180 seconds or less, the appearance becomes good and the weather resistance improves.

The active energy ray-curable composition can be used to modify the surface of various resin molded products as base materials. Examples of the resin molded product that is the base material include molded products containing synthetic resins such as various thermoplastic resins and thermosetting resins for which improvement in abrasion resistance, weather resistance, etc. is desired. Specifically, the synthetic resins include polymethyl methacrylic resin, polycarbonate resin, polyester resin, polystyrene resin, ABS (acrylonitrile-butadiene-styrene) resin, AS (acrylonitrile-styrene) resin, polyamide resin, polyarylate resin, Examples include polymethacrylimide resin, polyallyl diglycol carbonate resin, and the like. The synthetic resins include polymethyl methacrylic resin, polycarbonate resin, polystyrene resin, and polymethacrylic resin, since it is strongly desired to have excellent transparency and improved abrasion resistance, and the application of the composition is particularly effective. Imide resins are preferred. These may be used alone or in combination of two or more. Further, the resin molded product serving as the base material may be a sheet-like molded product, a film-like molded product, or various injection molded products containing these resins.

The cured product of the active energy ray-curable composition has excellent water sliding properties and appearance. Therefore, by applying the above composition to the surface of a polycarbonate resin molded product and irradiating it with active energy rays, a cured resin molded product is produced. It can be suitably used as molded products, polycarbonate resin molded products for automobile resin glass, and the like.

The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Measurement evaluations in Examples were performed by the following methods.

(1) Initial sliding angle For a resin molded product with a cured product of an active energy ray-curable composition formed on the surface of a base material, the sliding angle was measured using a contact angle meter (DM-500, manufactured by Kyowa Interface Science Co., Ltd.). The sliding angle of 20 μL of water was determined by the method. The initial sliding angle was evaluated using the following criteria.
"◎": 20 μL of water slides down at 30° or less.
"○": 20 μL of water slides down at an angle greater than 30° and less than or equal to 59°.
“△”: 20 μL of water slides down at angles greater than 59° and equal to or less than 85°.
"×": 20 μL of water does not slide down at 85° or more.

(2) Sliding angle after moisture resistance test For resin molded products with a cured product of active energy ray curable composition formed on the surface of the base material, after standing for 24 hours at 50°C and 99% humidity, resin molding After taking out the product and removing water droplets adhering to the surface of the resin molded product, the sliding angle of 20 μL of water was determined in the same manner as in (2). The sliding angle after the moisture resistance test was determined based on the following criteria.
"◎": 20 μL of water slides down at 50° or less.
"○": 20 μL of water slides down at an angle greater than 50° and less than 70°.
"Δ": 20 μL of water slides down at an angle greater than 70° and less than 90°.
"×": 20 μL of water does not slide down at 90°.

<Synthesis Example 1: Synthesis of urethane acrylate UA1>
In a 5-liter flask equipped with a dropping funnel with a heat-retaining function, a reflux condenser, a stirring blade, and a temperature sensor, 2 moles of dicyclohexylmethane-4,4'-diisocyanate and 300 ppm of n-butyltin dilaurate were charged as a diisocyanate, and the flask was opened. It was heated to 40°C in a hot water bath. With a dropping funnel with a heat-retaining function heated to 40°C, 1 mol of polycarbonate diol having a 3-methylpentane structure (number average molecular weight 800, manufactured by Kuraray Co., Ltd., trade name Kuraray Polyol C770) was added over 4 hours as a diol. It was dropped into the flask. The liquid in the flask was stirred at 40°C for 2 hours, and the temperature was further increased to 70°C over 1 hour. Thereafter, 2 moles of 2-hydroxyethyl acrylate as a mono(meth)acrylate containing a hydroxyl group was dropped into the flask over 2 hours, and the liquid in the flask was further stirred for 2 hours to obtain urethane acrylate UA1 (hereinafter referred to as (abbreviated as UA1) was synthesized.

(Example 1)
Active energy ray curable compositions were prepared using the blending ratios shown in Table 1. The composition was spray coated onto a 3 mm thick polycarbonate resin plate (trade name: Panlite L-1225Z, manufactured by Teijin Kasei Ltd.) so that the thickness of the cured product after curing was 10 μm. Next, the resin plate on which the coating film was formed was heated in an oven at 60° C. for 3 minutes to volatilize the organic solvent. Thereafter, the coating film is cured by irradiating the coating film with ultraviolet rays with a wavelength of 340 nm or more and 380 nm or less using a high-pressure mercury lamp at an integrated light amount of 3000 mJ/cm ² using a high-pressure mercury lamp to obtain a cured product of the active energy ray-curable composition. Obtained.

The above-mentioned evaluations were performed on the resin molded article in which the cured product of the obtained active energy ray-curable composition was formed. The evaluation results are listed in Table 1. In addition, the numerical value in the column of each component of the active energy ray curable composition in Table 1 means parts by mass. Moreover, the abbreviations in Table 1 mean the compounds or products shown in Table 2.

(Examples 2 to 5, Comparative Examples 1 and 2)
An active energy ray curable composition was prepared using the materials and compounding ratios shown in Table 1, and a resin molded article was obtained by forming a cured product of the active energy ray curable composition under the same conditions as in Example 1. The evaluation results are shown in Table 1.

As shown in Table 1, the resin compositions of Comparative Examples 1 and 2 used fluorine-based and silicone-based additives instead of copolymer A, so the initial slipping properties and the slipping properties after the humidity test were poor. there were.

The cured product obtained from the active energy ray-curable composition of the present invention is effective in improving the water sliding properties of various automotive lamp lenses, glazings, exteriors, covers for instruments, and other members.

Claims (7)

It contains a polysiloxane compound A having an ionic group and a polysiloxane structure, urethane (meth)acrylate B, and polyfunctional ( meth)acrylate C, and the blending amount of the urethane (meth)acrylate B is the same as that of the urethane (meth)acrylate. An active energy ray-curable composition in which the amount of B and the polyfunctional (meth)acrylate C is 10 parts by mass or more and 43 parts by mass or less based on 100 parts by mass of the radically polymerizable compound. The active energy ray curable composition according to claim 1, wherein the radically polymerizable compound in the active energy ray curable composition has a double bond equivalent of 3 mmol/g or more and 8 mmol/g or less. The active energy ray-curable composition according to claim 1 or 2, wherein the amount of the polysiloxane compound A is 0.1 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the total amount of radically polymerizable compounds. The activity according to any one of claims 1 to 3 , wherein the blending amount of the polyfunctional (meth)acrylate C is 20 parts by mass or more and 90 parts by mass or less based on 100 parts by mass of the total amount of the radically polymerizable compound. Energy ray curable composition. The active energy ray-curable composition according to any one of claims 1 to 4 , comprising 0.5 parts by mass or more and 20 parts by mass or less of an ultraviolet absorber, based on 100 parts by mass of the total amount of the radically polymerizable compound. The active energy ray-curable composition according to any one of claims 1 to 5 , which contains 0.1 parts by mass or more and 5 parts by mass or less of a hindered amine light stabilizer based on 100 parts by mass of the total amount of the radically polymerizable compound. thing. A resin molded article having a cured product of the active energy ray-curable composition according to any one of claims 1 to 6 on the surface of the resin molded article.