JP7276183B2 - Active energy ray-curable composition, coating agent, and coated article - Google Patents

Description

The present invention relates to active energy ray-curable compositions, coating agents, and coated articles containing organopolysiloxanes.

With the development of organic EL displays and wearable terminals, there is a demand for a coating agent that is hard enough to be applied to the outermost surface of a flexible substrate but that does not cause cracks or peeling. In particular, the outermost surface of an image display device, such as a touch panel, which is touched by a finger, is in need of a coating agent that is not scratched by fingernails or the like and that can maintain transparency.

Conventionally, an inorganic material such as glass was often used for the hard coat layer on the outermost surface of an image display device that is touched by a finger. An organic resin material is preferable because it is necessary to consider the safety of the case. However, when an organic resin material is used for the outermost surface of an image display device, various physical properties such as surface hardness, crack resistance, and adhesion to a substrate are required in addition to transparency.

Organopolysiloxanes containing organic functional groups have properties such as high hardness, transparency, flexibility, impact resistance, crack resistance, scratch resistance, abrasion resistance, moisture resistance, water resistance, heat resistance, weather resistance, and weather resistance. Hard coats, heat-resistant paints, building paints, medical materials, food It is widely used as resins, additives, adhesives, binders, and coating agents in fields such as industrial materials, automotive materials, electrical materials, flame retardant materials, molding materials, and various coating materials.

When various organic resins are blended with conventional organopolysiloxane containing organic functional groups for the purpose of imparting functionality or modifying the resin, shrinkage and cracks occur due to incompatibility and refractive index mismatch. problems such as whitening may occur. On the other hand, as unsaturated compounds having radical polymerizability, polyfunctional (meth)acrylates, unsaturated polyesters and the like are widely used. However, when an organopolysiloxane is mixed with a conventional radically polymerizable unsaturated compound, the compatibility between the two is poor, resulting in problems such as liberation of the organopolysiloxane component.

In this regard, by including urethane bonds in the constituent elements of the compound, the molecules are aggregated by the hydrogen bonds derived from the urethane bonds, improving compatibility and improving the flexibility and hardness of the cured product and coating layer. Consideration is underway.

For example, Patent Document 1 discloses an example in which a trifunctional alkoxysilane having a urethane acrylate structure is hydrolyzed to synthesize a silsesquioxane. Due to the presence of functional groups, there is a problem that changes over time may occur.
Patent Document 2 discloses an example of a cured film having both flexibility and surface hardness by using silsesquioxane having a urethane acrylate structure and having no condensable functional group at the terminal as a main component. However, a coating composition having excellent bending resistance while maintaining surface hardness has not yet been achieved.

Japanese Patent No. 5579072 JP 2019-38872 A

The present invention has been made in view of the above circumstances, and contains an organopolysiloxane that has excellent compatibility with various polymerizable unsaturated compounds, and has transparency, solvent resistance, hardness, crack resistance, and bending resistance. An object of the present invention is to provide an active energy ray-curable composition, a coating agent, and a coated article that give a cured film having excellent properties and adhesion to a substrate.

As a result of intensive studies to solve the above problems, the present inventors have found an organopolysiloxane having a urethane bond and a (meth)acryloyloxy group, an organopolysiloxane having a urethane bond and a (meth)acryloyloxy group without an organopolysiloxane skeleton. compound, silica fine particles, a poly(oxyalkylene) alkyl ether compound having a (meth)acryloyloxy group, and an aliphatic compound containing a small number of (meth)acryloyloxy groups, respectively, in predetermined amounts. The present inventors have found that it is suitable as a coating agent and that it gives a cured film that is transparent, has excellent solvent resistance, crack resistance, pencil hardness, bending resistance, and adhesion to substrates, and has completed the present invention.
In the present invention, the (meth)acryloyloxy group means an acryloyloxy group or a methacryloyloxy group.

（式中、Ｒ¹およびＲ²は、それぞれ独立して炭素原子数１～１０の２価の炭化水素基を表し、Ｒ³は、水素原子またはメチル基を表し、Ｒ⁴は、それぞれ独立して、水素原子、水素原子の一部もしくは全部がハロゲン原子で置換されていてもよい炭素原子数１～８のアルキル基、フェニル基、（メタ）アクリロイルオキシプロピル基、またはグリシドキシプロピル基を表し、Ｒ⁵は、水素原子、メチル基、エチル基、ｎ－プロピル基、またはｉ－プロピル基を表し、ａ、ｂ、ｃ、ｄおよびｅは、０．１≦ａ≦０．５、０≦ｂ≦０．２、０≦ｃ≦０．４、０≦ｄ≦０．４、０．２≦ｅ≦０．７、ａ＋ｂ＋ｃ＋ｄ＋ｅ＝１を満たす数を表し、ｆは、０≦ｆ≦０．３を満たす数を表す。）
（Ｂ）シロキサン骨格を含まず、かつ、ウレタン結合および（メタ）アクリロイルオキシ基を有する化合物
（Ｃ）平均粒子径が８０ｎｍ以下のシリカ微粒子
（Ｄ）（メタ）アクリロイルオキシ基を含有するポリ（オキシアルキレン）アルキルエーテル化合物
（Ｅ）（メタ）アクリロイルオキシ基の含有数が１以上３未満である脂肪族化合物
（Ｆ）活性エネルギー線によりラジカルを発生する重合開始剤
２． さらに、（Ａ）、（Ｂ）、（Ｄ）および（Ｅ）成分以外の重合性モノマーを含有する１に記載の活性エネルギー線硬化性組成物、
３． さらに、溶剤を含有する１または２に記載の活性エネルギー線硬化性組成物、
４． １～３のいずれかに記載の活性エネルギー線硬化性組成物からなるコーティング剤、
５． 基材と、この基材の少なくとも一方の面に直接または少なくとも１種のその他の層を介して積層された硬化膜とを有し、
前記硬化膜が、４に記載のコーティング剤から作製された硬化膜である被覆物品
を提供する。 That is, the present invention
1. including the following components (A) to (D), component (F) and, if necessary, component (E),
Of the total 100 parts by mass of components (A) to (E), 10 to 50 parts by mass of component (A), 10 to 50 parts by mass of component (B), 5 to 30 parts by mass of component (C), and (D ) contains 5 to 30 parts by mass of component, and 0 to 70 parts by mass of component (E),
An active energy ray-curable resin composition containing 0.1 to 10 parts by mass of component (F) with respect to a total of 100 parts by mass of components (A) to (E),
(A) Organopolysiloxane represented by the following average formula (I)

(wherein R ¹ and R ² each independently represent a divalent hydrocarbon group having 1 to 10 carbon atoms, R ³ represents a hydrogen atom or a methyl group, and R ⁴ each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be substituted with halogen atoms, a phenyl group, a (meth)acryloyloxypropyl group, or a glycidoxypropyl group; and R ⁵ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an i-propyl group, and a, b, c, d and e are 0.1≦a≦0.5, 0 ≤ b ≤ 0.2, 0 ≤ c ≤ 0.4, 0 ≤ d ≤ 0.4, 0.2 ≤ e ≤ 0.7, a + b + c + d + e = 1, and f represents a number satisfying 0 ≤ f ≤ 0 represents a number that satisfies .3.)
(B) A compound containing no siloxane skeleton and having a urethane bond and a (meth)acryloyloxy group (C) Silica fine particles having an average particle size of 80 nm or less (D) Poly(oxy) containing a (meth)acryloyloxy group (Alkylene) alkyl ether compound (E) Aliphatic compound containing 1 or more but less than 3 (meth)acryloyloxy groups (F) Polymerization initiator that generates radicals by actinic energy rays2. 1. The active energy ray-curable composition according to 1, further comprising polymerizable monomers other than components (A), (B), (D) and (E),
3. Furthermore, the active energy ray-curable composition according to 1 or 2 containing a solvent,
4. A coating agent comprising the active energy ray-curable composition according to any one of 1 to 3,
5. having a substrate and a cured film laminated directly or via at least one other layer on at least one surface of the substrate;
A coated article is provided, wherein the cured film is a cured film produced from the coating agent according to 4.

The active energy ray-curable composition of the present invention provides a cured film having excellent solvent resistance, crack resistance, high hardness, high flexibility, and adhesion. It is useful as a coating agent for surface layers and the like.

The present invention will be specifically described below.
The active energy ray-curable composition according to the present invention contains the following components (A) to (F).
(A) Organopolysiloxane represented by the following average formula (I) (B) A compound containing no siloxane skeleton and having a urethane bond and a (meth)acryloyloxy group (C) Fine silica particles (D) (meth) Poly (oxyalkylene) alkyl ether compound containing acryloyloxy group (E) (meth) aliphatic compound containing less than 3 (meth) acryloyloxy groups (F) polymerization initiator

(1) Component (A) Component (A) is an organopolysiloxane represented by the following formula (I), has high compatibility with other organic resins, and improves the flex resistance and crack resistance of the cured film. contribute to

In formula (I), R ¹ and R ² each independently represent a divalent hydrocarbon group having 1 to 10 carbon atoms, R ³ represents a hydrogen atom or a methyl group, and R ⁴ each represents independently, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be substituted with halogen atoms, a phenyl group, a (meth)acryloyloxypropyl group, or glycidoxypropyl R ⁵ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an i-propyl group, and a, b, c, d and e are 0.1≦a≦0.5 , 0 ≤ b ≤ 0.2, 0 ≤ c ≤ 0.4, 0 ≤ d ≤ 0.4, 0.2 ≤ e ≤ 0.7, a + b + c + d + e = 1, and f is 0 ≤ f represents a number that satisfies ≦0.3.

The divalent hydrocarbon group having 1 to 10 carbon atoms for R ¹ and R ² may be linear, branched or cyclic, and specific examples include methylene, ethylene, trimethylene, propylene, tetramethylene, hexa linear, branched or cyclic alkylene groups such as methylene, decamethylene and cyclohexylene groups; and arylene groups such as phenylene and xylylene groups.
Among these, an alkylene group having 1 to 5 carbon atoms is preferable, a linear alkylene group having 1 to 3 carbon atoms is more preferable, and an ethylene group and a trimethylene group are still more preferable.

The alkyl group having 1 to 8 carbon atoms for R ⁴ may be linear, branched or cyclic, and specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i- Butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl groups and the like, and these alkyl groups have some or all of their hydrogen atoms substituted with halogen atoms. may be
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
Halogen-substituted alkyl groups include chloromethyl, 3-chloropropyl and 3,3,3-trifluoropropyl groups.
Among these, R ⁴ is preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, more preferably a methyl group or a phenyl group.

a is a number that satisfies 0.1≤a≤0.5, preferably 0.2≤a≤0.5. If a is less than 0.1, the compatibility of the organopolysiloxane will be insufficient, and the curability of the composition containing the organopolysiloxane, as well as the hardness, scratch resistance, and crack resistance of the cured product. , and poor bending resistance.
b is a number that satisfies 0≦b≦0.2, preferably 0≦b≦0.1. If b exceeds 0.2, the resulting cured product will be inferior in crack resistance and flex resistance.
c is a number that satisfies 0≤c≤0.4, preferably 0≤c≤0.2. If c exceeds 0.4, the resulting cured product will be inferior in crack resistance and flex resistance.
d is a number that satisfies 0≤d≤0.4, preferably 0≤d≤0.3. If d exceeds 0.4, the resulting cured product will be inferior in hardness.
e is a number that satisfies 0.2≦e≦0.7, preferably 0.3≦e≦0.6. When e is less than 0.2, the organopolysiloxane becomes highly viscous, which is undesirable from the viewpoint of workability and processability. If e exceeds 0.7, the resulting cured product will be inferior in hardness.
f is a number that satisfies 0 ≤ f ≤ 0.3, but it is effective in suppressing the condensation reaction by the condensable functional group, and from the viewpoint of crack resistance, water resistance, and weather resistance of the resulting cured product. Considering , f is preferably a number that satisfies 0≦f≦0.1.

In particular, the compatibility with other polymerizable unsaturated compounds, the curability of the curable composition containing the organopolysiloxane, and the hardness, crack resistance, flex resistance, and hardness of the cured product obtained from the composition. From the viewpoint of water resistance, it is preferable that R ¹ is a trimethylene group, R ² is an ethylene group, R ³ is a hydrogen atom, and R ⁴ is a methyl group in the average formula (I).

Although the average molecular weight of the organopolysiloxane used in the present invention is not particularly limited, it is preferably 500 to 100,000, more preferably 700 to 10,000, in terms of polystyrene equivalent weight average molecular weight by gel permeation chromatography (GPC). preferable. If it is less than 500, the condensation does not proceed sufficiently, and the storage stability of the organopolysiloxane may deteriorate, and the condensation reaction may occur over time, failing to obtain good results in the heat and humidity resistance test. With a high molecular weight of more than 100,000, the film or coated article obtained by curing the active energy ray-curable composition containing the organopolysiloxane may not have good hardness and flexibility.

The viscosity of the organopolysiloxane used in the present invention is not particularly limited, but from the viewpoint of workability and processability, the viscosity at 25° C. measured by a rotational viscometer should be 200 to 50,000 mPa·s. It is preferably from 300 to 5,000 mPa·s.
Furthermore, the organopolysiloxane used in the present invention preferably has a non-volatile content of 96% by mass or more, excluding organic solvents and the like. If the volatile matter content increases, voids may be generated when the composition is cured, which may result in deterioration of appearance and deterioration of mechanical properties.
(A) component can be used individually by 1 type or in combination of 2 or more types.

The organopolysiloxane used in the present invention can be produced according to a general organopolysiloxane production method, for example, by condensing a hydrolyzable silane containing an organic group having a urethane bond and a (meth)acryloyloxy group. Obtainable.
Specifically, a hydrolyzable silane represented by the following formula (II) and, if necessary, other hydrolyzable silanes are used to perform hydrolytic condensation in the presence of a catalyst to produce organopolysiloxane. method.

In the formula, R ¹ to R ³ have the same meanings as above. Each X independently represents a chlorine atom or an alkoxy group having 1 to 6 carbon atoms.
As for the alkoxy group having 1 to 6 carbon atoms for X, the alkyl group therein may be linear, branched or cyclic. Specific examples thereof include methoxy, ethoxy, n-propoxy, i-propoxy, n -butoxy, t-butoxy, n-pentyloxy groups and the like.

Other hydrolyzable silanes used as necessary are not particularly limited as long as they can produce organopolysiloxane by hydrolytic condensation together with the hydrolyzable silane represented by the above formula (II). not something.
Specific examples include dimethyldimethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldiethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, and methyltrimethoxysilane. ethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropylmethyldiethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri Alkoxysilanes such as ethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, and hydrolytic condensation of these things are mentioned.

The amount of the other hydrolyzable silane and/or its hydrolytic condensate to be added is preferably 0.1 to 3 mol, more preferably 0.5 to 2 mol, per 1 mol of the silane of formula (II). be.

The catalyst used for condensation is not particularly limited, but acidic catalysts are preferred, and specific examples include hydrochloric acid, formic acid, acetic acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, and lactic acid. , carbonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and the like.
The amount of the catalyst to be used is not particularly limited, but considering the rapid progress of the reaction and the ease of removal of the catalyst after the reaction, the amount is 0.0002 to 0.002 to 0.0002 to 0.000 per mole of hydrolyzable silane. A 5 molar range is preferred.

The amount ratio between the hydrolyzable silane and the water required for the hydrolytic condensation reaction is not particularly limited. Considering easiness, it is preferable to use 0.1 to 10 mol of water with respect to 1 mol of hydrolyzable silane.
The reaction temperature during hydrolytic condensation is not particularly limited, but in consideration of improving the reaction rate and preventing decomposition of the organic functional group of the hydrolyzable silane, -10 to 150°C is preferred. Preferably, the reaction time is 1 to 6 hours.

In addition, you may use an organic solvent in the case of hydrolysis condensation. Specific examples of organic solvents include methanol, ethanol, propanol, acetone, methyl isobutyl ketone, tetrahydrofuran, toluene, and xylene.

The organopolysiloxane represented by the formula (I) is 10 to 50 parts by mass in a total of 100 parts by mass of the components (A) to (E). 15 to 40 parts by mass is preferable in consideration of flex resistance and pencil hardness.

(2) Component (B) The compound (B), which does not contain a siloxane skeleton and has a urethane bond and a (meth)acryloyloxy group, is not particularly limited, but is a polyol compound and an isocyanate compound. , a compound (urethane acrylate) synthesized using an acrylic acid ester compound as a starting material, and the like, and examples thereof include a monofunctional type, a polyfunctional type, a polymer type, and the like.
The number of functional groups ((meth)acryloyloxy groups) in the compound of component (B) is arbitrary, but in consideration of further increasing the adhesion, hardness, crack resistance, and flex resistance of the resulting resin or coating, 1 to 20 are preferred, 2 to 15 are more preferred, and 2 to 8 are even more preferred.
Examples of polymer type compounds include urethane acrylates containing a polyethylene skeleton, polyether skeleton, polycarbonate skeleton, polyester skeleton, or polyimide skeleton, and urethane acrylates containing a polyether skeleton or polyester skeleton are preferred.

Component (B) can be obtained as a commercial product, for example, U-2PPA, U-6LPA, U-10hA, U-10PA, UA-1100H, U-15HA, UA-53H, UA-33H, U- 200PA, UA-160TM, UA-290TM, UA-4200, UA-4400, UA-122P, UA-7100, UA-W2A (all manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 (all manufactured by Kyoeisha Chemical Co., Ltd.), KUA-4I, KUA-6I, KUA-9N, KUA-10H, KUA-15N, KUA-C2I, KUA-PC2I, KUA-PEA2I, KUA-PEB2I, KUA-PEC2I (all manufactured by KSM Co., Ltd.), EBECRYL 210, EBECRYL 220, EBECRYL 225, EBECRYL 230, EBECRYL 246, EBECRYL 270, E BECRYL 280, EBECRYL 284, EBECRYL 286, EBECRYL 294, EBECRYL 1258, EBECRYL 1271, EBECRYL 1290, EBECRYL 1291, EBECRYL 2221, EBECRYL 4101, EBECRYL 4141, EBECR YL 4201, EBECRYL 4220, EBECRYL 4250, EBECRYL 4265, EBECRYL 4396, EBECRYL 4397, EBECRYL 4491 , EBECRYL 4501, EBECRYL 4510, EBECRYL 4531, EBECRYL 4587, EBECRYL 4666, EBECRYL 4680, EBECRYL 4683, EBECRYL 4738, EBECRYL 4740, EBECRYL 4820, EBECRYL 4858, EBECRYL 4859, EBECRYL 5129, EBECRYL 8209, EBECRYL 8210, EBECRYL 8301R, EBECRYL 8307, EBECRYL 8311, EBECRYL 8402, EBECRYL 8405, EBECRYL 8409, EBECRYL 8411, EBECRYL 8413, EBECRYL 8465, EBECRYL 8602, EBECRYL 8701, EBECRYL 8 800, EBECRYL 8804, EBECRYL 8807, EBECRYL 8809, EBECRYL 8810, EBECRYL 8811, EBECRYL 9260, EBECRYL 9270, KRM7735, KRM8200, KRM8200AE, KRM8296, KRM8452, KRM8528, KRM8530, KRM8531BA, KRM8667, KRM8904, KRM8961, KRM8191 (all Daicel Allnex ( Co., Ltd.) and the like.

The content of the compound that does not contain a siloxane skeleton and has a urethane bond and a (meth)acryloyloxy group is 10 to 50 parts by mass based on the total of 100 parts by mass of components (A) to (E). 15 to 40 parts by mass is preferable in consideration of improving the adhesion of the cured product to the substrate, the smoothness, transparency and surface hardness of the film.

(3) Component (C) The fine silica particles of component (C) contribute to improving the surface hardness, scratch resistance and crack resistance of the cured film.
The silica fine particles are not particularly limited, and examples include those synthesized using tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane as starting materials.
As the silica fine particles, porous silica fine particles, hollow silica fine particles, and composite metal oxides of aluminum, magnesium, zinc, zirconium, titanium, etc. and silicon may be used. A low refractive index effect is also expected for hollow or porous fine particles.

The average particle diameter of the silica fine particles is 80 nm or less, preferably 50 nm or less, more preferably 30 nm or less, from the viewpoint of suitably adjusting the dispersion stability of the silica fine particles and the viscosity of the curable composition. If a particle size larger than 80 nm is used, the coated article obtained using the composition will have foreign matter and coating unevenness, and the transparency will be impaired.

The silica fine particles are preferably surface-modified with active energy ray-curable reactive groups. Such surface-modified silica fine particles have improved dispersion stability in the composition, and are fixed in the polymer matrix by irradiation with active energy rays to cause a cross-linking reaction.
Examples of surface-modified silica fine particles include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, and 3-glycidoxysilane. Silica fine particles surface-treated with propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and the like can be mentioned.

The silica fine particles used in the present invention may be used as a composition of silica fine particles and component (D) described later or other polymerizable unsaturated compounds. Such compositions are commercially available, e.g. -10, NANOCRYL E114, NANOCRYL E129, NANOCRYL E134, NANOCRYL E137, NANOCRYL E139, NANOCRYL E149, NANOCRYL E334 (all manufactured by Evonik Industries AG), SIRHDDA30WT%-E06, SIRHDDA30WT%-E01, SIRTPGDA30WT%-P01, SIRTP GDA30WT%-P02 (both CIK Nanotech ( Co., Ltd.) and the like.

The content of silica particles is 5 to 30 parts by mass in a total of 100 parts by mass of components (A) to (E). Considering this, 5 to 20 parts by mass is preferable.

(4) Component (D) The poly(oxyalkylene) alkyl ether compound containing a (meth)acryloyloxy group of component (D) improves the adhesion between the base material and the cured coating, and improves the smoothness and transparency of the coating. It contributes to improvement of durability and scratch resistance.
The hydrocarbon moiety in the (meth)acryloyloxy group-containing poly(oxyalkylene)alkyl ether compound may be linear, branched or cyclic.

Specific examples include ethoxydiethylene glycol (meth)acrylate, methoxytriethyleneglycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, triethyleneglycol di(meth)acrylate, polyethyleneglycol di(meth)acrylate, hexanediol EO. modified di(meth)acrylates, trimethylolpropane EO-modified tri(meth)acrylates, pentaerythritol EO-modified tetra(meth)acrylates, and the like.

Poly(oxyalkylene) alkyl ether compounds containing (meth)acryloyloxy groups are commercially available, e.g. , MIRAMER M282, MIRAMER M283, MIRAMER M284, MIRAMER M286, MIRAMER M287, MIRAMER M3130, MIRAMER M3150, MIRAMER M3160, MIRAMER M3190, MIRAMER M4004 (all manufactured by Bigen Specialty Chemical Co., Ltd.), Viscote #MTG, MPE400 A, MPE550A (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), light acrylate EC-A, light acrylate MTG-A, light acrylate EHDG-AT, light acrylate 130A, light acrylate 3EG-A, light acrylate 4EG-A, light acrylate 9EG -A, light acrylate 14EG-A, light acrylate PTMGA-250, light ester BC, light ester 130MA, light ester 041MA, light ester 2EG, light ester 3EG, light ester 4EG, light ester 9EG, light ester 14EG, (both Kyoeisha Chemical Co., Ltd.), AM-90G, AM-130G, A-200, A-400, A-600, A-1000, M-90G, M-230G, 2G, 3G, 4G, 9G, 14G, 23G (all manufactured by Shin-Nakamura Chemical Co., Ltd.).

The content of the (meth)acryloyloxy group-containing poly(oxyalkylene) alkyl ether compound is 5 to 30 parts by mass in the total of 100 parts by mass of the components (A) to (E), but the resulting cured product 5 to 20 parts by mass is preferable in consideration of enhancing adhesion to the base material, smoothness, transparency, and surface hardness of the film.

(5) Component (E) Aliphatic compounds containing 1 or more and less than 3 (meth)acryloyloxy groups in component (E) are effective in reducing the viscosity and curability of the coating liquid, and It also contributes to the improvement of adhesion with the coating film.
Low-molecular-weight compounds are highly volatile and many of them are designated as poisonous and deleterious substances. Therefore, considering the impact on the human body and the environment, it is recommended to use compounds containing two (meth)acryloyloxy groups. is preferred.
The hydrocarbon portion of the aliphatic compound containing 1 or more but less than 3 (meth)acryloyloxy groups may be linear, branched or cyclic.

Specific examples include ethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, isodecyl ( meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, isobornyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, 3, 3,5-trimethylcyclohexyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate acrylates, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di( meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate and the like.

An aliphatic compound containing 1 or more and less than 3 (meth)acryloyloxy groups is available as a commercial product.
Specific examples include MIRAMER M120, MIRAMER M121, MIRAMER M130, MIRAMER M131, MIRAMER M180, MIRAMER M181, MIRAMER M200, MIRAMER M201, MIRAMER M205, MIRAMER M213, MIRAMER M221, MIRAMER M251, MIRAMER M262 , MIRAMER M1130, MIRAMER M1140 , MIRAMER M1150 (all manufactured by Bigen Specialty Chemical Co., Ltd.), AIB, TBA, NOAA, INAA, IDAA, LA, STA, ISTA, IBXA, Viscoat #155, Viscoat #195, Viscoat #197, Viscoat #230, Viscoat #260 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), light acrylate IAA, light acrylate LA, light acrylate SA, light acrylate IB-XA, light acrylate NP-A, light acrylate MPD-A, Light acrylate 1.6HX-A, Light acrylate 1.9ND-A, Light acrylate DCP-A, Light ester E, Light ester NB, Light ester IB, Light ester TB, Light ester EH, Light ester ID, Light ester L, Light ester L-7, Light ester S, Light ester IB-X, Light ester EG, Light ester 1.4BG, Light ester NP, Light ester 1.6HX, Light ester 1.9ND (all manufactured by Kyoeisha Chemical Co., Ltd. ), S-1800A, A-DCP, A-HD-N, A-NOD-N, A-DOD-N (all manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

(Meth) The content of the aliphatic compound containing 1 or more acryloyloxy groups and less than 3 is 0 to 70 parts by mass in a total of 100 parts by mass of components (A) to (E), but (E ) is preferably 1 to 20 parts by mass, considering that a sufficient crosslink density can be obtained when the composition is cured and the coated article has excellent surface hardness and scratch resistance.

(6) Component (F) The photopolymerization initiator of component (F) is not particularly limited as long as it is an initiator that generates radical species by active energy rays. It may be appropriately selected from known photopolymerization initiators such as fin oxide type, benzophenone type, and thioxanthone type.
Specific examples include benzophenone, benzyl, Michler's ketone, thioxanthone derivatives, benzoin ethyl ether, diethoxyacetophenone, benzyl dimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, acylphosphine oxide derivatives. , 2-methyl-1-{4-(methylthio)phenyl}-2-morpholinopropan-1-one, 4-benzoyl-4'-methyldiphenylsulfide, 2,4,6-trimethylbenzoyldiphenylphosphine, etc. These may be used alone or in combination of two or more.

Photoinitiators are commercially available, e.g. Omnirad 1173, Omnirad MBF, Omnirad 127, Omnirad 184, Omnirad 369, Omnirad 379, Omnirad 379EG, Omnirad 651, Omnirad 754, Omnirad 784, Omnirad 819, Omnirad 819DW, Omnirad 907, Omnirad 2959, Omnirad TPO (all manufactured by IGM Resins B.V.) and the like.

The content of the photopolymerization initiator is 0.1 to 10 parts by mass with respect to the total of 100 parts by mass of the components (A) to (E), but the curability of the composition is improved and the resulting curing 0.5 to 5 parts by mass is preferable in consideration of preventing a decrease in the surface hardness of the film.

(7) Other Components The active energy ray-curable composition of the present invention may contain polymerizable monomers other than components (A), (B), (D) and (E).
Other polymerizable monomers (polymerizable unsaturated compounds) include epoxy acrylate, ester acrylate, thiourethane acrylate, fluorine-containing acrylate, and the like.
When other polymerizable unsaturated compounds are used, the content thereof is preferably 1 to 1,000 parts by mass, more preferably 5 to 500 parts by mass, with respect to 100 parts by mass of the active energy ray-curable composition of the present invention. preferable.
Specific examples of polymerizable monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and pentaerythritol tri(meth)acrylate. acrylates and the like.

The active energy ray-curable composition of the present invention may contain a solvent, if necessary. Preferred solvents include alcohols such as isopropanol and butanol, ethers such as tetrahydrofuran and diethylene glycol dimethyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and ethyl lactate, and glycols such as propylene glycol monomethyl ether acetate. Ether esters and the like can be mentioned.
When a solvent is contained, its content is not particularly limited, but the total amount of components (A), (B), (D) and (E) is 100 parts by mass (when other polymerizable monomers are included, the above components and It is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass based on the total amount of other polymerizable monomers (100 parts by mass).

The active energy ray-curable composition of the present invention further includes metal oxide fine particles, a silicone resin, a silane coupling agent, a diluent solvent, a filler, a plasticizer, an adhesion aid, a processing aid, a sensitizer, and a light absorber. agent, light stabilizer, polymerization inhibitor, heat ray reflector, antistatic agent, antioxidant, desiccant, preservative, anti-mold agent, antifouling agent, water repellent agent, oil repellent agent, anti-slip agent agent, anti-cratering agent, matting agent, coloring agent, anti-color separation agent, defoaming agent, defoaming agent, foam stabilizer, thickener, viscosity reducing agent, emulsifier, surfactant, wetting and dispersing agent, compatibilizer Various additives such as agents, rheology control agents, anti-sagging agents, anti-skin agents, surface conditioners, and leveling agents may be contained within the range that does not impair the object of the present invention.

The active energy ray-curable composition of the present invention is obtained by uniformly mixing the above components according to a conventional method.
The viscosity of the active energy ray-curable composition is not particularly limited. is preferably 50,000 mPa·s or less, more preferably 10,000 mPa·s or less. The lower limit of the viscosity at 25°C is preferably 10 mPa·s or more.

The active energy ray-curable composition of the present invention can be suitably used as a coating agent, and is applied directly or via at least one other layer to at least one surface of a substrate and cured. Thus, a coated article having a film formed thereon can be obtained.
Examples of the base material include, but are not limited to, plastic moldings, wood-based products, ceramics, glass, metals, and composites thereof.
In addition, the surface of these substrates has been treated with chemical conversion treatment, corona discharge treatment, plasma treatment, acid or alkaline solution, and decorative plywood coated with a different type of paint on the surface of the base material. can also be used.

Furthermore, the substrate surface on which other functional layers have been formed in advance may be coated with the coating agent of the present invention. A shielding layer and the like may be mentioned, and any one layer or a plurality of layers thereof may be formed in advance on the substrate.

The coated article has a surface on which a coating film made of the coating agent of the present invention is formed, and further a deposition layer by a CVD (chemical vapor deposition) method, a hard coat layer, an antirust layer, a gas barrier layer, a waterproof layer, and a heat ray shielding layer. It may be coated with one or more layers such as a layer, an antifouling layer, a photocatalyst layer, an antistatic layer, and the like.
Furthermore, the coated article has a hard coat layer, an antirust layer, a gas barrier layer, a waterproof layer, a heat ray shielding layer, an antifouling layer, It may be coated with one or more layers such as a photocatalyst layer and an antistatic layer.

The coating agent of the present invention is applied to the surface of articles that require surface hardness and surface scratch resistance, particularly various display elements such as liquid crystal displays and EL displays, to form a cured film, thereby improving these properties. It is possible to impart high hardness, bending resistance and crack resistance to the surface.
The method of applying the coating agent may be appropriately selected from known methods, and various coating methods such as bar coater, brush coating, spraying, immersion, flow coating, roll coating, curtain coating, spin coating, and knife coating may be used. can be used.

As the light source for curing the active energy ray-curable composition (coating agent), a light source containing light having a wavelength in the range of 200 to 450 nm, such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a xenon lamp, carbon An arc lamp etc. are mentioned. Although the irradiation dose is not particularly limited, it is preferably 10 to 5,000 mJ/cm ² , more preferably 20 to 1,000 mJ/cm ² .
The curing time is usually 0.5 seconds to 2 minutes, preferably 1 second to 1 minute.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples.
In the following, the volatile content is a value measured according to JIS C2133, and the weight average molecular weight is measured using GPC (gel permeation chromatography, HLC-8220 manufactured by Tosoh Corporation) using tetrahydrofuran (THF) as a developing solvent. It is a value measured as
Also, the values a to f in the average formula (I) were calculated from the results of ¹ H-NMR and ²⁹ Si-NMR measurements.

[1] Synthesis of organopolysiloxane represented by the average formula (I) [Synthesis Example 1] Synthesis of organopolysiloxane 1 With reference to the synthesis method described in Example 1-2 of JP-A-2019-38872, organopolysiloxane Siloxane 1 was synthesized. The obtained reactant was a viscous liquid at 25° C. having a viscosity of 2,980 mPa·s, a volatile content of 0.8 mass % and a weight average molecular weight of 1,970.
The values of a to f in the average formula (I) calculated from the NMR results are a=0.32, b=0, c=0.16, d=0, e=0.52, f=0. was 08.

[Synthesis Example 2] Synthesis of Organopolysiloxane 2 Organopolysiloxane 2 was synthesized with reference to the synthesis method described in Examples 1 to 3 of JP-A-2019-38872. The obtained reactant was a viscous liquid at 25° C. having a viscosity of 1,680 mPa·s, a volatile content of 0.6 mass %, and a weight average molecular weight of 1,550.
The values of a to f in the average formula (I) calculated from the NMR results are a=0.30, b=0, c=0, d=0.21, e=0.49, f=0. was 09.

[2] Production of active energy ray-curable composition (coating composition) [Examples 1-1 to 1-18, Comparative Examples 1-1 to 1-16]
Organopolysiloxane 1 obtained in Synthesis Example 1, Organopolysiloxane 2 obtained in Synthesis Example 2, KRM8200 (manufactured by Daicel Ornex Co., Ltd.), UA-122P (manufactured by Shin-Nakamura Chemical Co., Ltd.), NANOCRYL A235 (50 mass% pentaerythritol EO-modified tetraacrylate (PE (EO) TTA) dispersion of silica particles with a particle diameter of 20 nm, manufactured by Evonik Industries AG), 1,6-hexanediol diacrylate (HDDA, Osaka Organic Chemical Industry ( Co., Ltd.), Omnirad TPO, and Omnirad 184 (both radical photopolymerization initiators, manufactured by IGM Resins B.V.) were mixed at the compounding ratio (parts by mass) shown in Table 1 to prepare an active energy ray-curable composition. prepared the product. Table 2 shows the ratios of components (A) to (E).

[3] Production and evaluation of coated articles [Examples 2-1 to 2-18, Comparative Examples 2-1 to 2-16]
The compositions prepared in each of the above examples and comparative examples were coated on a PET substrate (A4100, manufactured by Toyobo Co., Ltd.) using a bar coater so that the film thickness after curing was 10 μm, and the composition was irradiated integrally with a high-pressure mercury lamp. A coated article was manufactured by irradiating with light so as to have an amount of 600 mJ/cm ² and curing to form a cured film.

Appearance, adhesion, solvent resistance, pencil hardness, flex resistance, and flex durability were evaluated for each cured film of the coated article obtained. Table 3 shows the results.
(1) Observation of Appearance When cracks or agglomeration was visually observed on the surface, it was evaluated as NG.
(2) Adhesion test A cross-cut test was performed using 25 squares according to JIS K5600-5-6, and the result was expressed as (the number of squares remaining without peeling)/25.
(3) Solvent resistance Absorbent cotton was impregnated with acetone and reciprocated on the cured film 50 times.
(4) Pencil hardness (surface hardness)
It was measured with a load of 750 g according to JIS K5600-5-4.
(5) Bending resistance Measured using a cylindrical mandrel (type 1) according to JIS K5600-5-1, and regarding bending resistance, for films that cracked in the 8 mm φ test, it was set to > 8 mm φ. .
(6) Durability The coated article was fixed to a durability tester (DMLHB-P150, manufactured by Yuasa System Co., Ltd.), suspended with a weight of 500 g, and bent 90 degrees using a bending R jig with a radius of 5 mm. Return to a straight shape, then bend it 90 degrees in the opposite direction and then return it to a straight shape. Repeat this operation 20,000 times at a speed of about 30 times per minute. It was judged as OK when the properties and adhesiveness were maintained.

As shown in Table 3, the cured films obtained by curing the active energy ray-curable compositions (coating agents) obtained in Examples 1-1 to 1-18 had adhesion and solvent resistance. , pencil hardness, flex resistance, and excellent durability. Therefore, the present invention can be suitably used for applications requiring hardness and bending resistance, such as flexible devices such as organic EL, surface layers of touch panels, and the like.

Claims (5)

including the following components (A) to (D), component (F) and, if necessary, component (E),
Of the total 100 parts by mass of components (A) to (E), 10 to 50 parts by mass of component (A), 10 to 50 parts by mass of component (B), 5 to 30 parts by mass of component (C), and (D ) contains 5 to 30 parts by mass of component, and 0 to 70 parts by mass of component (E),
An active energy ray-curable resin composition containing 0.1 to 10 parts by mass of component (F) with respect to a total of 100 parts by mass of components (A) to (E).
(A) Organopolysiloxane represented by the following average formula (I)

(wherein R ¹ and R ² each independently represent a divalent hydrocarbon group having 1 to 10 carbon atoms, R ³ represents a hydrogen atom or a methyl group, and R ⁴ each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be substituted with halogen atoms, a phenyl group, a (meth)acryloyloxypropyl group, or a glycidoxypropyl group; and R ⁵ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an i-propyl group, and a, b, c, d and e are 0.1≦a≦0.5, 0 ≤ b ≤ 0.2, 0 ≤ c ≤ 0.4, 0 ≤ d ≤ 0.4, 0.2 ≤ e ≤ 0.7, a + b + c + d + e = 1, and f represents a number satisfying 0 ≤ f ≤ 0 represents a number that satisfies .3.)
(B) Compounds containing no siloxane skeleton and having a urethane bond and (meth) acryloyloxy group (C) Silica fine particles having an average particle size of 80 nm or less (D) Ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol ( meth)acrylate, methoxypolyethylene glycol (meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hexanediol EO-modified di(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate and Compound selected from pentaerythritol EO-modified tetra(meth)acrylates (E) Ethyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate Acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, isoamyl (meth)acrylate, lauryl (meth)acrylate, n-stearyl (meth)acrylate, isostearyl (meth)acrylate, isobornyl (meth)acrylate, 4-t -butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate ) acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth) The number of (meth)acryloyloxy groups selected from acrylates, 1,10-decanediol di(meth)acrylates and dimethylol-tricyclodecanedi(meth)acrylates is 1 or more and less than 3. Aliphatic compound (F) activity Polymerization initiator that generates radicals by energy rays 2. The active energy ray-curable composition according to claim 1, further comprising polymerizable monomers other than components (A), (B), (D) and (E). 3. The active energy ray-curable composition according to claim 1, further comprising a solvent. A coating agent comprising the active energy ray-curable composition according to any one of claims 1 to 3. having a substrate and a cured film laminated directly or via at least one other layer on at least one surface of the substrate;
A coated article, wherein the cured film is a cured film prepared from the coating agent according to claim 4.