JP6973333B2 - An active energy ray-curable composition containing an organopolysiloxane compound having a polymerizable functional group. - Google Patents

Description

The present invention relates to an active energy ray-curable composition containing an organopolysiloxane compound having a polymerizable functional group.

Organopolysiloxane compounds containing organic functional groups have high hardness, flexibility, heat resistance, weather resistance, impact resistance, crack resistance, abrasion resistance, corrosion resistance, water resistance, water repellency, and mold release resistance. Since it provides a cured product with properties such as electrical insulation and processability, it is widely used as a resin and coating agent in the fields of hard coats, paints for building materials, molding materials, medical materials, automobile materials, various coating materials, etc. Has been done.

In recent years, a touch panel is often installed on the outermost surface of a display such as a smartphone. In this touch panel, when the outermost surface is touched by a finger, the slipperiness that allows the finger in contact with the ground to move smoothly is important, and therefore, the surface thereof is generally coated to improve the slipperiness.
Recently, the rise of flexible devices typified by organic EL has been remarkable, and along with this, a material having excellent flexibility while maintaining surface hardness has been required as a coating material.

When various resins are blended with a conventional organopolysiloxane compound containing an organic functional group to impart functionality, the compatibility is insufficient, and the cured resin, coating film, etc. May cause problems such as shrinkage and cracking. In particular, in a mixed composition with a modifier that imparts slipperiness, compatibility is poor, and a bleeding phenomenon or a whitening phenomenon is often observed on the cured resin or coating surface.
Further, as an unsaturated compound having radical polymerization properties, polyfunctional (meth) acrylate, unsaturated polyester and the like are widely used. However, when an organopolysiloxane compound is mixed with a conventional unsaturated compound having radical polymerization property, there is a problem that the organopolysiloxane component is liberated because the compatibility between the two is poor.

In this regard, studies have been conducted to improve compatibility and toughness of cured products by aggregating molecules by hydrogen bonds derived from urethane bonds by incorporating urethane bonds in the constituent elements of the compound. ..
Further, studies have been conducted to improve the compatibility with various resins by containing a polyalkylene ether bond in the constituent elements of the compound, and to improve the slipperiness, smoothness, and elasticity of the cured product. ..

For example, Patent Document 1 discloses an example in which a trifunctional alkoxysilane having a urethane acrylate structure is hydrolyzed to synthesize silsesquioxane, but the terminal of the obtained silsesquioxane is condensable. Since the functional group is present, there is a problem that the change with time may occur.
Further, in Patent Document 2, an active energy ray-curable fluorine-containing silicon polymer is used for forming a surface-treated layer having surface slipperiness, but since it contains fluorine, it is compatible with other constituents. It is low and has a problem that it is difficult to achieve both high hardness and bending resistance.

Japanese Patent No. 5579072 Japanese Patent No. 5614509

The present invention has been made in view of the above circumstances, and contains an organopolysiloxane compound having excellent compatibility with various polymerizable unsaturated compounds, and has properties such as hardness, crack resistance, bending resistance, and slipperiness. It is an object of the present invention to provide an active energy ray-curable composition which can give an excellent cured product and a coating film.

As a result of diligent studies to achieve the above object, the present inventor has a predetermined organopolysiloxane compound having a urethane bond and a (meth) acryloyloxy group, a polyalkylene ether bond, and a (meth) acryloyloxy group. The present invention has been completed by finding that the above-mentioned problems can be solved in an active energy ray-curable composition containing a predetermined organopolysiloxane compound.
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、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。）

（式中、Ｒ¹およびＲ³〜Ｒ⁵は、前記と同じ意味を表し、Ｒ⁶は、炭素原子数１〜１０の２価の炭化水素基を表し、ａ′、ｂ′、ｃ′およびｄ′は、０．０５≦ａ′≦０．５、０≦ｂ′≦０．２、０≦ｃ′≦０．９５、０≦ｄ′≦０．５、ａ′＋ｂ′＋ｃ′＋ｄ′＝１を満たす数を表し、ｅ′は、０≦ｅ′≦０．３を満たす数を表し、ｎは、１≦ｎ≦５０を満たす整数を表す。）
２． 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を含有する１の活性エネルギー線硬化性組成物、
３． 前記平均式（Ｉ）および（ＩＩ）で表されるオルガノポリシロキサン化合物以外の重合性不飽和化合物を含有する２の活性エネルギー線硬化性組成物、
４． 溶剤を含有する２または３の活性エネルギー線硬化性組成物、
５． ２〜４のいずれか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、
６． 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、５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. 1. An active energy ray-curable composition comprising (A) an organopolysiloxane compound represented by the following average formula (I) and (B) an organopolysiloxane compound represented by the following average formula (II). Stuff,

(In the formula, 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 is independent of each other. It represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, a phenyl group, a (meth) acryloyloxypropyl group, or a glycidoxypropyl group, and R ⁵ is a hydrogen atom. , Methyl group, ethyl group, n-propyl group, or i-propyl group, where 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 represents a number, and f represents a number satisfying 0 ≦ f ≦ 0.3. )

(In the formula, R ¹ and R ^{3 to} R ⁵ have the same meanings as described above, and R ⁶ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and a ′, b ′, c ′ and d ′ is 0.05 ≦ a ′ ≦ 0.5, 0 ≦ b ′ ≦ 0.2, 0 ≦ c ′ ≦ 0.95, 0 ≦ d ′ ≦ 0.5, a ′ + b ′ + c ′ + d ′ = 1 represents a number, e'represents a number satisfying 0≤e'≤0.3, and n represents an integer satisfying 1≤n≤50.)
2. 2. 1. An active energy ray-curable composition containing a polymerization initiator that generates radicals by active energy rays.
3. 3. 2. The active energy ray-curable composition of 2, which contains a polymerizable unsaturated compound other than the organopolysiloxane compound represented by the average formulas (I) and (II).
4. 2 or 3 active energy ray-curable compositions containing a solvent,
5. A coating agent comprising any of 2 to 4 active energy ray-curable compositions,
6. It has a substrate and a cured film laminated directly on at least one surface of the substrate or via at least one other layer.
Provided is a coated article in which the cured film is a cured film made from the coating agent of 5.

The active energy ray-curable composition of the present invention comprises an organopolysiloxane compound having a urethane bond and a (meth) acryloyloxy group and an organopolysiloxane compound having a polyalkylene ether bond and a (meth) acryloyloxy group. Therefore, it can be suitably used for producing a resin or coating having excellent slipperiness, hardness, crack resistance, and bending resistance.
Further, since the active energy ray-curable composition of the present invention contains a condensable functional group within a predetermined range, the resin or coating obtained from the composition is excellent in water resistance and crack resistance. At the same time, deterioration due to aging can be suppressed.

Hereinafter, the present invention will be specifically described.
The active energy ray-curable composition according to the present invention comprises (A) an organopolysiloxane compound represented by the following average formula (I) and (B) an organopolysiloxane compound represented by the following average formula (II). It is characterized by including.

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 represents a hydrogen atom or a methyl group, respectively. Independently, an alkyl group having 1 to 8 carbon atoms, which may be substituted with a hydrogen atom or a halogen atom, a phenyl group, a (meth) acryloyloxypropyl group, or a glycidoxypropyl group is represented, and R ⁵ is Represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an i-propyl group, where 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 ≦ 0.3. show.

The ^{divalent hydrocarbon group having 1 to 10 carbon atoms of R 1} and R ² may be linear, branched or cyclic, and specific examples thereof include methylene, ethylene, trimethylene, propylene, butylene and hexylene. Linear, branched or cyclic alkylene groups such as decylene and cyclohexylene groups; arylene groups such as phenylene and xylylene groups may be mentioned.
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 even more preferable.

The alkyl group having 1 to 8 carbon atoms of R ⁴ may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl and i-. Butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl group and the like can be mentioned, and some or all of these alkyl groups are replaced with halogen atoms. May be.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Among them, as R ⁴ , an alkyl group or a phenyl group having 1 to 4 carbon atoms is preferable, and a methyl group or a phenyl group is more preferable.

The above a is a number satisfying 0.1 ≦ a ≦ 0.5, but 0.2 ≦ a ≦ 0.5 is preferable. When a is less than 0.1, the compatibility of the organopolysiloxane compound is insufficient, and the curability of the composition containing the organopolysiloxane compound, as well as the hardness, scratch resistance, and scratch resistance of the cured product are sufficient. It may be inferior in crack resistance and bending resistance.
The above b is a number satisfying 0 ≦ b ≦ 0.2, but 0 ≦ b ≦ 0.1 is preferable. If b exceeds 0.2, the obtained cured product may be inferior in crack resistance and bending resistance.
The above c is a number satisfying 0 ≦ c ≦ 0.4, but 0 ≦ c ≦ 0.2 is preferable. If c exceeds 0.4, the obtained cured product may be inferior in crack resistance and bending resistance.
The above d is a number satisfying 0 ≦ d ≦ 0.4, but 0 ≦ d ≦ 0.3 is preferable. If d exceeds 0.4, the obtained cured product may be inferior in hardness.
The above e is a number satisfying 0.2 ≦ e ≦ 0.7, but 0.3 ≦ e ≦ 0.6 is preferable. When e is less than 0.2, the organopolysiloxane compound may have a high viscosity, which is not preferable from the viewpoint of workability and processability. If e exceeds 0.7, the obtained cured product may be inferior in hardness.
Although the above f is a number satisfying 0 ≦ f ≦ 0.3, it is effective in suppressing the condensation reaction by the condensing functional group, and the obtained cured product has crack resistance, water resistance, and weather resistance. Considering the viewpoint, f is preferably a number satisfying 0 ≦ f ≦ 0.1.

In particular, the compatibility with the polymerizable unsaturated compound, the curability of the curable composition containing the organopolysiloxane compound, and the hardness, crack resistance, bending resistance, and water resistance of the cured product obtained from the composition. From the viewpoint of sex, ^{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 general formula (I).

On the other hand, in the formula (II), R ⁶ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ¹ and R ^{3 to} R ⁵ have the same meaning as in the formula (I), and a ′. , B', c'and d'are 0.05≤a'≤0.5, 0≤b'≤0.2, 0≤c'≤0.95, 0≤d'≤0.5, a ′ + B ′ + c ′ + d ′ = 1 represents a number, e ′ represents a number satisfying 0 ≦ e ′ ≦ 0.3, and n represents an integer satisfying 1 ≦ n ≦ 50.

Specific examples of the divalent hydrocarbon group having 1 to 10 carbon atoms of R ¹ include the same groups as those exemplified by the above formula (I), but among them, the carbon atom in the formula (II). An alkylene group having a number of 1 to 5 is preferable, and an ethylene group and a trimethylene group are more preferable.
Specific examples of the alkyl group having 1 to 8 carbon atoms of R ⁴ include the same groups as those exemplified by the above formula (I). Among them, in the formula (II), as R ⁴ , an alkyl group or a phenyl group having 1 to 4 carbon atoms is preferable, and a methyl group or a phenyl group is more preferable.

The ^{divalent hydrocarbon group having 1 to 10 carbon atoms of R 6} may be linear, branched or cyclic, and specific examples thereof include methylene, ethylene, trimethylene, propylene, butylene, hexylene and decylene. Linear, branched or cyclic alkylene groups such as cyclohexylene groups; arylene groups such as phenylene and xylylene groups may be mentioned.
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 even more preferable.

The above a'is a number satisfying 0.05 ≦ a ′ ≦ 0.5, but 0.07 ≦ a ′ ≦ 0.2 is preferable. If a'is less than 0.05, the compatibility of the organopolysiloxane compound may be insufficient, and the slipperiness and crack resistance of the composition containing the organopolysiloxane compound may be inferior. be.
The above b ′ is a number satisfying 0 ≦ b ′ ≦ 0.2, but 0 ≦ b ′ ≦ 0.1 is preferable. If b'exceeds 0.2, the obtained cured product may be inferior in crack resistance and bending resistance.
The above c ′ is a number satisfying 0 ≦ c ′ ≦ 0.95, but 0.3 ≦ c ′ ≦ 0.95 is preferable from the viewpoint of slipperiness, crack resistance and bending resistance.
The above d ′ is a number satisfying 0 ≦ d ′ ≦ 0.5, but 0 ≦ d ′ ≦ 0.3 is preferable. If d'exceeds 0.5, the compatibility of the organopolysiloxane compound becomes insufficient, and the obtained cured product may be inferior in hardness.
The above e'is a number satisfying 0≤e'≤0.3, but it is effective in suppressing the condensation reaction by the condensing functional group, and the obtained cured product has crack resistance, water resistance, and weather resistance. From the viewpoint of sex, e'preferably a number satisfying 0≤e'≤0.1.

The above n is an integer satisfying 1 ≦ n ≦ 50, but 5 ≦ n ≦ 30 is preferable. When n is less than 1, the slipperiness of the obtained cured product (coating film) may be inferior, and when n is more than 50, the compatibility of the organopolysiloxane compound with the polymerizable unsaturated compound is incompatible. It may be enough.

In particular, the compatibility with the polymerizable unsaturated compound, the curability of the curable composition containing the organopolysiloxane compound, and the hardness, crack resistance, bending resistance, and water resistance of the cured product obtained from the composition. From the viewpoint of sex, ^{it is preferable that R 1} is a trimethylene group, R ⁶ is an ethylene group, R ³ is a hydrogen atom, and R ⁴ is a methyl group in the general formula (II).

The average molecular weight of the organopolysiloxane compound used in the present invention is not particularly limited, but both the organopolysiloxane compounds of the formulas (I) and (II) are polystyrene-equivalent weights obtained by gel permeation chromatography (GPC). The average molecular weight is preferably 500 to 100,000, more preferably 700 to 10,000. If it is less than 500, the condensation does not proceed sufficiently, the storage stability of the organopolysiloxane compound may be lowered, and the condensation reaction may occur over time, and good results may not be obtained in the heat and moisture resistance test. .. On the other hand, in the case of a high molecular weight substance exceeding 100,000, good hardness and bending resistance may not be obtained in a film or a coated article obtained by curing an active energy ray-curable composition containing the organopolysiloxane compound. be.

The viscosity of the organopolysiloxane compound used in the present invention is not particularly limited, but all of the organopolysiloxane compounds of the formulas (I) and (II) rotate from the viewpoint of workability and workability. The viscosity at 25 ° C. measured by a viscometer is preferably 200 to 50,000 mPa · s, more preferably 300 to 5,000 mPa · s.
Further, the organopolysiloxane compound 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 amount of volatile matter is large, it may cause deterioration of appearance and deterioration of mechanical properties due to the generation of voids when the composition is cured.

In the active energy ray-curable composition of the present invention, the blending ratio of the organopolysiloxane compound of the formula (I) and the organopolysiloxane compound of the formula (II) is not particularly limited, but the obtained resin. In consideration of further enhancing the slipperiness, hardness, crack resistance, and bending resistance of the coating, the organopolysiloxane compound of the formula (II) is 0.1 with respect to 100 parts by mass of the organopolysiloxane compound of the formula (I). ~ 100 parts by mass is preferable, 1 to 50 parts by mass is more preferable, 2 to 25 parts by mass is further preferable, and 3 to 10 parts by mass is further preferable.

The active energy ray-curable composition of the present invention may be a mixture of a plurality of organopolysiloxane compounds having different compositions.

The organopolysiloxane compound used in the present invention can be produced according to a general method for producing an organopolysiloxane.
The organopolysiloxane compound of the formula (I) can be obtained, for example, by condensing a hydrolyzable silane containing an organic group having a urethane bond and a (meth) acryloyloxy group.
Specifically, a hydrolyzable silane represented by the following formula (III) and, if necessary, other hydrolyzable silanes are used to hydrolyze and condense in the presence of a catalyst to obtain an organopolysiloxane compound. The manufacturing method can be mentioned.

（式中、Ｒ¹〜Ｒ³は、上記と同じ意味を表す。Ｘは、それぞれ独立して、塩素原子または炭素原子数１〜６のアルコキシ基を表す。）

(In the formula, R ^{1 to} R ³ have the same meanings as described above. X independently represents a chlorine atom or an alkoxy group having 1 to 6 carbon atoms.)

As the alkoxy group having 1 to 6 carbon atoms of X, the alkyl group thereof may be linear, branched or cyclic, and specific examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy and n-. Examples thereof include butoxy, t-butoxy, n-pentyloxy group and the like.

Further, as the other hydrolyzable silane used as needed, in particular, any hydrolyzable silane that can be hydrolyzed and condensed with the hydrolyzable silane represented by the above general formula (III) to produce an organopolysiloxane compound. Not limited.
Specific examples thereof include dimethyldimethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldiethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, and methyltri. Ethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycydoxypropylmethyldiethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri Examples thereof include alkoxysilanes such as ethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltriethoxysilane.

The catalyst used for condensation is not particularly limited, but an acidic catalyst is preferable, and specific examples thereof include hydrochloric acid, formic acid, acetic acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, and lactic acid. , Carbonate, methanesulfonic acid, trifluoromethanesulfonic acid and the like.
The amount of the catalyst used is not particularly limited, but in consideration of the rapid progress of the reaction and the ease of removal of the catalyst after the reaction, 0.0002 to 0. For 1 mol of hydrolyzable silane. A range of 5 mol is preferred.

The amount ratio of the hydrolyzable silane to the water required for the hydrolyzed condensation reaction is not particularly limited, but it is possible to prevent the catalyst from being deactivated to allow the reaction to proceed sufficiently and to remove water after the reaction. Considering the ease, the ratio of 0.1 to 10 mol of water is preferable with respect to 1 mol of hydrolyzable silane.
The reaction temperature at the time of hydrolysis condensation is not particularly limited, but is -10 to 150 ° C. in consideration of improving the reaction rate and preventing the decomposition of the organic functional group of the hydrolyzable silane. preferable.

An organic solvent may be used for hydrolysis condensation. Specific examples of the organic solvent include methanol, ethanol, propanol, acetone, methyl isobutyl ketone, tetrahydrofuran, toluene, xylene and the like.

On the other hand, the organopolysiloxane compound of the formula (II) can be obtained, for example, by condensing a hydrolyzable silane containing an organic group having an oxyalkylene bond and a (meth) acryloyloxy group.
Specifically, a hydrolyzable silane represented by the following formula (IV) and, if necessary, other hydrolyzable silanes are used to hydrolyze and condense in the presence of a catalyst to obtain an organopolysiloxane compound. The manufacturing method can be mentioned.
In this case, other hydrolyzable silanes, catalysts, amounts of water used, organic solvent species, reaction conditions and the like are the same as in the case of using the hydrolyzable silanes of the above formula (III).

（式中、Ｒ¹、Ｒ³、Ｒ⁶およびＸは、上記と同じ意味を表す。）

(In the equation, R ¹ , R ³ , R ⁶ and X have the same meanings as above.)

The active energy ray-curable composition of the present invention may contain a photopolymerization initiator in addition to the organopolysiloxane compounds of the above formulas (I) and (II).
The photopolymerization initiator is not particularly limited as long as it is an initiator that generates radical species by active energy rays, and known examples such as acetophenone type, benzoin type, acylphosphine oxide type, benzophenone type, and thioxanthone type. It can be appropriately selected from the photopolymerization initiators and used.
Specific examples of the photopolymerization initiator include benzophenone, benzyl, Michler's ketone, thioxanthone derivative, benzoin ethyl ether, diethoxyacetophenone, benzyldimethylketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone, and acyl. Phosphine oxide derivative, 2-methyl-1- {4- (methylthio) phenyl} -2-morpholinopropane-1-one, 4-benzoyl-4'-methyldiphenylsulfide, 2,4,6-trimethylbenzoyl Examples thereof include diphenylphosphine, which may be used alone or in combination of two or more.

The photopolymerization initiator can be obtained as a commercial product, and specific examples thereof include DaroCure 1173, DaroCure MBF, Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 379, Irgacure 379EG, Irgacure 651, Irgacure 754, Irgacure 784, Examples thereof include Irgacure 819, Irgacure 819DW, Irgacure 907, Irgacure 1800, Irgacure 2959, Lucillin TPO (all manufactured by BASF Japan Ltd.) and the like.

The amount of the photopolymerization initiator used is the total amount of the organopolysiloxane compound and the polymerizable unsaturated compound used as necessary, considering that the curability is improved and the surface hardness is prevented from being lowered after curing. 0.1 to 20 parts by mass is preferable with respect to 100 parts by mass.

Further, the active energy ray-curable composition of the present invention may contain a polymerizable unsaturated compound other than the organopolysiloxane compounds of the formulas (I) and (II).
Specific examples of the polymerizable unsaturated compound include 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, and trimethyl propantri (meth). Acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, 3- (meth) acryloyloxyglycerin mono (meth) acrylate, Examples thereof include urethane acrylate, epoxy acrylate, and ester acrylate.
When a polymerizable unsaturated compound is used, the content thereof is preferably 1 to 1,000 parts by mass with respect to 100 parts by mass of the organopolysiloxane compound of the formulas (I) and (II).

The active energy ray-curable composition of the present invention contains metal oxide fine particles, silicone resin, silane coupling agent, diluting solvent, plasticizer, filler, sensitizer, light absorber, light stabilizer, and polymerization inhibitor. Various additives such as agents, heat ray reflective agents, antistatic agents, antioxidants, antifouling agents, water repellent agents, defoaming agents, colorants, thickeners, leveling agents, etc. impair the object of the present invention. It may be included in the range not included.

The active energy ray-curable composition of the present invention can be obtained by uniformly mixing each of the above components according to a conventional method.
The viscosity of the active energy ray-curable composition of the present invention is not particularly limited, but is measured by a rotational viscometer in consideration of improving molding or coating workability and suppressing the generation of streaks and the like. The viscosity at 25 ° C. is preferably 500 mPa · s or less, more preferably 300 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 described above can be suitably used as a coating agent, and is applied directly to at least one surface of a substrate or through at least one other layer, and applied thereto. By curing, a coated article having a film formed can be obtained.
Further, the cured product of the active energy ray-curable composition of the present invention can be suitably used as a film.

The base material is not particularly limited, and examples thereof include plastic molded bodies, wood-based products, ceramics, glass, metals, and composites thereof.
In addition, the surface of these base materials is treated with chemical conversion treatment, corona discharge treatment, plasma treatment, acid or alkaline solution, or decorative plywood whose surface layer is coated with a different type of paint from the base material body. Can also be used.

Further, the surface of the base material on which other functional layers are formed may be coated with the coating agent of the present invention, and the other functional layers include a primer layer, a rust preventive layer, a gas barrier layer, a waterproof layer, and a heat ray. Shielding layers and the like may be mentioned, and any one or a plurality of these layers may be pre-formed on the substrate.

In the coated article, a vapor deposition layer, a hard coat layer, a rust preventive layer, a gas barrier layer, a waterproof layer, and a heat ray shield by a CVD (chemical vapor deposition) method are further formed on a surface on which a coating film made of the coating agent of the present invention is formed. It may be covered with one or more layers such as a layer, an antifouling layer, a photocatalyst layer, and an antistatic layer.
Further, in the coated article, the surface opposite to the surface on which the coating film made of the coating agent of the present invention is formed is a hard coat layer, a rust preventive layer, a gas barrier layer, a waterproof layer, a heat ray shielding layer, an antifouling layer, and the like. It may be covered 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 various display elements such as liquid crystal displays, CRT displays, plasma displays, EL displays, etc., in which scratch resistance and abrasion resistance are required to be imparted to the surface. By forming a cured film, it is possible to impart scratch resistance, abrasion resistance, bending resistance, and crack resistance to these surfaces.

The coating agent may be appropriately selected from known methods. For example, various coating methods such as bar coater, brush coating, spraying, dipping, flow coating, roll coating, curtain coating, spin coating, and knife coating may be used. Can be used.

As a light source for curing the active energy ray-curable composition, a light source containing light having a wavelength in the range of 200 to 450 nm, for example, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, or the like is used. Can be mentioned.
Although the irradiation amount is not particularly limited but is preferably ^{10~5,000mJ / cm 2, 20~1,000mJ / cm} 2 is more preferable.
The curing time is usually 0.5 seconds to 2 minutes, preferably 1 second to 1 minute.

Hereinafter, the present invention will be described in more detail with reference to 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 a developing solvent of tetrahydrofuran (THF) using GPC (gel permeation chromatography, manufactured by HLC-8220 Tosoh Corporation). It is a value measured as.
The values of a to f in the average formula (I) and a'to e'in the average formula (II) were calculated from the results of ¹ H-NMR and ^{29 Si-NMR measurements.}

[1] Synthesis of organopolysiloxane compound represented by the average formula (I) [Synthesis Example 1-1] Synthesis of organopolysiloxane 1-1 964.2 g (3.0 mol) of the compound represented by the following formula (V). ), dimethyldimethoxysilane 360.7 g (3.0 mol), hexamethyldisiloxane 487.1 g (3.0 mol), and methanesulfonic acid 7.3 g in a reactor, and when they become uniform, ion-exchanged water 162. .0 g was added and stirred at 25 ° C. for 4 hours. 36.7 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 2 hours to neutralize. Volatile components such as methanol were distilled off under reduced pressure, toluene and sodium sulfate water were added and washed with water, toluene was distilled off with a strip, and then pressure filtration was performed.
The obtained reaction product was a viscous liquid having a viscosity of 1,210 mPa · s, a volatile content of 1.6% by mass, and a weight average molecular weight of 1,210 at 25 ° C. The values of a to f in the average formula (II) calculated from the results of NMR are a = 0.27, b = 0, c = 0, d = 0.25, e = 0.48, and f = 0, respectively. It was 15.

[Synthesis Example 1-2] Synthesis of Organopolysiloxane 1-2 Compounds 1,285.6 g (4.0 mol) represented by the above formula (V), trimethylmethoxysilane 136.22 g (1.0 mol), dimethyldimethoxy Mix 360.7 g (3.0 mol) of silane, 487.1 g (3.0 mol) of hexamethyldisiloxane, and 8.9 g of methanesulfonic acid in a reactor, and add 226.8 g of ion-exchanged water when the mixture becomes uniform. Then, the mixture was stirred at 25 ° C. for 4 hours. 44.7 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 2 hours to neutralize. Volatile components such as methanol were distilled off under reduced pressure, toluene and sodium sulfate water were added and washed with water, toluene was distilled off with a strip, and then pressure filtration was performed.
The obtained reaction product was a viscous liquid at 25 ° C. with a viscosity of 2,200 mPa · s, a volatile content of 1.6% by mass, and a weight average molecular weight of 1,870. The values of a to f in the average formula (I) calculated from the results of NMR are a = 0.30, b = 0, c = 0.08, d = 0.22, e = 0.40, f =, respectively. It was 0.05.

[Synthesis Example 1-3] Synthesis of Organopolysiloxane 1-3 Compounds 1,285.6 g (4.0 mol) represented by the above formula (V), tetramethoxysilane 30.5 g (0.1 mol), dimethyldimethoxy 721.3 g (6.0 mol) of silane, 487.1 g (3.0 mol) of hexamethyldisiloxane, and 9.8 g of methanesulfonic acid were mixed in a reactor, and 265.7 g of ion-exchanged water was added when the mixture became uniform. Then, the mixture was stirred at 25 ° C. for 4 hours. 49.0 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 2 hours to neutralize. Volatile components such as methanol were distilled off under reduced pressure, toluene and sodium sulfate water were added and washed with water, toluene was distilled off with a strip, and then pressure filtration was performed.
The obtained reaction product was a viscous liquid at 25 ° C. with a viscosity of 4,400 mPa · s, a volatile content of 0.9% by mass, and a weight average molecular weight of 3,250. The values of a to f in the average formula (I) calculated from the results of NMR are a = 0.30, b = 0, c = 0.15, d = 0, e = 0.55, f = 0, respectively. It was 06.

[2] Synthesis of organopolysiloxane compound represented by the average formula (II) [Synthesis Example 2-1] Synthesis of organopolysiloxane 2-1 1,462.0 g (2) of the compound represented by the following formula (VI) .0 mol), 2,164.0 g (18.0 mol) of dimethyldimethoxysilane, and 13.8 g of methanesulfonic acid were blended in a reactor, and when they became uniform, 410.4 g of ion-exchanged water was added, and the temperature was 25 ° C. The mixture was stirred for 4 hours. 68.8 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 2 hours to neutralize. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.
The obtained reaction product was a viscous liquid at 25 ° C. with a viscosity of 320 mPa · s, a volatile content of 0.8% by mass, and a weight average molecular weight of 2,700. The values of a'to e'in the average formula (II) calculated from the NMR results are a'= 0.11, b'= 0, c'= 0.89, d'= 0, e'= 0, respectively. It was 0.02.

[Synthesis Example 2-2] Synthesis of Organopolysiloxane 2-2 1,462.0 g (2.0 mol) of the compound represented by the above formula (VI), 136.2 g (1.0 mol) of trimethylmethoxysilane, dimethyldimethoxy Silane 1,683.1 g (14.0 mol), hexamethyldisiloxane 324.8 g (2.0 mol), and methanesulfonic acid 14.2 g were blended in a reactor, and when uniform, ion-exchanged water 356.4 g. Was added, and the mixture was stirred at 25 ° C. for 4 hours. 71.2 g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 2 hours to neutralize. Volatile components such as methanol were distilled off under reduced pressure, and pressure filtration was performed.
The obtained reaction product was a viscous liquid at 25 ° C. with a viscosity of 160 mPa · s, a volatile content of 0.9% by mass, and a weight average molecular weight of 2,900. The values of a'to e'in the average formula (II) calculated from the NMR results are a'= 0.10, b'= 0.06, c'= 0.67, d'= 0.17, respectively. e'= 0.06.

[3] Preparation of active energy ray-curable composition and production of cured product thereof [Examples 1-1 to 1-6, Comparative Examples 1-1 to 1-6]
Each organopolysiloxane compound obtained in the above synthesis examples 1-1 to 1-3, 2-1 and 2-2, dipentaerythritol hexaacrylate (DPHA, manufactured by MIWON), DaroCure 1173 (radical photopolymerization initiator). , BASF) was mixed at the blending ratios (parts by mass) shown in Tables 1 and 2, poured into a mold with a release film attached so that the thickness was 0.2 mm, and the integrated irradiation amount was 600 mJ with a high-pressure mercury lamp. A cured product was produced by irradiating light to a ratio of / cm ^{2 and curing the mixture.}

[4] Evaluation of film characteristics of active energy ray-curable composition The films obtained in Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-5 have pencil hardness, bending resistance and slipperiness. Was measured by the following method. The results are shown in Tables 3 and 4.
(1) Pencil hardness Measured under a load of 750 g according to JIS K5600-5-4.
(2) Bending resistance Measured using a cylindrical mandrel (type 1) according to JIS K5600-5-1, the bending resistance was set to> 8 mmφ for films with cracks in the 8 mmφ test. ..
(3) Slippery The surface was traced with a finger, and the one with slipperiness was regarded as OK, and the one without slipperiness was regarded as NG.

As shown in Tables 3 and 4, the active energy ray-cured product containing an organopolysiloxane having a urethane bond and an organopolysiloxane having a polyalkylene ether bond has both high bending resistance and slipperiness. In Comparative Examples 1-1 to 1-3 which do not contain a polyalkylene ether bond, no slipperiness is observed, and in Comparative Examples 1-4 and 1-5 which do not have a urethane bond, bending resistance is not exhibited. Recognize.

[5] Production of coating composition and coated article [Examples 2-1 to 2-6, Comparative Examples 2-1 to 2-5]
Organopolysiloxane compounds obtained in Synthetic Examples 1-1 to 1-3, 2-1 and 2-2, polyester skeleton urethane acrylate UA-122P (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), dipentaerythritol hexa. Acrylate (manufactured by MIWON), ethyl acetate, and DaroCure 1173 (manufactured by BASF) were mixed at the compounding ratios (parts by mass) shown in Tables 5 and 6 to prepare a coating composition.
Each of the obtained coating compositions was referred to as Barcoter No. 3 was applied onto a PET substrate (A4100), dried at 100 ° C. for 5 minutes, irradiated with light with a high-pressure mercury lamp so as to have an integrated irradiation amount of 600 mJ / cm ^2, and cured to produce a coated article.

[6] Evaluation of characteristics of the coated article The pencil hardness, bending resistance, slipperiness and boiling adhesion of the obtained cured film of the coated article were evaluated. The results are shown in Tables 7 and 8. The pencil hardness, bending resistance, and slipperiness were measured and evaluated by the same procedure as described above, and the boiling adhesion was evaluated by the following method.
(4) Boiling adhesion test After immersing the test piece in boiling water at 100 ° C for 2 hours, perform a cross-cut test with 25 cells according to JIS K5600-5-6 (number of cells remaining without peeling) / Expressed as 25.

As shown in Tables 7 and 8, in the coated articles coated with the coating composition, only the articles containing the organopolysiloxane having a polyalkylene ether bond and the organopolysiloxane having a urethane bond have bending resistance and slipperiness. Good results were obtained in all of the boiling adhesion tests, demonstrating the superiority of the organopolysiloxane compound having a polymerizable functional group of the present invention.

Claims (6)

An active energy ray-curable composition comprising (A) an organopolysiloxane compound represented by the following average formula (I) and (B) an organopolysiloxane compound represented by the following average formula (II). thing.

(In the formula, 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 is independent of each other. It represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, a phenyl group, a (meth) acryloyloxypropyl group, or a glycidoxypropyl group, and R ⁵ is a hydrogen atom. , Methyl group, ethyl group, n-propyl group, or i-propyl group, where 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 represents a number, and f represents a number satisfying 0 ≦ f ≦ 0.3. )

(In the formula, R ¹ and R ^{3 to} R ⁵ have the same meanings as described above, and R ⁶ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and a ′, b ′, c ′ and d ′ is 0.05 ≦ a ′ ≦ 0.5, 0 ≦ b ′ ≦ 0.2, 0 ≦ c ′ ≦ 0.95, 0 ≦ d ′ ≦ 0.5, a ′ + b ′ + c ′ + d ′ = 1 represents a number, e'represents a number satisfying 0≤e'≤0.3, and n represents an integer satisfying 1≤n≤50.) The active energy ray-curable composition according to claim 1, which contains a polymerization initiator that generates radicals by active energy rays. It contains a polymerizable unsaturated compound other than the organopolysiloxane compound represented by the average formulas (I) and (II) .
The polymerizable unsaturated compound is 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, trimethyl propanthry (meth) acrylate, and penta. Elythritol tetra (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate, 3- (meth) acryloyloxyglycerin mono (meth) acrylate, urethane acrylate, The active energy ray-curable composition according to claim 2, which is at least one selected from epoxy acrylates and ester acrylates. The active energy ray-curable composition according to claim 2 or 3, which contains a solvent. A coating agent comprising the active energy ray-curable composition according to any one of claims 2 to 4. It has a substrate and a cured film laminated directly on at least one surface of the substrate or via at least one other layer.
A coated article in which the cured film is a cured film produced from the coating agent according to claim 5.