JP5393497B2 - Active energy ray-curable composition and coated article - Google Patents

Description

  The present invention relates to an active energy ray-curable composition and a coated article.

  Synthetic resins such as polymethyl methacrylate resin, polystyrene resin, and polycarbonate resin are excellent in impact resistance, transparency, light weight, and easy to process. Used in windows, lamp lenses, and instrument covers. However, since the synthetic resin is inferior in surface properties such as scratch resistance, chemical resistance, and weather resistance as compared with glass, the surface properties of the synthetic resin are improved. As methods for improving the surface properties of synthetic resins, methods for applying polyorganosiloxane-based and melamine-based thermosetting coating compositions and methods for applying polyfunctional acrylate-based active energy ray-curable compositions have been proposed. Yes.

  In connection with these methods, Patent Documents 1 and 2 disclose poly (meth) acrylates of mono- or polypentaerythritol, urethane (meth) acrylates having at least two (meth) acryloyl groups in the molecule, and poly (meth) acrylates. An invention relating to a coating composition obtained by blending [(meth) acryloyloxyalkyl] (iso) cyanurate in a specific ratio is disclosed.

  In recent years, as the use of synthetic resins in the outdoors expands, further improvements in the surface properties of synthetic resins are required, and particularly high scratch resistance is required. However, the inventions described in Patent Documents 1 and 2 do not satisfy the requirement for high scratch resistance.

  On the other hand, as a method for improving the scratch resistance of the coating composition, there is a method of blending an inorganic material or an inorganic-organic hybrid material in the coating composition. For example, Patent Document 3 discloses reactive particles obtained by chemically modifying colloidal silica fine particles with a radically polymerizable silane compound, poly [(meth) acryloyloxyalkyl] isocyanurate, and at least two (meth) acryloyloxy molecules per molecule. An invention relating to an abrasion-resistant coating-forming composition containing a urethane (meth) acrylate having a group and an alicyclic skeleton, and a photopolymerization initiator is disclosed. Although this invention can obtain a cured coating film having scratch resistance, the scratch resistance is not yet sufficient for the high scratch resistance requirement recently required. Moreover, in this invention, when it is going to increase the compounding quantity of a reactive particle so that abrasion resistance may be made high, the transparency of the cured coating film obtained will fall.

  Patent Document 4 discloses reactive particles obtained by bonding specific oxide particles and an organic compound having a polymerizable unsaturated group and a hydrolyzable silyl group, and an organic compound having two or more polymerizable unsaturated groups. An invention relating to a curable composition containing a compound and a both-end reactive polydimethylsiloxane compound is disclosed. Although this invention can provide a cured coating film having scratch resistance and transparency, the scratch resistance is not yet sufficient for the demand for high scratch resistance recently required. In this invention, the both-end reactive polysiloxane compound is a component that imparts slipperiness to the cured coating film, and the scratch resistance does not increase even if the blending amount of the both-end reactive polysiloxane compound is increased. When the blending amount of the both-end reactive polysiloxane compound is increased, the transparency of the cured coating film obtained is lowered.

Japanese Patent Laid-Open No. 5-230397 JP-A-6-128502 International Publication 97/011129 JP-A-2005-36018

  The present invention has been made in view of the above circumstances, and an object of the present invention is to obtain an active energy ray-curable composition that can obtain a cured coating film having high scratch resistance and excellent transparency. It is.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used the above-mentioned problems by using an active energy ray-curable composition containing a specific silsesquioxane compound and specific reactive particles. As a result, the present invention has been completed.

That is, the present invention
1. An organic group directly bonded to a silicon atom, and part or all of the organic groups directly bonded to the silicon atom are at least one (meth) acryloyloxy group and at least one isocyanurate ring structure; The silsesquioxane compound (A), which is an organic group having both of the above, and silica fine particles (b-1) are reacted with hydrolyzable silane (b-2) having a (meth) acryloyloxy group in the molecule. An active energy ray-curable composition characterized by containing reactive particles (B) obtained by
2. The active energy ray-curable composition according to item 1, containing a photopolymerization initiator (C),
3. The active energy ray-curable composition according to 1 or 2, comprising a polymerizable unsaturated compound (D) other than the component (A) and the component (B),
4.1 A coated article obtained by coating the active energy ray-curable composition according to any one of items 1 to 3 on an object to be coated,
About.

  With the active energy ray-curable composition of the present invention, a cured coating film having high scratch resistance and excellent transparency can be obtained.

  The active energy ray-curable composition of the present invention has an organic group directly bonded to a silicon atom, and part or all of the organic group directly bonded to the silicon atom is at least one (meta). Silsesquioxane compound (A) which is an organic group having both an acryloyloxy group and at least one isocyanurate ring structure [hereinafter referred to as “component (A)” or “silsesquioxane compound which is component (A)” "May be abbreviated. ], And reactive particles (B) obtained by reacting silica fine particles (b-1) with hydrolyzable silane (b-2) having a (meth) acryloyloxy group in the molecule [hereinafter referred to as "( It may be abbreviated as “B) component” or “reactive particle (B)”. ] Is contained.

The silsesquioxane compound “ silsesquioxane compound ” as the component (A) is a polysiloxane whose basic structural unit is a T unit.

  In the present specification, the “silsesquioxane compound” does not mean only a silsesquioxane compound having a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed, but Si—OH groups remain. It is also possible to include a silsesquioxane compound having a ladder structure, an incomplete cage structure, or a random condensate.

  The ratio of the silsesquioxane compound having a structure in which all of the Si—OH groups are hydrolyzed and condensed is 80 mass in the silsesquioxane compound as the component (A). % Or more, preferably 90% by mass or more, and more preferably 100% by mass from the viewpoint of liquid stability.

  The silsesquioxane compound as the component (A) has an organic group directly bonded to a silicon atom. Of the organic groups directly bonded to the silicon atom, 1 to 100 mol% of the organic groups are organic groups having both at least one (meth) acryloyloxy group and at least one isocyanurate ring structure. . By having the organic group, the silsesquioxane compound as the component (A) is excellent in compatibility with various polymerizable unsaturated compounds and is irradiated with active energy rays in the presence of a photopolymerization initiator. Harden. Therefore, the cured coating film obtained by the active energy ray-curable composition of the present invention is excellent in transparency.

  The organic group having both at least one (meth) acryloyloxy group and at least one isocyanurate ring structure in the silsesquioxane compound as the component (A) is the silsesquioxane as the component (A). It is a part or all of the organic group directly bonded to the silicon atom of the compound, preferably 1 to 70 mol%, more preferably 2 to 50 mol% of them. The lower limit of these ranges is significant in terms of the transparency of the resulting cured coating film. The upper limit of these ranges is significant in terms of the scratch resistance of the resulting cured coating film.

  As the organic group having both at least one (meth) acryloyloxy group and at least one isocyanurate ring structure, the silsesquioxane compound as the component (A) has, for example, the following general formula (AI )

[In formula (AI), R ¹ is the same or different and represents a hydrogen atom or a methyl group. R ² is the same or different and represents a divalent organic group. R ³ represents a divalent organic group. ] The organic group represented by this is mentioned. In addition, R < ³ > in general formula (AI) has couple | bonded with the silicon atom which comprises a silsesquioxane compound.

The R ² is not particularly limited as long as it is a divalent organic group. As a bivalent organic group, a C1-C100 bivalent organic group is mentioned, for example. Preferably it is a C1-C30 bivalent organic group. The divalent organic group is not limited to a hydrocarbon group, and may have, for example, a urethane bond, an ester bond, an ether bond, or the like.

The R ³ is not particularly limited as long as it is a divalent organic group. As a bivalent organic group, a C1-C100 bivalent organic group is mentioned, for example. Preferably it is a C1-C30 bivalent organic group. The divalent organic group is not limited to a hydrocarbon group, and may have, for example, a urethane bond, an ester bond, an ether bond, or the like.

  More specific examples of the organic group represented by the general formula (AI) include, for example, the following general formula (A-II) and the following general formula (A-III).

[In formula (A-II), R ⁴ is the same or different and represents a hydrogen atom or a methyl group. R ⁵ is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. R ⁶ represents a divalent hydrocarbon group having 1 to 4 carbon atoms. m is the same or different and represents an integer of 0 to 5. In formula (A-III), R ⁷ is the same or different and represents a hydrogen atom or a methyl group. R ⁸ is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. R ⁹ represents a divalent hydrocarbon group having 1 to 4 carbon atoms. ] The organic group represented by this is mentioned.

R ⁵ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and the like. Especially, it is preferable from the transparency point of the cured coating film obtained that it is a C2-C4 bivalent hydrocarbon group.

R ⁶ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 4 carbon atoms. Specific examples include ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group and the like.

The organic group represented by the general formula (A-II) is more excellent in scratch resistance, compatibility with a highly polar polymerizable unsaturated compound, and active energy ray curability in the presence of a photopolymerization initiator. From the viewpoint, an organic group in which R ⁴ is a hydrogen atom, R ⁵ is an ethylene group, R ⁶ is a 1,3-propylene group, and m is 0 is preferable.

R ⁸ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and the like. Especially, it is preferable that it is a C2-C4 bivalent hydrocarbon group, especially an ethylene group.

R ⁹ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 4 carbon atoms. Specific examples include ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group and the like.

The organic group represented by the general formula (A-III) is more excellent in scratch resistance, compatibility with a highly polar polymerizable unsaturated compound, and active energy ray curability in the presence of a photopolymerization initiator. From the viewpoint, an organic group in which R ⁷ is a hydrogen atom, R ⁸ is an ethylene group, and R ⁹ is a 1,3-propylene group is preferable.

  The silsesquioxane compound as component (A) is an organic group in which an organic group having both the at least one (meth) acryloyloxy group and at least one isocyanurate ring structure is directly bonded to a silicon atom. Other organic groups having a specific ratio but directly bonded to the silicon atom are not particularly limited. Other organic groups include, for example, an organic group having an alkyl group such as a methyl group or an ethyl group, or a (meth) acryloyloxy group such as a 3- (meth) acryloyloxypropyl group (provided that the organic group has an isocyanurate ring structure). And organic groups having a vinyl group. Among these, from the viewpoint that the active energy ray curability is more excellent, an organic group having a (meth) acryloyloxy group (excluding an organic group having an isocyanurate ring structure), particularly a 3- (meth) acryloyloxypropyl group, preferable.

  The silsesquioxane compound as the component (A) may be a compound having a single composition or a mixture of compounds having different compositions.

  The weight average molecular weight of the silsesquioxane compound as the component (A) is not particularly limited. The weight average molecular weight is preferably 1,000 to 100,000, more preferably 1,000 to 10,000. These ranges are significant in terms of viscosity and paintability of the active energy ray-curable composition containing the silsesquioxane compound as the component (A).

  In this specification, the weight average molecular weight is a weight average molecular weight measured by a light scattering method. Zetasizer Nano Nano-ZS (Malvern Instruments Ltd.) was used for the measurement of the weight average molecular weight by the light-scattering method. The samples used for the measurement were 10 samples having different concentrations in which the silsesquioxane compound (A) component was dissolved in propylene glycol monomethyl ether and the concentration was adjusted to 0.5 to 5.0% by mass. . The weight average molecular weight was determined by measuring the light scattering intensity of these 10 samples.

(A) Production method of silsesquioxane compound as component (A) Silsesquioxane compound as component (A) is a production method used in the production of general silsesquioxane and conventionally known chemical reactions. It can obtain by combining. For example, it can also manufacture using the following manufacturing method a or manufacturing method b.

Manufacturing method a
As the production method a, a hydrolyzable silane which is an organic group directly bonded to a silicon atom and has an organic group having both at least one (meth) acryloyloxy group and at least one isocyanurate ring structure is used. The production method used as a starting material is mentioned.

  Specifically, for example, a hydrolysis product other than the hydrolyzable silane represented by the following general formula (A-IV) and, if necessary, the hydrolyzable silane represented by the following general formula (A-IV) as a starting material And a method of producing a silsesquioxane compound as the component (A) by hydrolytic condensation in the presence of a catalyst using a functional silane.

R ¹⁰ SiX ₃ (A-IV)
R ¹⁰ in the general formula (A-IV) represents an organic group having both at least one (meth) acryloyloxy group and at least one isocyanurate ring structure. X is chlorine or a C1-C6 alkoxy group, and X may be the same or different. Specific examples of X include chlorine, methoxy group, ethoxy group, propoxy group, butoxy group and the like.

  Examples of the hydrolyzable silane other than the hydrolyzable silane represented by the general formula (A-IV) include silsesquiskies by hydrolytic condensation together with the hydrolyzable silane represented by the general formula (A-IV). It will not specifically limit if an oxane compound can be manufactured. Specifically, for example, alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane; 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyl Examples include 3- (meth) acryloyloxypropyltrialkoxysilane such as oxypropyltriethoxysilane; vinyltrialkoxysilane such as vinyltrimethoxysilane and vinyltriethoxysilane.

  The silsesquioxane as the component (A) of the organic group having both the at least one (meth) acryloyloxy group and the at least one isocyanurate ring structure, which the silsesquioxane compound as the component (A) has The ratio of the organic group directly bonded to the silicon atom of the compound is adjusted by the hydrolyzable silane represented by the general formula (A-IV) used as a starting material and the general formula (if necessary) A-IV) can be carried out by arbitrarily changing the ratio of the hydrolyzable silane other than the hydrolyzable silane.

  Examples of the hydrolyzable silane represented by the general formula (A-IV) include hydrolyzable silanes represented by the following general formula (A-V).

R ¹ , R ² , R ³ and X in the general formula (A-V) are the same as described above. X may be the same or different.

  More specifically, examples of the hydrolyzable silane represented by the general formula (A-V) include a hydrolyzable silane represented by the following general formula (A-VI) and the following general formula (A-VII). ) Represented by a hydrolyzable silane.

R ⁴ , R ⁵ , R ⁶ , m and X in the general formula (A-VI) are the same as described above. X may be the same or different.

R ⁷ , R ⁸ , R ⁹ and X in the general formula (A-VII) are the same as described above. X may be the same or different.

  A method for producing a hydrolyzable silane represented by the general formula (A-VI) will be exemplified. Examples of the hydrolyzable silane represented by the general formula (A-VI) include a hydrolyzable silane represented by the following general formula (A-VIII) and a compound represented by the following general formula (A-IX). It can obtain by making it react.

R ⁶ and X in the general formula (A-VIII) are the same as described above. X may be the same or different.

R ⁴ , R ⁵ and m in the general formula (A-IX) are the same as described above.

  Specific examples of the hydrolyzable silane represented by the general formula (A-VIII) include 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

  The mixing ratio of the hydrolyzable silane represented by the general formula (A-VIII) and the compound represented by the general formula (A-IX) is not particularly limited. Usually, the reaction is carried out using equimolar amounts of the isocyanate group of the compound represented by the general formula (A-IX) with respect to the number of moles of the amino group of the hydrolyzable silane represented by the general formula (A-VIII). Is done.

  This reaction can be performed according to a conventional method in which an amino group and an isocyanate group are reacted. The reaction temperature is, for example, -78 ° C to 200 ° C, preferably -78 ° C to 100 ° C, more preferably -10 ° C to 40 ° C. Although this reaction can be carried out regardless of pressure, a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable.

  In the reaction, a solvent may be appropriately used. Specific examples of the solvent include esters such as ethyl acetate, butyl acetate, methyl benzoate and methyl propionate; ethers such as tetrahydrofuran, dioxane and dimethoxyethane; propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Examples include glycol ethers such as 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons.

  The compound represented by the general formula (A-IX) is obtained by, for example, reacting a compound represented by the following general formula (AX) with a compound represented by the following general formula (A-XI). Can be obtained.

  The compound represented by the general formula (AX) is a so-called isocyanurate cycloadduct of 1,6-hexamethylene diisocyanate, and trade names include Sumijour N3300 (manufactured by Sumika Bayer Urethane Co., Ltd.), Duranate. Examples thereof include TPA100 (manufactured by Asahi Kasei Chemicals Corporation).

R ⁴ , R ⁵ and m in the general formula (A-XI) are the same as described above.

  The compound represented by the general formula (A-XI) is, for example, as a compound in the case where m is 0, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl ( Examples include meth) acrylate and 4-hydroxybutyl (meth) acrylate. Examples of the compound when m is 1 to 5 include caprolactone-modified hydroxyalkyl (meth) acrylate. Specifically, “Placcel FA-1”, “Plaxel FA-2”, “Plaxel FA-2D”, “Plaxel FA-3”, “Plaxel FA-4”, “Plaxel FA-5” are trade names. , "Placcel FM-1", "Placcel FM-2", "Placcel FM-2D", "Placcel FM-3", "Placcel FM-4", "Placcel FM-5" (all manufactured by Daicel Chemical Industries) Etc.

  The mixing ratio of the compound represented by the general formula (AX) and the compound represented by the general formula (A-XI) is not particularly limited, but the general formula ( The isocyanate group of the compound represented by AX) and the hydroxyl group of the compound represented by the general formula (A-XI) are usually in a molar ratio, usually NCO / OH = 1.05 to 2.00, preferably The blending ratio is 1.10 to 1.50.

  This reaction can be performed according to a conventional method in which an isocyanate group and a hydroxyl group are reacted. The reaction temperature is, for example, 0 to 200 ° C, preferably 20 to 200 ° C, more preferably 20 ° C to 120 ° C. Although this reaction can be carried out regardless of pressure, a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable. The reaction is usually completed in about 2 to 10 hours.

  In the reaction, a solvent may be appropriately used. Specific examples of the solvent include esters such as ethyl acetate, butyl acetate, methyl benzoate and methyl propionate; ethers such as tetrahydrofuran, dioxane and dimethoxyethane; propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Examples include glycol ethers such as 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons.

  In addition, the product obtained by reacting the compound represented by the general formula (AX) with the compound represented by the general formula (A-XI) includes the general formula (A-IX). In addition to the compound represented by general formula (A-XII)

[R ⁴ , R ⁵ and m in Formula (A-XII) are the same as above. ] May be included.

  And when manufacturing the hydrolyzable silane represented by the said general formula (A-VI), and using the hydrolyzable silane represented by the said general formula (A-VI), it is a sil which is (A) component When the sesquioxane compound is produced, there is no particular problem even if the compound represented by the general formula (A-XII) is contained in the raw material for the production.

  Then, the method to manufacture the hydrolysable silane represented by the said general formula (A-VII) is illustrated. Examples of the hydrolyzable silane represented by the general formula (A-VII) include a hydrolyzable silane represented by the following general formula (A-XIII) and a compound represented by the following general formula (A-XIV). It can obtain by making it react.

R ⁹ and X in the general formula (A-XIII) are the same as described above. X may be the same or different.

R ⁷ and R ^{8 in the} general formula (A-XIV) are the same as described above.

  Specific examples of the hydrolyzable silane represented by the general formula (A-XIII) include 3-isocyanatopropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane.

  Examples of the compound represented by the general formula (A-XIV) include bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate, bis (2-acryloyloxypropyl) hydroxyethyl isocyanurate, and the like. Examples of product names include Aronix M-215 and Aronix M-313 (both manufactured by Toagosei Co., Ltd.).

  The mixing ratio of the hydrolyzable silane represented by the general formula (A-XIII) and the compound represented by the general formula (A-XIV) is not particularly limited. Usually, the reaction is carried out using an equimolar amount of the hydroxyl group of the compound represented by the general formula (A-XIV) with respect to the number of moles of the isocyanate group of the hydrolyzable silane represented by the general formula (A-XIII). Done.

  This reaction can be performed according to a conventional method in which an isocyanate group and a hydroxyl group are reacted. The reaction temperature is, for example, 0 to 200 ° C, preferably 20 to 200 ° C, more preferably 20 ° C to 120 ° C. Although this reaction can be carried out regardless of pressure, a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable. The reaction is usually completed in about 2 to 10 hours.

  In the reaction, a solvent may be appropriately used. Specific examples of the solvent include esters such as ethyl acetate, butyl acetate, methyl benzoate and methyl propionate; ethers such as tetrahydrofuran, dioxane and dimethoxyethane; propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Examples include glycol ethers such as 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons.

  In addition, the compound represented by the general formula (A-XIV) is usually tris (2- (2)) as represented by, for example, Aronix M-215, Aronix M-313 (both manufactured by Toagosei Co., Ltd.) and the like. The following general formula (A-XV) such as acryloyloxyethyl) isocyanurate, tris (2-acryloyloxypropyl) isocyanurate

[In formula (A-XV), R ⁷ and R ⁸ are the same as defined above. It is sold as a mixture with a compound represented by

  And when manufacturing the hydrolyzable silane represented by the said general formula (A-VII), and using the hydrolyzable silane represented by the said general formula (A-VII), it is silyl which is (A) component When the sesquioxane compound is produced, there is no particular problem even if the compound represented by the general formula (A-XV) is contained in the raw material for the production.

  Using a hydrolyzable silane represented by the general formula (A-IV) as a starting material and, if necessary, a hydrolyzable silane other than the hydrolyzable silane represented by the general formula (A-IV), When producing the silsesquioxane compound which is (A) component by performing hydrolysis condensation, a catalyst is usually used.

  As the catalyst, a basic catalyst is preferably used. Specific examples of the basic catalyst include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethyl Examples thereof include ammonium hydroxide salts such as ammonium hydroxide and ammonium fluoride salts such as tetrabutylammonium fluoride.

  The amount of the catalyst used is not particularly limited, but if it is too much, there are problems such as high cost and difficulty in removal, while if too little, the reaction is slowed. Therefore, the usage-amount of a catalyst becomes like this. Preferably it is 0.0001-1.0 mol with respect to 1 mol of hydrolysable silane, More preferably, it is the range of 0.0005-0.1 mol.

  When hydrolyzing and condensing a hydrolyzable silane, water is usually used. The quantity ratio of hydrolyzable silane and water is not particularly limited. The amount of water used is preferably 0.1 to 100 mol of water, more preferably 0.5 to 3 mol, per mol of hydrolyzable silane. If the amount of water is too small, the reaction may be slowed and the yield of the desired silsesquioxane compound may be reduced. If the amount of water is too large, the product will have a high molecular weight, resulting in a product with the desired structure. May decrease. Moreover, when using a basic catalyst as aqueous solution, the water to be used may be substituted with the water, and water may be added separately.

  In the hydrolysis condensation, an organic solvent may be used or may not be used. It is preferable to use an organic solvent from the viewpoint of preventing gelation and adjusting the viscosity during production. As the organic solvent, polar organic solvents and nonpolar organic solvents can be used alone or as a mixture.

  As the polar organic solvent, lower alcohols such as methanol, ethanol and 2-propanol, ketones such as acetone and methyl isobutyl ketone, and ethers such as tetrahydrofuran are used. Particularly, acetone and tetrahydrofuran have a low boiling point and the system is uniform. And the reactivity is improved. As the nonpolar organic solvent, a hydrocarbon solvent is preferable, and an organic solvent having a boiling point higher than that of water such as toluene and xylene is preferable. In particular, an organic solvent azeotropic with water such as toluene efficiently removes water from the system. This is preferable because it is possible. In particular, mixing a polar organic solvent and a nonpolar organic solvent provides the above-described advantages, so that it is preferably used as a mixed solvent.

  As reaction temperature at the time of hydrolysis condensation, it is 0-200 degreeC normally, Preferably it is 10-200 degreeC, More preferably, it is 10-120 degreeC. Moreover, although this reaction can be implemented irrespective of a pressure, the pressure range of 0.02-0.2 MPa is preferable, and the pressure range of 0.08-0.15 MPa is especially preferable.

  In the hydrolysis-condensation reaction, the condensation reaction proceeds with hydrolysis, and most of the hydrolyzable group of the hydrolyzable silane [specifically, for example, X in the general formula (A-IV)], preferably 100 % Is hydrolyzed into hydroxyl groups (OH groups), and most of the OH groups, preferably 80% or more, more preferably 90% or more, particularly preferably 100%, are condensed from the viewpoint of liquid stability. preferable.

  The alcohol, solvent, and catalyst generated by the reaction may be removed from the mixed solution after hydrolysis condensation by a known method. The obtained product may be further purified by removing the catalyst by various purification methods such as washing, column separation, and solid adsorbent according to the purpose. Preferably, the catalyst is removed by washing with water from the viewpoint of efficiency.

  Here, when 100% condensation does not occur in the hydrolysis condensation, the product obtained by the present production method includes a silsesquioxane compound having a structure in which all of the Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed. In addition to this, there may be a ladder structure in which Si-OH groups remain, an incomplete cage structure and / or a silsesquioxane compound of a random condensate, which is the component (A) obtained by this production method. The silsesquioxane compound may contain these ladder structures, incomplete cage structures, and / or random condensates. In addition, the ratio of the silsesquioxane compound having a structure in which all of the Si—OH groups are hydrolyzed and condensed is preferably 80% by mass or more in the silsesquioxane compound as the component (A) obtained by the present production method. More preferably, it is 90 mass% or more from the viewpoint of liquid stability.

Manufacturing method b
As the production method b, a silsesquioxane obtained by the step b-1 and the step b-1 of producing a silsesquioxane compound having an amino group using a hydrolyzable silane having an amino group Examples of the production method include a step b-2 in which an amino group of a compound is reacted with at least one (meth) acryloyloxy group, at least one isocyanurate ring structure, and an isocyanate group of a compound having one isocyanate group. .

  The production method b can be used, for example, when producing a silsesquioxane compound which is a component (A) having an organic group represented by the general formula (A-II). Below, the manufacturing method of the silsesquioxane compound which is (A) component which has the organic group represented by the said general formula (A-II) by the manufacturing method b is shown.

Step b-1 Specific examples of the hydrolyzable silane having an amino group used in the step b-1 include hydrolyzable silanes represented by the following general formula (A-XVI).

R ⁶ in the general formula (A-XVI) is the same as described above. X is chlorine or a C1-C6 alkoxy group, and X may be the same or different. Specific examples of X include chlorine, methoxy group, ethoxy group, propoxy group, butoxy group and the like.

  Specific examples of the hydrolyzable silane represented by the general formula (A-XVI) include 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

In order to obtain a silsesquioxane compound having an amino group in the step b-1, specifically,
Hydrolytic condensation using the hydrolyzable silane represented by the general formula (A-XVI) as a starting material in the presence of a catalyst, or
Hydrolysis-condensation in the presence of a catalyst using a hydrolyzable silane represented by the general formula (A-XVI) and a hydrolyzable silane other than a hydrolyzable silane having an amino group as a starting material;
Can be mentioned.

  As the hydrolyzable silane other than the hydrolyzable silane having an amino group, a silsesquioxane compound can be produced by hydrolytic condensation together with the hydrolyzable silane represented by the general formula (A-XVI). There is no particular limitation as long as it is present. Specifically, for example, alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane; 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyl Examples include 3- (meth) acryloyloxypropyltrialkoxysilane such as oxypropyltriethoxysilane; vinyltrialkoxysilane such as vinyltrimethoxysilane and vinyltriethoxysilane.

  Here, in this production method, the organic group having both the at least one (meth) acryloyloxy group and the at least one isocyanurate ring structure included in the silsesquioxane compound as the component (A) (A The ratio of the organic group directly bonded to the silicon atom of the component silsesquioxane compound is adjusted with the hydrolyzable silane represented by the general formula (A-XVI) used as a starting material. It can carry out by changing arbitrarily the ratio with hydrolysable silanes other than the hydrolysable silane which has the said amino group used according to it.

  As the catalyst, a basic catalyst is preferably used. Specific examples of the basic catalyst include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethyl Examples thereof include ammonium hydroxide salts such as ammonium hydroxide and ammonium fluoride salts such as tetrabutylammonium fluoride.

  The amount of the catalyst used is not particularly limited, but if it is too much, there are problems such as high cost and difficulty in removal, while if too little, the reaction is slowed. Therefore, the usage-amount of a catalyst becomes like this. Preferably it is 0.0001-1.0 mol with respect to 1 mol of hydrolysable silane, More preferably, it is the range of 0.0005-0.1 mol.

  When hydrolyzing and condensing a hydrolyzable silane, water is usually used. The quantity ratio of hydrolyzable silane and water is not particularly limited. The amount of water used is preferably 0.1 to 100 mol of water, more preferably 0.5 to 3 mol, per mol of hydrolyzable silane. If the amount of water is too small, the reaction may be slowed and the yield of the desired silsesquioxane compound may be reduced. If the amount of water is too large, the product will have a high molecular weight, resulting in a product with the desired structure. May decrease. Moreover, when using a basic catalyst as aqueous solution, the water to be used may be substituted with the water, and water may be added separately.

  In the hydrolysis condensation, an organic solvent may be used or may not be used. It is preferable to use an organic solvent from the viewpoint of preventing gelation and adjusting the viscosity during production. As the organic solvent, polar organic solvents and nonpolar organic solvents can be used alone or as a mixture.

  As the polar organic solvent, lower alcohols such as methanol, ethanol and 2-propanol, ketones such as acetone and methyl isobutyl ketone, and ethers such as tetrahydrofuran are used. Particularly, acetone and tetrahydrofuran have a low boiling point and the system is uniform. And the reactivity is improved. As the nonpolar organic solvent, a hydrocarbon solvent is preferable, and an organic solvent having a boiling point higher than that of water such as toluene and xylene is preferable. In particular, an organic solvent azeotropic with water such as toluene efficiently removes water from the system. This is preferable because it is possible. In particular, mixing a polar organic solvent and a nonpolar organic solvent provides the above-described advantages, so that it is preferably used as a mixed solvent.

  As reaction temperature at the time of hydrolysis condensation, it is 0-200 degreeC normally, Preferably it is 10-200 degreeC, More preferably, it is 10-120 degreeC. Moreover, although this reaction can be implemented irrespective of a pressure, the pressure range of 0.02-0.2 MPa is preferable, and the pressure range of 0.08-0.15 MPa is especially preferable.

  In the hydrolysis-condensation reaction, the condensation reaction proceeds together with hydrolysis, and most of the hydrolyzable group of the hydrolyzable silane [specifically, for example, X in the general formula (A-XVI)], preferably 100 % Is hydrolyzed into hydroxyl groups (OH groups), and most of the OH groups, preferably 80% or more, more preferably 90% or more, particularly preferably 100%, are condensed from the viewpoint of liquid stability. preferable.

  The alcohol, solvent, and catalyst generated by the reaction may be removed from the mixed solution after hydrolysis condensation by a known method. The obtained product may be further purified by removing the catalyst by various purification methods such as washing, column separation, and solid adsorbent according to the purpose. Preferably, the catalyst is removed by washing with water from the viewpoint of efficiency.

Step b-2 In the step b-2, at least one (meth) acryloyloxy group, at least one isocyanurate ring structure is added to the amino group of the silsesquioxane compound obtained in the step b-1. And the isocyanate group of the compound having one isocyanate group is reacted.

  Examples of the compound having at least one (meth) acryloyloxy group, at least one isocyanurate ring structure, and one isocyanate group include compounds represented by the following general formula (A-XVII).

R ⁴ , R ⁵ and m in the general formula (A-XVII) are the same as described above.

  The mixing ratio of both of the amino group of the silsesquioxane compound obtained by the step b-1 and the isocyanate group of the compound represented by the general formula (A-XVII) is particularly limited. However, usually, the isocyanate group of the compound represented by the general formula (A-XVII) is used in an equimolar amount with respect to the number of moles of the amino group of the silsesquioxane compound obtained in the step b-1. Reaction.

  This reaction can be performed according to a conventional method in which an amino group and an isocyanate group are reacted. The reaction temperature is, for example, -78 ° C to 200 ° C, preferably -78 ° C to 100 ° C, more preferably -10 ° C to 40 ° C. Although this reaction can be carried out regardless of pressure, a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable.

  In the reaction, a solvent may be appropriately used. Specific examples of the solvent include esters such as ethyl acetate, butyl acetate, methyl benzoate and methyl propionate; ethers such as tetrahydrofuran, dioxane and dimethoxyethane; propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Examples include glycol ethers such as 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons.

  The compound represented by the general formula (A-XVII) is the same compound as the compound represented by the general formula (A-IX). Therefore, the compound represented by the general formula (A-XVII) can be obtained by the same production method as the compound represented by the general formula (A-IX) described in the above production method a. In addition to the compound represented by the general formula (A-IX), the product obtained by the method for producing the compound represented by the general formula (A-IX) described in the production method a described above , A compound represented by the general formula (A-XII) may be included.

  However, there is no particular problem if the compound represented by the general formula (A-XII) is contained in the raw material for production in the step b-2.

  The silsesquioxane compound which is (A) component is manufactured by the above manufacturing method.

  Here, in the case where 100% condensation is not performed in the hydrolysis and condensation in the step b-1, the product obtained by the production method b has a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed. In addition to the silsesquioxane compound, a ladder structure in which a Si—OH group remains, an incomplete cage structure, and / or a random condensate silsesquioxane compound may be contained, but this is obtained by this production method. The silsesquioxane compound as the component (A) may contain a ladder structure, an incomplete cage structure and / or a random condensate. In addition, the ratio of the silsesquioxane compound having a structure in which all of the Si—OH groups are hydrolyzed and condensed is preferably 80% by mass or more in the silsesquioxane compound as the component (A) obtained by the present production method. More preferably, it is 90 mass% or more from the viewpoint of liquid stability.

  The blending ratio of the silsesquioxane compound as the component (A) in the active energy ray-curable composition of the present invention is not particularly limited. From the viewpoint of scratch resistance, adhesion to an object to be coated and weather resistance, the cured coating film obtained is preferably 1 to 95 parts by mass with respect to 100 parts by mass of the nonvolatile content of the active energy ray-curable composition. More preferably, it is 10-80 mass parts, Most preferably, it is 15-50 mass parts.

Reactive particles (B)
The reactive particles (B) are obtained by reacting silica fine particles (b-1) with hydrolyzable silane (b-2) having a (meth) acryloyloxy group in the molecule.

Silica fine particles (b-1)
Examples of the silica fine particles (b-1) include colloidal silica fine particles and powdery fine particle silica.

  Colloidal silica fine particles are obtained by dispersing ultrafine particles of silica in a dispersion medium.

  As a dispersion medium, water; alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol; polyhydric alcohol solvents such as ethylene glycol; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc. Polyhydric alcohol derivatives; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol; monomers such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and tetrahydrofurfuryl acrylate. Of these, water, methanol, ethanol, isopropanol and the like are preferable from the viewpoint of ease of production.

  As colloidal silica fine particles, methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, PGM-ST, ST-UP, ST-OUP, ST-20, ST-40, ST -C, ST-N, ST-O, ST-50, ST-OL (all manufactured by Nissan Chemical Industries, Ltd.) and the like.

  As the fine powder silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50 (all manufactured by Nippon Aerosil), Sildex H31, H32, H51, H52, H121, H122 (all manufactured by Asahi Glass) , E220A, E220 (all manufactured by Nippon Silica Kogyo Co., Ltd.), SYLYSIA470 (manufactured by Fuji Silysia Chemical Ltd.), and the like.

  The average primary particle diameter of the silica fine particles (b-1) is preferably 1 to 200 nm, and more preferably 5 to 80 nm. The lower limit of these ranges is significant in terms of suppressing gelation when reacted with the compound (b-2). The upper limit of these ranges is significant in terms of the transparency of the cured coating film obtained with the active energy ray-curable composition of the present invention.

  The average primary particle diameter in the present invention is a median diameter (d50) of a volume-based particle size distribution measured by a dynamic light scattering method, and can be measured using, for example, a nanotrack particle size distribution measuring apparatus manufactured by Nikkiso Co., Ltd. it can.

Hydrolyzable silane (b-2) having a (meth) acryloyloxy group in the molecule
Hydrolyzable silane (b-2) having a (meth) acryloyloxy group in the molecule [hereinafter sometimes referred to as “compound (b-2)”. ] Has a hydrolyzable silyl group. The hydrolyzable silyl group is a silanol group or a group that generates a silanol group by hydrolysis. Examples of the group that forms a silanol group include groups in which an alkoxy group, an aryloxy group, an acetoxy group, a halogen atom, or the like is bonded to a silicon atom. Here, the alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and the aryloxy group is preferably an aryloxy group having 6 to 18 carbon atoms.

  The compound (b-2) is not particularly limited as long as it is a compound having a (meth) acryloyloxy group and a hydrolyzable silyl group in the molecule.

  As the compound (b-2), for example, the following general formula (BI)

[In formula (BI), Z represents a (meth) acryloyloxy group. R ¹¹ represents a divalent hydrocarbon group having 1 to 8 carbon atoms. At least one of R ^a , R ^b and R ^c represents a halogen atom, a hydroxy group, an alkoxy group or an aryloxy group, and the remainder represents a hydrogen atom, an alkyl group or an aryl group. ] Compound (b-2-1) [Hereinafter, it may be abbreviated as "Compound (b-2-1)." ].

R ¹¹ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 8 carbon atoms. Specifically, for example, methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group, octylene group and the like can be mentioned. It is done.

Examples of the alkoxy group represented by R ^a , R ^b and R ^c include those having 1 to 8 carbon atoms, and a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an octyloxy group and the like are preferable.

Examples of the alkyl group represented by R ^a , R ^b and R ^c include those having 1 to 8 carbon atoms, and a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group and the like are preferable.

Examples of the aryloxy group represented by R ^a , R ^b and R ^c include those having 6 to 18 carbon atoms, and a phenoxy group, a xylyloxy group and the like are preferable.

Examples of the aryl group represented by R ^a , R ^b and R ^c include those having 6 to 18 carbon atoms, and a phenyl group, a xylyl group and the like are preferable.

Examples of the group represented by R ^a (R ^b ) (R ^c ) Si— include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. it can. Of these groups, a trimethoxysilyl group, a triethoxysilyl group, and the like are preferable.

  Examples of the compound (b-2-1) include 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 2-methacryloyloxyethyltrimethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 3 -Methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyl Examples thereof include at least one compound selected from dimethoxysilane and the like.

  As the compound (b-2), in addition to the compound (b-2-1), for example, a hydrolyzable silane having both a (meth) acryloyloxy group and a urethane bond in the molecule [hereinafter referred to as “compound (B-2-2) ". ].

  Examples of the hydrolyzable silane having both a (meth) acryloyloxy group and a urethane bond in the molecule include the following general formula (B-II):

[In the formula (B-II), R ¹² represents a hydrogen atom or a methyl group. R ¹³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. R ¹⁴ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. At least one of R ^a , R ^b and R ^c represents a halogen atom, a hydroxy group, an alkoxy group or an aryloxy group, and the remainder represents a hydrogen atom, an alkyl group or an aryl group. n shows the integer of 1-10. ] The hydrolysable silane represented by this is mentioned.

The R ¹³ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specifically, for example, methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and other alkylene groups; cyclohexylene group And aralkylene groups such as a phenylene group and a xylylene group. Especially, it is preferable that it is a C1-C6 bivalent hydrocarbon group, especially an ethylene group, a 1, 2- propylene group, and a 1, 4- butylene group.

The R ¹⁴ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specifically, for example, methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and other alkylene groups; cyclohexylene group And aralkylene groups such as a phenylene group and a xylylene group. Especially, it is preferable that it is a C1-C6 bivalent hydrocarbon group, especially an ethylene group and a 1, 3- propylene group.

  The n is not particularly limited as long as it is an integer of 1 to 10. n is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1.

  The hydrolyzable silane represented by the general formula (B-II) is represented by, for example, a hydrolyzable silane represented by the following general formula (B-III) and the following general formula (B-IV). It can be obtained by reacting with a compound.

[In the formula (B-III), R ¹⁴ , R ^a , R ^b and R ^c are the same as above. ]

[In the formula (B-IV), R ¹² , R ¹³ and n are the same as defined above. ]
Examples of the hydrolyzable silane represented by the general formula (B-III) include 3-isocyanatopropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane.

  Examples of the compound represented by the general formula (B-IV) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Examples include meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and dipropylene glycol mono (meth) acrylate.

  The reaction between the hydrolyzable silane represented by the general formula (B-III) and the compound represented by the general formula (B-IV) can be performed according to a conventional method in which an isocyanate group and a hydroxyl group are reacted. .

  The use ratio of the hydrolyzable silane represented by the general formula (B-III) and the compound represented by the general formula (B-IV) in the above reaction formula is usually 0.90 with respect to 1 mol of the former. About 1.10 mol, preferably about 0.95 to 1.05 mol.

  The reaction temperature is, for example, 0 to 200 ° C, preferably 20 to 200 ° C, more preferably 20 to 120 ° C. Although this reaction can be carried out regardless of pressure, a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable. The reaction is usually completed in about 2 to 10 hours.

  In the reaction, a catalyst may be appropriately used. Examples of the catalyst include tertiary amines such as triethylamine and organometallic compounds such as dibutyltin dilaurate.

  In the reaction, a solvent may be appropriately used. Specific examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, ethyl isoamyl ketone, diisobutyl ketone, and methyl hexyl ketone; ethyl acetate, butyl acetate, methyl benzoate, propion Esters such as methyl acid; Ethers such as tetrahydrofuran, dioxane and dimethoxyethane; Glycol ethers such as propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; Aromatic hydrocarbons such as toluene and xylene; Aliphatic hydrocarbons And the like.

  Examples of the compound (b-2) include, in addition to the compound (b-2-1) and the compound (b-2-2), both a (meth) acryloyloxy group and an isocyanurate ring structure in the molecule. Hydrolyzable silane [hereinafter, referred to as “compound (b-2-3)”. ].

  Examples of the hydrolyzable silane having both a (meth) acryloyloxy group and an isocyanurate ring structure in the molecule include the following general formula (B-V)

[In the formula (B-V), R ¹⁵ are the same or different and each represents a hydrogen atom or a methyl group. R ¹⁶ is the same or different and represents a divalent organic group. R ¹⁷ represents a divalent organic group. At least one of R ^a , R ^b and R ^c represents a halogen atom, a hydroxy group, an alkoxy group or an aryloxy group, and the remainder represents a hydrogen atom, an alkyl group or an aryl group. ] The hydrolysable silane represented by this is mentioned.

The R ¹⁶ is not particularly limited as long as it is a divalent organic group. As a bivalent organic group, a C1-C100 bivalent organic group is mentioned, for example. Preferably it is a C1-C30 bivalent organic group. The divalent organic group is not limited to a hydrocarbon group, and may have, for example, a urethane bond, an ester bond, an ether bond, or the like.

R ¹⁷ is not particularly limited as long as it is a divalent organic group. As a bivalent organic group, a C1-C100 bivalent organic group is mentioned, for example. Preferably it is a C1-C30 bivalent organic group. The divalent organic group is not limited to a hydrocarbon group, and may have, for example, a urethane bond, an ester bond, an ether bond, or the like.

  More specifically, examples of the hydrolyzable silane represented by the general formula (B-V) include a hydrolyzable silane represented by the following general formula (B-VI) and the following general formula (B-VII). ) Represented by a hydrolyzable silane.

[In formula (B-VI), R ¹⁸ are the same or different and each represents a hydrogen atom or a methyl group. R ¹⁹ is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. R ²⁰ represents a divalent hydrocarbon group having 1 to 4 carbon atoms. p is the same or different and represents an integer of 0 to 5. R ^a , R ^b and R ^c are the same as described above. In formula (B-VII), R ²¹ are the same or different and each represents a hydrogen atom or a methyl group. R ²² is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. R ²³ represents a divalent hydrocarbon group having 1 to 4 carbon atoms. R ^a , R ^b and R ^c are the same as described above. ].

R ¹⁹ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and the like. Especially, it is preferable from the transparency point of the cured coating film obtained that it is a C2-C4 bivalent hydrocarbon group, especially ethylene group.

The R ²⁰ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 4 carbon atoms. Specific examples include ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group and the like.

As the organic group represented by the general formula (B-VI), R ¹⁸ is a hydrogen atom from the viewpoint of better scratch resistance, transparency, and active energy ray curability in the presence of a photopolymerization initiator. R ¹⁹ is an ethylene group, R ²⁰ is a 1,3-propylene group, and an organic group in which p is 0 is preferable.

R ²² is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and the like. Especially, it is preferable from the transparency point of the cured coating film obtained that it is a C2-C4 bivalent hydrocarbon group, especially ethylene group.

R ²³ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 4 carbon atoms. Specific examples include ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group and the like.

As the organic group represented by the general formula (B-VII), R ²¹ is a hydrogen atom from the viewpoint of better scratch resistance, transparency, and active energy ray curability in the presence of a photopolymerization initiator. And an organic group in which R ²² is an ethylene group and R ²³ is a 1,3-propylene group.

  A method for producing a hydrolyzable silane represented by the general formula (B-VI) will be exemplified. Examples of the hydrolyzable silane represented by the general formula (B-VI) include a hydrolyzable silane represented by the following general formula (B-VIII) and a compound represented by the following general formula (B-IX). It can obtain by making it react.

R ²⁰ , R ^a , R ^b, and R ^c in the general formula (B-VIII) are the same as described above.

R ¹⁸ , R ¹⁹ and p in the general formula (B-IX) are the same as described above.

  Specific examples of the hydrolyzable silane represented by the general formula (B-VIII) include 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

  The mixing ratio of the hydrolyzable silane represented by the general formula (B-VIII) and the compound represented by the general formula (B-IX) is not particularly limited. Usually, the reaction is carried out using an equimolar amount of the isocyanate group of the compound represented by the general formula (B-IX) with respect to the number of moles of the amino group of the hydrolyzable silane represented by the general formula (B-VIII). Is done.

  This reaction can be performed according to a conventional method in which an amino group and an isocyanate group are reacted. The reaction temperature is, for example, -78 ° C to 200 ° C, preferably -78 ° C to 100 ° C, more preferably -10 ° C to 40 ° C. Although this reaction can be carried out regardless of pressure, a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable.

  In the reaction, a solvent may be appropriately used. Specific examples of the solvent include esters such as ethyl acetate, butyl acetate, methyl benzoate and methyl propionate; ethers such as tetrahydrofuran, dioxane and dimethoxyethane; propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Examples include glycol ethers such as 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons.

  The compound represented by the general formula (B-IX) is obtained by, for example, reacting a compound represented by the following general formula (BX) with a compound represented by the following general formula (B-XI). Can be obtained.

  The compound represented by the general formula (BX) is a so-called isocyanurate cycloadduct of 1,6-hexamethylene diisocyanate, and trade names include Sumijour N3300 (manufactured by Sumika Bayer Urethane Co., Ltd.) Examples thereof include TPA100 (manufactured by Asahi Kasei Chemicals Corporation).

R ¹⁸ , R ¹⁹ and p in the general formula (B-XI) are the same as described above. As the compound represented by the general formula (B-XI), for example, when p is 0, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl ( Examples include meth) acrylate and 4-hydroxybutyl (meth) acrylate. Examples of the compound when p is 1 to 5 include caprolactone-modified hydroxyalkyl (meth) acrylate. Specifically, “Placcel FA-1”, “Plaxel FA-2”, “Plaxel FA-2D”, “Plaxel FA-3”, “Plaxel FA-4”, “Plaxel FA-5” are trade names. , "Placcel FM-1", "Placcel FM-2", "Placcel FM-2D", "Placcel FM-3", "Placcel FM-4", "Placcel FM-5" (all manufactured by Daicel Chemical Industries) Etc.

  The mixing ratio of the compound represented by the general formula (BX) and the compound represented by the general formula (B-XI) is not particularly limited. The isocyanate group of the compound represented by (BX) and the hydroxyl group of the compound represented by the general formula (B-XI) are usually in a molar ratio of NCO / OH = 1.05 to 2.00, preferably Is a blending ratio of 1.10 to 1.50.

  This reaction can be performed according to a conventional method in which an isocyanate group and a hydroxyl group are reacted. The reaction temperature is, for example, 0 to 200 ° C, preferably 20 to 200 ° C, more preferably 20 ° C to 120 ° C. Although this reaction can be carried out regardless of pressure, a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable. The reaction is usually completed in about 2 to 10 hours.

  In the reaction, a solvent may be appropriately used. Specific examples of the solvent include esters such as ethyl acetate, butyl acetate, methyl benzoate and methyl propionate; ethers such as tetrahydrofuran, dioxane and dimethoxyethane; propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Examples include glycol ethers such as 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons.

  In addition, the product obtained by reacting the compound represented by the general formula (BX) with the compound represented by the general formula (B-XI) includes the general formula (B-IX). In addition to the compound represented by general formula (B-XII)

[In the formula (B-XII), R ¹⁸ , R ¹⁹ and p are the same as defined above. ] May be included.

  And when manufacturing the hydrolyzable silane represented by the said general formula (B-VI), and using the hydrolyzable silane represented by the said general formula (B-VI), reactive particle | grains (B) are used. When manufacturing, even if the compound represented by the general formula (B-XII) or the like is contained in the raw materials for the manufacturing, there is no particular problem.

  Then, the method to manufacture the hydrolysable silane represented by the said general formula (B-VII) is illustrated. Examples of the hydrolyzable silane represented by the general formula (B-VII) include a hydrolyzable silane represented by the following general formula (B-XIII) and a compound represented by the following general formula (B-XIV). It can obtain by making it react.

R ²³ , R ^a , R ^b and R ^c in the general formula (B-XIII) are the same as described above.

R ²¹ and R ^{22 in the} general formula (B-XIV) are the same as described above.

  Specific examples of the hydrolyzable silane represented by the general formula (B-XIII) include 3-isocyanatopropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane.

  Examples of the compound represented by the general formula (B-XIV) include bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate, bis (2-acryloyloxypropyl) hydroxyethyl isocyanurate, and the like. Examples of product names include Aronix M-215 and Aronix M-313 (both manufactured by Toagosei Co., Ltd.).

  The mixing ratio of the hydrolyzable silane represented by the general formula (B-XIII) and the compound represented by the general formula (B-XIV) is not particularly limited. Usually, the reaction is carried out using equimolar amounts of the hydroxyl group of the compound represented by the general formula (B-XIV) with respect to the number of moles of the isocyanate group of the hydrolyzable silane represented by the general formula (B-XIII). Done.

  This reaction can be performed according to a conventional method in which an isocyanate group and a hydroxyl group are reacted. The reaction temperature is, for example, 0 to 200 ° C, preferably 20 to 200 ° C, more preferably 20 ° C to 120 ° C. Although this reaction can be carried out regardless of pressure, a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable. The reaction is usually completed in about 2 to 10 hours.

  In the reaction, a solvent may be appropriately used. Specific examples of the solvent include esters such as ethyl acetate, butyl acetate, methyl benzoate and methyl propionate; ethers such as tetrahydrofuran, dioxane and dimethoxyethane; propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Examples include glycol ethers such as 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons.

  In addition, the compound represented by the general formula (B-XIV) is usually tris (2- (2)) as typified by, for example, Aronix M-215, Aronix M-313 (both manufactured by Toagosei Co., Ltd.) and the like. The following general formula (B-XV) such as acryloyloxyethyl) isocyanurate, tris (2-acryloyloxypropyl) isocyanurate

[In the formula (B-XV), R ²¹ and R ²² are the same as defined above. It is sold as a mixture with a compound represented by

  And when manufacturing the hydrolysable silane represented by the said general formula (B-VII), and using the hydrolysable silane represented by the said general formula (B-VII), reactive particle | grains (B) are used. When manufacturing, even if the compound represented by the general formula (B-XV) is contained in the raw material for the manufacturing, there is no particular problem.

  As the compound (b-2), the compounds exemplified above may be used alone or in combination of two or more kinds. From the viewpoint of active energy ray curability in the presence of a photopolymerization initiator, the compound (b-2-1) and / or the compound (b-2-1) and the compound (b-2-3) are used in combination. It is preferable that the compound (b-2-2) and the compound (b-2-3) are used in combination. The compounding ratio when the compound (b-2-1) and / or the compound (b-2-2) and the compound (b-2-3) are used in combination is the compound (b-2-1) and the compound (b -2-2) Total amount / Compound (b-2-3) = 10/90 to 90/10 (mass ratio), preferably 20/80 to 80/20 (mass ratio). More preferred.

  The reactive particles (B) are obtained by reacting the silica fine particles (b-1) with the compound (b-2). The method for reacting the silica fine particles (b-1) with the compound (b-2) is not particularly limited. For example, [i] a method in which silica fine particles (b-1) and a compound (b-2) are mixed in the presence of an organic solvent containing water and hydrolytic condensation is performed; [ii] in the presence of an organic solvent containing water. A method of condensing the hydrolyzate of the compound (b-2) with the silica fine particles (b-1) after hydrolyzing the compound (b-2) with [iii] the silica fine particles (b-1) and the compound ( b-2) may be mixed in the presence of other components such as water, an organic solvent and a polymerizable unsaturated compound, and hydrolysis condensation may be performed at once. Here, the water used in these production methods may be water contained in the raw material, for example, water that is a dispersion medium of colloidal silica fine particles.

  The method for producing the reactive particles (B) will be described more specifically. The reactive particles (B) are, for example, in the presence of colloidal silica fine particles that are silica fine particles (b-1), a compound (b-2), optionally a lower alcohol, and optionally a polymerizable unsaturated compound. , A dispersion medium in colloidal silica fine particles, and a lower alcohol [including lower alcohol produced by hydrolyzing compound (b-2). ] Is azeotropically distilled together with a solvent having a boiling point higher than that of the lower alcohol under normal pressure or reduced pressure, and the dispersion medium is replaced with the solvent, followed by a dehydration condensation reaction under heating.

  In this production method, a hydrolysis catalyst is optionally added to a mixture of the colloidal silica fine particles (b-1), the compound (b-2), optionally a lower alcohol, and optionally a polymerizable unsaturated compound. And the compound (b-2) is hydrolyzed by a conventional method such as stirring at room temperature or under heating. Subsequently, the dispersion medium in the colloidal silica fine particles and the lower alcohol were azeotropically distilled together with a solvent having a boiling point higher than that of the lower alcohol under normal pressure or reduced pressure, and the dispersion medium was replaced with the solvent. The reaction is usually carried out at a temperature of 80 to 130 ° C. with stirring for 0.5 to 10 hours while maintaining the nonvolatile content concentration in the range of 30 to 90% by mass, preferably in the range of 50 to 80% by mass. After the reaction, it is preferable to azeotropically distill water and lower alcohol generated by condensation reaction or hydrolysis together with a solvent having a boiling point higher than that of the lower alcohol.

  Examples of the solvent used in the above reaction include hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cyclohexane; halogenated hydrocarbons such as trichloroethylene and tetrachloroethylene; 1,4-dioxane, dibutyl ether, and the like. Ethers; ketones such as methyl isobutyl ketone; esters such as n-butyl acetate, isobutyl acetate, ethyl acetate and ethyl propionate; polyhydric alcohol derivatives such as ethylene glycol monobutyl ether;

  The non-volatile content concentration during the reaction is preferably in the range of 5 to 50% by mass. When the nonvolatile content concentration is less than 5% by mass, that is, when the solvent exceeds 95% by mass, the reaction between the silica fine particles (b-1) and the compound (b-2) is insufficient, and active energy curing including reactive particles. The cured film obtained by the conductive composition may be inferior in transparency. On the other hand, if the nonvolatile content concentration exceeds 50% by mass, the product may be gelled.

  By these production methods, the silicon atom on the surface of the silica fine particle (b-1) and the silicon atom in the compound (b-2) molecule are bonded via an oxygen atom, whereby the silica fine particle (b-1) and the compound ( Reactive particles (B) chemically bonded to b-2) are obtained.

  The compounding ratio of the compound (b-2) when obtaining the reactive particles (B) is preferably 1 part by mass or more, more preferably 2 parts by mass with respect to 100 parts by mass of the silica fine particles (b-1). As described above, it is particularly preferably 5 parts by mass or more. When the amount of the compound (b-2) bonded to the silica fine particles (b-1) is less than 1 part by mass, the dispersibility of the reactive particles (B) in the active energy ray-curable composition is not sufficient, The cured film obtained may not have sufficient transparency. Moreover, the compounding ratio of the silica fine particles (b-1) in the raw material during the production of the reactive particles (B) is preferably 5 to 99 parts by mass with respect to 100 parts by mass of the obtained reactive particles (B). More preferably, it is 10 to 98 parts by mass.

  The content of the reactive particles (B) in the active energy ray-curable composition is not particularly limited. From the viewpoint of scratch resistance and transparency of the cured coating, it is preferably 1 to 95 parts by mass, more preferably 5 to 70 parts by mass with respect to 100 parts by mass of the nonvolatile content of the active energy ray-curable composition. Especially preferably, it is 10-50 mass parts.

Photopolymerization initiator (C)
The active energy ray-curable composition of the present invention may further contain a photopolymerization initiator (C). As a photoinitiator (C), if it is an initiator which absorbs an active energy ray and generate | occur | produces a radical, it can be used without being specifically limited.

  Examples of the photopolymerization initiator (C) include α-diketones such as benzyl and diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2, Thioxanthones such as 4-diethylthioxanthone, 2-isopropylthioxanthone, thioxanthone-4-sulfonic acid; benzophenones such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; Michler's ketones; acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, α, α'-dimethoxyacetoxybenzophenone, 2,2'- Methoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Acetophenones such as -butan-1-one, α-isohydroxyisobutylphenone, α, α'-dichloro-4-phenoxyacetophenone, 1-hydroxy-cyclohexyl-phenyl-ketone; 2,4,6-trimethylbenzoyldiphenylphosphine Acylphosphine oxides such as oxide and bis (acyl) phosphine oxide; quinones such as anthraquinone and 1,4-naphthoquinone; phenacyl chloride, trihalomethylphenylsulfone, tris (trihalomethyl) -s-triazine Halogen compounds; peroxides such as di -t- butyl peroxide and the like. These can be used as one or a mixture of two or more.

  Examples of commercially available photopolymerization initiators (C) include IRGACURE-184, IRGACURE-261, IRGACURE-500, IRGACURE-651, IRGACURE-819, IRGACURE-907, IRGACURE-CGI-1700 (Ciba Specialty Chemicals, trade name, English notation IRGACURE), Darocur-1173, Darocur-1116, Darocur-2959, Darocur-1664, Darocur-4043 (Merck Japan, trade name, English notation Darocur), Kayacure (KAYACURE) -MBP, Kayacure-DETX-S, Kayacure-DMBI, Kayacure-EPA, Kayacure-OA (manufactured by Nippon Kayaku Co., Ltd., trade name English notation KAYACURE), Vicure-10, Vicure-55 [Stoufer (STAUFFER Co., L TD.), Product name], TRIGONAL P1 [manufactured by AKZO Co., LTD., Product name], SANDORAY 1000 [SANDOZ Co., LTD., Product Name], Deep (DEAP) (manufactured by APJOHN Co., LTD., Trade name), CANTACURE-PDO, CANTACURE-ITX, CANTACURE-EPD [WARD BLEKINSOP Co., LTD.), Product name] and the like.

  The photopolymerization initiator (C) is preferably one or a mixture of two or more of thioxanthones, acetophenones and acylphosphine oxides from the viewpoint of photocurability. Particularly preferred are mixtures with fin oxides.

  Although the usage-amount of a photoinitiator (C) is not specifically limited, 0.5-10 mass parts is preferable with respect to 100 mass parts of non volatile matters of an active energy ray-curable composition, More preferably Is in the range of 1-5 parts by mass. The lower limit of this range is significant in terms of improving active energy ray curability, and the upper limit is significant in terms of cost and deep curability.

Polymerizable unsaturated compound (D)
The active energy ray-curable composition of the present invention may further contain a polymerizable unsaturated compound (D). The polymerizable unsaturated compound (D) is particularly limited as long as it is a compound other than the components (A) and (B) and has at least one polymerizable unsaturated double bond in its chemical structure. Not.

  Examples of the polymerizable unsaturated compound (D) include a monofunctional polymerizable unsaturated compound and a polyfunctional polymerizable unsaturated compound.

  Examples of the monofunctional polymerizable unsaturated compound include esterified products of monohydric alcohol and (meth) acrylic acid. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, N-acryloyloxyethylhexahydro Examples include phthalimide. Also, for example, hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate; acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid Carboxyl group-containing (meth) acrylates such as 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate and 5-carboxypentyl (meth) acrylate; glycidyl groups such as glycidyl (meth) acrylate and allyl glycidyl ether Containing polymerizable unsaturated compounds; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl Nitrogen-containing alkyl (meth) acrylates such as ru (meth) acrylate and Nt-butylaminoethyl (meth) acrylate; acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N- Methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N- Examples thereof include polymerizable amides such as dimethylaminoethyl (meth) acrylamide.

  Examples of the polyfunctional polymerizable unsaturated compound include an esterified product of a polyhydric alcohol and (meth) acrylic acid. Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, Dipentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, etc. Meth) acrylate compounds; glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, ε-caprolactone modified tris (acryloxyethyl) isocyanurate, etc. tri (meth) acrylate compound; pentaerythritol tetra (meth) acrylate etc. tetra (meth) acrylate compound; other dipentaerythritol penta (meth) acrylate And dipentaerythritol hexa (meth) acrylate. Furthermore, a polymerizable unsaturated group containing acrylic resin, urethane (meth) acrylate resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin, etc. are mentioned. Examples of the polymerizable unsaturated group-containing acrylic resin include a polymerizable unsaturated group-containing acrylic resin obtained by adding a glycidyl group-containing polymerizable unsaturated compound such as glycidyl (meth) acrylate to a carboxyl group-containing acrylic resin, hydroxyl group, and the like. Examples include polymerizable unsaturated group-containing acrylic resins obtained by adding a compound having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate and a polymerizable unsaturated group to the group-containing acrylic resin. These polymerizable unsaturated compounds can be used alone or in combination of two or more.

  Furthermore, examples of the polyfunctional polymerizable unsaturated compound include a polymerizable unsaturated compound represented by the following general formula (DI) and / or a polymerizable unsaturated compound represented by the following general formula (D-II). It is done.

[In the formula (DI), R ²⁴ are the same or different and each represents a hydrogen atom or a methyl group. R ²⁵ is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. q is the same or different and represents an integer of 0 to 5. In formula (D-II), R ²⁶ is the same or different and represents a hydrogen atom or a methyl group. R ²⁷ is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. ]
R ²⁵ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and the like. Especially, it is preferable that it is a C2-C4 bivalent hydrocarbon group, especially an ethylene group.

R ²⁷ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and the like. Especially, it is preferable that it is a C2-C4 bivalent hydrocarbon group, especially an ethylene group.

  The polymerizable unsaturated compound represented by the general formula (DI) includes, for example, 1,6-hexamethylene diisocyanate isocyanurate cycloadduct, and hydroxyalkyl (meth) acrylate or caprolactone-modified hydroxyalkyl (meth). The acrylate can be obtained by heating at 60 to 70 ° C. for several hours using an acrylate in the presence of a tin-based catalyst such as di-n-butyltin dilaurate so that the isocyanate group and the hydroxyl group are approximately equal.

  Examples of the polymerizable unsaturated compound represented by the general formula (D-II) include tris (2-acryloyloxyethyl) isocyanurate, tris (2-acryloyloxypropyl) isocyanurate, and the like.

  Here, the polymerizable unsaturated compound represented by the general formula (DI) includes the compound represented by the general formula (A-XII) described in the above-described method for producing the component (A) and the above-described compound. It is the same compound as the compound represented by the general formula (B-XII) described in the method for producing the component (B). The polymerizable unsaturated compound represented by the general formula (D-II) includes the compound represented by the general formula (A-XV) described in the above-described method for producing the component (A) and the above-described ( B) The same compound as the compound represented by the general formula (B-XV) described in the method for producing the component. Therefore, when manufacturing (A) component or (B) component, the polymerizable unsaturated compound represented by the said general formula (DI), or the polymeric property represented by the said general formula (D-II) Although unsaturated compounds may be contained, the polymerizable unsaturated compound represented by the general formula (D-I) and the polymerizable unsaturated compound represented by the general formula (D-II) are In invention, it shall be contained in a polymerizable unsaturated compound (D).

  Furthermore, as the polyfunctional polymerizable unsaturated compound, for example, hexamethylene disissocyanate trimer having iminooxadiazinedione group and hydroxyalkyl (meth) acrylate are present in the presence of a catalyst, and the isocyanate group and the hydroxyl group are approximately equal. Urethane (meth) acrylates obtained by reacting with each other can also be used. Examples of commercially available hexamethylene disissocyanate trimer having an iminooxadiazinedione group include Desmodur XP2410 (manufactured by Bayer MaterialScience). Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. .

  The reaction of the hexamethylene disissocyanate trimer and the hydroxyalkyl (meth) acrylate can be performed at a temperature of, for example, 0 to 200 ° C, preferably 20 to 200 ° C, more preferably 20 to 120 ° C. The reaction is usually completed in about 2 to 10 hours. In the reaction, a catalyst may be appropriately used. Examples of the catalyst include tertiary amines such as triethylamine and organometallic compounds such as dibutyltin dilaurate.

  In the reaction, a solvent may be appropriately used. Specific examples of the solvent include esters such as ethyl acetate, butyl acetate, methyl benzoate and methyl propionate; ethers such as tetrahydrofuran, dioxane and dimethoxyethane; propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Examples include glycol ethers such as 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons.

  The active energy ray-curable composition of the present invention comprises a polymerizable unsaturated compound represented by the above general formula (D-I), from the viewpoint of weather resistance of the resulting cured coating film and adhesion to an object to be coated, and It is preferable to contain a polymerizable unsaturated compound represented by the general formula (D-II).

  The compounding ratio of the polymerizable unsaturated compound (D) in the active energy ray-curable composition of the present invention is not particularly limited. From the point of the weather resistance of the cured coating film to be obtained and the adhesion to an object to be coated, it is preferably 1 to 95 parts by mass, more preferably 100 parts by mass of the nonvolatile content of the active energy ray-curable composition. Is 10 to 80 parts by mass, particularly preferably 20 to 70 parts by mass.

  The active energy ray-curable composition of the present invention may be blended with various additives, saturated resins and the like as necessary, and may be diluted with a solvent as desired. Examples of the additive include a sensitizer, an ultraviolet absorber, a light stabilizer, a polymerization inhibitor, an antioxidant, an antifoaming agent, a surface conditioner, a plasticizer, and a colorant. Examples of the saturated resin include saturated acrylic resin, saturated polyester resin, saturated urethane resin, and the like.

  Examples of the solvent used for dilution include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, methyl benzoate, and methyl propionate; ethers such as tetrahydrofuran, dioxane, and dimethoxyethane; Examples include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; aromatic hydrocarbons and aliphatic hydrocarbons. These can be used in appropriate combination depending on the purpose such as adjustment of viscosity and adjustment of coating property.

  The nonvolatile content of the active energy ray-curable composition of the present invention is not particularly limited. For example, Preferably it is 20-100 mass%, More preferably, it is 25-70 mass%. These ranges are significant in terms of smoothness of the coating film and shortening of the drying time.

  The method for applying the active energy ray-curable composition of the present invention to the surface of an object to be coated is not particularly limited. For example, roller coating, roll coater coating, spin coater coating, curtain roll coater coating, slit coater coating, Examples include spray coating, electrostatic coating, dip coating, silk printing, and spin coating.

  The article to be coated is not particularly limited. Specific examples include metals, ceramics, glass, plastics, wood, and the like. In addition, a primer layer, an electrodeposition coating layer, an intermediate coating layer, a top coating layer, etc. are formed in advance by applying a primer coating, a cationic electrodeposition coating, an intermediate coating, a top coating, etc. May be.

  When forming a coating film from the said active energy ray curable composition, it can dry as needed. The drying is not particularly limited as long as the solvent that is added can be removed. For example, it can be performed at a drying temperature of 20 to 100 ° C. for a drying time of 3 to 20 minutes.

  The film thickness of the coating film is appropriately set according to the purpose. For example, the film thickness is preferably 1 to 100 μm, and more preferably 1 to 20 μm. When the film thickness is at least the lower limit of these ranges, the coating film is excellent in smoothness and appearance. Moreover, when it is below the upper limit value of these ranges, the curability and crack resistance of the coating film are excellent.

An active energy ray-curable composition is applied to the surface of an object to be coated and dried as necessary, and then irradiated with active energy rays to form a cured coating film. The irradiation source and irradiation amount of active energy ray irradiation are not particularly limited. For example, the active energy ray irradiation source includes ultra-high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, sunlight and the like. Dose, for example preferably 5~20,000J / ^{m 2,} more preferably include a range of 100~10,000J / ^{m 2.}

  The active energy ray irradiation may be performed in an air atmosphere or in an inert gas atmosphere. Examples of the inert gas include nitrogen and carbon dioxide. Active energy ray irradiation in an inert gas atmosphere is preferable from the viewpoint of curability.

  Moreover, you may heat a coating film as needed after active energy ray irradiation. By heating, distortion of the coating film generated by curing of the coating film by active energy ray irradiation can be alleviated. Further, the heating may improve the hardness or adhesion of the coating film. Heating can usually be performed at an ambient temperature of 150 to 250 ° C. for 1 to 30 minutes.

  Hereinafter, the present invention will be described in more detail with reference to examples. “Part” and “%” indicate “part by mass” and “% by mass” unless otherwise specified. In addition, the structural analysis and measurement in this example were performed by the following analyzer and measurement method in addition to the analyzer described in this specification.

( ²⁹ Si-NMR, ¹ H-NMR analysis)
Apparatus: FT-NMR EX-400 manufactured by JEOL
Solvent: CDCl ₃
Internal standard: Tetramethylsilane.

(Production Example 1)
In a four-necked flask equipped with a reflux condenser, a thermometer, an air introduction tube and a stirrer, 179 parts of Sumidur N3300 (manufactured by Sumika Bayer Urethane Co., Ltd.), 87 parts of 2-hydroxyethyl acrylate, 205 parts of isobutyl acetate and p-methoxy 1 part of phenol was blended and stirred. While blowing air, the temperature was raised to 100 ° C., and the reaction was carried out at 100 ° C. for 8 hours. After the reaction, the mixture was cooled to 5 ° C., and 41 parts of 3-aminopropyltriethoxysilane was added dropwise over 1 hour. At this time, the temperature in the flask was controlled so as not to exceed 20 ° C. Subsequently, 205 parts of ethylene glycol monobutyl ether was added, the temperature was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 1 hour. Then, isobutyl acetate was removed by distillation under reduced pressure, and a 60% non-volatile solution of the product (P1) Got.

The obtained product (A1) had an NCO value = 0 mgNCO / g and an amine value = 0 mgKOH / g. As a result of ¹ H-NMR analysis of the product (P1), the molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy group to the methylene group bonded to Si of the product (A1) was 4.0. It was. Further, as a result of ²⁹ Si-NMR analysis of the product (A1), hydrolysis of the ethoxysilyl group in the product (A1) was not confirmed.

  From the above results, the product (A1) is a mixture of a compound represented by the following formula (P-I) and a compound represented by the following formula (P-II),

The ratio was the compound represented by the formula (PI) / the compound represented by the formula (P-II) = 60/40 (molar ratio).

(Production Example 2)
In a four-necked flask equipped with a reflux condenser, a thermometer, an air introduction tube and a stirrer, 207 parts of a 60% non-volatile solution of the product (A1) obtained in Production Example 1, and 3-methacryloyloxypropyltrimethoxysilane 75 Then, 700 parts of tetrahydrofuran and 700 parts of tetrahydrofuran were mixed, and the flask was cooled to 0 ° C. with vigorous stirring, and 2 parts of tetrabutylammonium fluoride trihydrate and 20 parts of deionized water were added. Then, after making it react for 24 hours, controlling so that reaction temperature does not exceed 10 degreeC, vacuum distillation was performed and tetrahydrofuran and deionized water were removed. Subsequently, 88 parts of ethylene glycol monobutyl ether was blended to obtain 340 parts of a 50% nonvolatile solution of the product (A2).

As a result of ²⁹ Si-NMR analysis of the product (A2), only a peak near −70 ppm derived from T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si was confirmed, and hydroxysilyl group The T1 structure and the T2 structure indicating the presence of were not confirmed.

  From the above results, the product (A2) is a mixture of the silsesquioxane compound and the compound represented by the formula (P-II), and the ratio thereof is calculated as silsesquioxane compound / formula (P -II) = 73/27 (mass ratio). And this silsesquioxane compound has the organic group couple | bonded directly with the silicon atom, 20 mol% of organic groups represented by a following formula (P-III) among this organic group, and a following formula ( It was a silsesquioxane compound which has 80 mol% of organic groups represented by P-IV).

(Production Example 3)
A four-necked flask equipped with a reflux condenser, a thermometer, an air introduction tube, and a stirrer, 86 parts of a non-volatile content 60% solution of the product (A1) obtained in Production Example 1, and 3-methacryloyloxypropyltrimethoxysilane 148 Then, 700 parts of tetrahydrofuran and 700 parts of tetrahydrofuran were mixed, and the flask was cooled to 0 ° C. with vigorous stirring, and 2 parts of tetrabutylammonium fluoride trihydrate and 35 parts of deionized water were added. Then, after making it react for 24 hours, controlling so that reaction temperature does not exceed 10 degreeC, vacuum distillation was performed and tetrahydrofuran and deionized water were removed. Subsequently, 121 parts of ethylene glycol monobutyl ether was blended to obtain 310 parts of a 50% nonvolatile solution of the product (A3).

As a result of ²⁹ Si-NMR analysis of the product (A3), only a peak near −70 ppm derived from the T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si was confirmed. The T1 structure and the T2 structure indicating the presence of were not confirmed.

  From the above results, the product (A3) is a mixture of the silsesquioxane compound and the compound represented by the formula (P-II), and the ratio is calculated as silsesquioxane compound / formula (P -II) = 88/12 (mass ratio). And this silsesquioxane compound has the organic group couple | bonded directly with the silicon atom, 5 mol% of organic groups represented by said Formula (P-III) among this organic group, and said Formula ( It was a silsesquioxane compound which has 95 mol% of organic groups represented by P-IV).

(Production Example 4)
In a four-necked flask equipped with a reflux condenser, a thermometer, an air introduction tube and a stirrer, 272 parts of a 60% nonvolatile solution of the product (A1) obtained in Preparation Example 1, 3-methacryloyloxypropyltrimethoxysilane 37 Then, 700 parts of tetrahydrofuran and 700 parts of tetrahydrofuran were mixed, and the flask was cooled to 0 ° C. with vigorous stirring, and 2 parts of tetrabutylammonium fluoride trihydrate and 20 parts of deionized water were added. Then, after making it react for 24 hours, controlling so that reaction temperature does not exceed 10 degreeC, vacuum distillation was performed and tetrahydrofuran and deionized water were removed. Subsequently, 70 parts of ethylene glycol monobutyl ether was blended to obtain 357 parts of a 50% nonvolatile solution of the product (A4).

As a result of ²⁹ Si-NMR analysis of the product (A4), only a peak around −70 ppm derived from T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si was confirmed, and hydroxysilyl group The T1 structure and the T2 structure indicating the presence of were not confirmed.

  From the above results, the product (A4) is a mixture of the silsesquioxane compound and the compound represented by the formula (P-II), and the ratio thereof is calculated as silsesquioxane compound / formula (P -II) = 34/66 (mass ratio). And this silsesquioxane compound has an organic group directly bonded to a silicon atom, and among the organic groups, 40 mol% of the organic group represented by the formula (P-III) and the formula ( It was a silsesquioxane compound which has 60 mol% of organic groups represented by P-IV).

(Production Example 5)
In a four-necked flask equipped with a reflux condenser, a thermometer, an air introduction tube and a stirrer, 179 parts of Sumidur N3300 (manufactured by Sumika Bayer Urethane Co., Ltd.), 108 parts of 4-hydroxybutyl acrylate, 205 parts of isobutyl acetate and p-methoxy 1 part of phenol was blended and stirred. While blowing air, the temperature was raised to 100 ° C., and the reaction was carried out at 100 ° C. for 8 hours. After the reaction, the mixture was cooled to 5 ° C., and 41 parts of 3-aminopropyltriethoxysilane was added dropwise over 1 hour. At this time, the temperature of the reaction product in the flask was controlled so as not to exceed 20 ° C. Subsequently, 219 parts of ethylene glycol monobutyl ether was added, the temperature was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 1 hour. Then, isobutyl acetate was removed by distillation under reduced pressure, and a 60% non-volatile solution of the product (A5) Got.

The obtained product (A5) had an NCO value = 0 mgNCO / g and an amine value = 0 mgKOH / g. As a result of ¹ H-NMR analysis of the product (A5), the molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy group to the methylene group bonded to Si of the product (A5) was 4.0. It was. Further, as a result of ²⁹ Si-NMR analysis of the product (A5), hydrolysis of the ethoxysilyl group in the product (A5) was not confirmed.

  From the above results, the product (A5) is a mixture of a compound represented by the following formula (P-V) and a compound represented by the following formula (P-VI),

The ratio was the compound represented by the formula (P-V) / the compound represented by the formula (P-VI) = 60/40 (molar ratio).

(Production Example 6)
In a four-necked flask equipped with a reflux condenser, a thermometer, an air introduction tube and a stirrer, 213 parts of a 60% non-volatile solution of the product (A5) obtained in Production Example 5, 72-methacryloyloxypropyltrimethoxysilane 72 Then, 700 parts of tetrahydrofuran and 700 parts of tetrahydrofuran were mixed, and the flask was cooled to 0 ° C. with vigorous stirring, and 2 parts of tetrabutylammonium fluoride trihydrate and 20 parts of deionized water were added. Then, after making it react for 24 hours, controlling so that reaction temperature does not exceed 10 degreeC, vacuum distillation was performed and tetrahydrofuran and deionized water were removed. Subsequently, 87 parts of ethylene glycol monobutyl ether was blended to obtain 357 parts of a 50% nonvolatile solution of the product (A6).

As a result of ²⁹ Si-NMR analysis of the product (A6), only a peak near −70 ppm derived from T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si was confirmed, and hydroxysilyl group The T1 structure and the T2 structure indicating the presence of were not confirmed.

  From the above results, the product (A6) is a mixture of the silsesquioxane compound and the compound represented by the formula (P-VI), and the ratio thereof is calculated as silsesquioxane compound / formula (P -VI) = 72/28 (mass ratio). And this silsesquioxane compound has the organic group couple | bonded directly with the silicon atom, 20 mol% of organic groups represented by a following formula (P-VII) among this organic group, and a following formula ( P-VIII) was a silsesquioxane compound having an organic group represented by 80 mol%.

(Production Example 7)
In a four-necked flask equipped with a reflux condenser, thermometer, air inlet tube and stirrer, 179 parts of Sumidur N3300 (manufactured by Sumika Bayer Urethane Co., Ltd.), Plaxel FA-2D (trade name, ε-caprolactone modified 2-hydroxyethyl) Acrylate, manufactured by Daicel Chemical Industries, Ltd.) 258 parts, 319 parts of isobutyl acetate and 1 part of p-methoxyphenol were mixed and stirred. While blowing air, the temperature was raised to 100 ° C., and the reaction was carried out at 100 ° C. for 8 hours. After the reaction, the mixture was cooled to 5 ° C., and 41 parts of 3-aminopropyltriethoxysilane was added dropwise over 1 hour. At this time, the temperature of the reaction product in the flask was controlled so as not to exceed 20 ° C. Subsequently, 319 parts of ethylene glycol monobutyl ether was added, the temperature was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 1 hour. Then, isobutyl acetate was removed by distillation under reduced pressure, and a 60% nonvolatile solution of the product (A7) Got.

The obtained product (A7) had an NCO value = 0 mgNCO / g and an amine value = 0 mgKOH / g. As a result of ¹ H-NMR analysis of the product (A7), the molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy group to the methylene group bonded to Si of the product (A7) was 4.0. It was. As a result of ²⁹ Si-NMR analysis of the product (A7), hydrolysis of the ethoxysilyl group in the product (A7) was not confirmed.

  From the above results, the product (A7) is a mixture of a compound represented by the following formula (P-IX) and a compound represented by the following formula (PX),

The ratio was the compound represented by the formula (P-IX) / the compound represented by the formula (PX) = 60/40 (molar ratio).

(Production Example 8)
In a four-necked flask equipped with a reflux condenser, a thermometer, an air introduction tube and a stirrer, 240 parts of a non-volatile content 60% solution of the product (A7) obtained in Production Example 7, 3-methacryloyloxypropyltrimethoxysilane 56 Then, 700 parts of tetrahydrofuran and 700 parts of tetrahydrofuran were mixed, and the flask was cooled to 0 ° C. with vigorous stirring, and 2 parts of tetrabutylammonium fluoride trihydrate and 20 parts of deionized water were added. Then, after making it react for 24 hours, controlling so that reaction temperature does not exceed 10 degreeC, vacuum distillation was performed and tetrahydrofuran and deionized water were removed. Subsequently, 82 parts of ethylene glycol monobutyl ether was blended to obtain 356 parts of a 50% nonvolatile solution of the product (A8).

As a result of ²⁹ Si-NMR analysis of the product (A8), only a peak near −70 ppm derived from the T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si was confirmed. The T1 structure and the T2 structure indicating the presence of were not confirmed.

  From the above results, the product (A8) is a mixture of the silsesquioxane compound and the compound represented by the formula (PX), and the ratio is calculated as silsesquioxane compound / formula (P -X) = 66/34 (mass ratio). And this silsesquioxane compound has the organic group couple | bonded directly with the silicon atom, 20 mol% of organic groups represented by a following formula (P-XI) among this organic group, and a following formula ( It was a silsesquioxane compound which has 80 mol% of organic groups represented by P-XII).

(Production Example 9)
A four-necked flask equipped with a reflux condenser, a thermometer, an air introduction tube, and a stirrer was added to 179 parts of Aronix M-313 (manufactured by Toagosei Co., Ltd., isocyanuric acid EO-modified di- and triacrylate), 3-isocyanatopropyltriethoxysilane 38 Parts, 145 parts of isobutyl acetate and 1 part of p-methoxyphenol were mixed and stirred. While blowing air, the temperature was raised to 100 ° C., and the reaction was carried out at 100 ° C. for 8 hours. After the reaction, 145 parts of ethylene glycol monobutyl ether was added, the temperature was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 1 hour. Then, isobutyl acetate was removed by distillation under reduced pressure, and a 60% nonvolatile solution of the product (A9) Got.

The obtained product (A9) had an NCO value of 0 mg NCO / g. As a result of ¹ H-NMR analysis of the product (A9), the molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy group to the methylene group bonded to Si of the product (A9) was 7.7. It was. Further, as a result of ²⁹ Si-NMR analysis of the product (A9), hydrolysis of the ethoxysilyl group in the product (A9) was not confirmed.

  From the above results, the product (A9) is a mixture of a compound represented by the following formula (P-XIII) and a compound represented by the following formula (P-XIV),

The ratio was the compound represented by the formula (P-XIII) / the compound represented by the formula (P-XIV) = 35/65 (molar ratio).

(Production Example 10)
In a four-necked flask equipped with a reflux condenser, a thermometer, an air introduction tube, and a stirrer, 196 parts of a 60% nonvolatile solution of the product (A9) obtained in Production Example 9, 3-methacryloyloxypropyltrimethoxysilane 82 Then, 700 parts of tetrahydrofuran and 700 parts of tetrahydrofuran were mixed, and the flask was cooled to 0 ° C. with vigorous stirring, and 2 parts of tetrabutylammonium fluoride trihydrate and 20 parts of deionized water were added. Then, after making it react for 24 hours, controlling so that reaction temperature does not exceed 10 degreeC, vacuum distillation was performed and tetrahydrofuran and deionized water were removed. Subsequently, 90 parts of ethylene glycol monobutyl ether was blended to obtain 336 parts of a 50% nonvolatile solution of the product (A10).

As a result of ²⁹ Si-NMR analysis of the product (A10), only a peak near −70 ppm derived from T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si was confirmed, and hydroxysilyl group The T1 structure and the T2 structure indicating the presence of were not confirmed.

  From the above results, the product (A10) is a mixture of a silsesquioxane compound and a compound represented by the formula (P-XIV), and the ratio is calculated as silsesquioxane compound / formula (P -XIV) = 60/40 (mass ratio). And this silsesquioxane compound has the organic group couple | bonded directly with the silicon atom, 20 mol% of organic groups represented by a following formula (P-XV) among this organic group, and a following formula ( P-XVI) was a silsesquioxane compound having an organic group represented by 80 mol%.

(Production Example 11)
In a four-necked flask equipped with a reflux condenser, a thermometer, an air introduction tube and a stirrer, 179 parts of Sumidur N3300 (manufactured by Sumika Bayer Urethane Co., Ltd.), 87 parts of 2-hydroxyethyl acrylate, 205 parts of isobutyl acetate and p-methoxy 1 part of phenol was blended and stirred. While blowing air, the temperature was raised to 100 ° C., and the reaction was carried out at 100 ° C. for 8 hours. After the reaction, the mixture was cooled to 5 ° C., and 41 parts of 3-aminopropyltriethoxysilane was added dropwise over 1 hour. At this time, the temperature of the reaction product in the flask was controlled so as not to exceed 20 ° C. Subsequently, 205 parts of ethylene glycol monobutyl ether was added, the temperature was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 1 hour. Then, isobutyl acetate was removed by distillation under reduced pressure, and a 60% nonvolatile solution of the product (B1) Got.

The obtained product (B1) had an NCO value = 0 mgNCO / g and an amine value = 0 mgKOH / g. As a result of ¹ H-NMR analysis of the product (B1), the molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy group to the methylene group bonded to Si of the product (B1) was 4.0. It was. Further, as a result of ²⁹ Si-NMR analysis of the product (B1), hydrolysis of the ethoxysilyl group in the product (B1) was not confirmed.

  From the above results, the product (B1) is a mixture of a compound represented by the following formula (P-XVII) and a compound represented by the following formula (P-XVIII),

The ratio was the compound represented by the formula (P-XVII) / the compound represented by the formula (P-XVIII) = 60/40 (molar ratio).

(Production Example 12)
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica fine particles (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, Nissan Chemical Industries, Ltd.) 333 parts (silica fine particles: 100 parts), 3-methacryloyloxypropyltrimethoxysilane (10 parts), p-methoxyphenol (0.2 parts) and isopropanol (227 parts) were added, and the mixture was heated with stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system. Subsequently, 17 parts of a non-volatile content 60% solution of the product (B1) obtained in Production Example 11 [6 parts of the compound represented by the formula (P-XVII)] was added and stirred at 95 ° C. for 2 hours. Then, the dehydration condensation reaction was carried out, the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the mixture was further reacted for 1 hour with stirring. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent was replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a mixture of reactive particles and a compound represented by the formula (P-XVIII) having a nonvolatile content of 40%. It was. The ratio between the reactive particles calculated from the blending amount and the compound represented by the formula (P-XVIII) is as follows: reactive particles / compound represented by the formula (P-XVIII) = 100/3 (mass ratio) )Met. In addition, the mixture of the reactive particle obtained by this manufacture example and the compound represented by said Formula (P-XVIII) is called a product (B2).

(Production Example 13)
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica fine particles (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, Nissan Chemical Industries, Ltd.) Manufactured) 333 parts (silica fine particles 100 parts), 3-methacryloyloxypropyltrimethoxysilane 14 parts, p-methoxyphenol 0.2 parts and isopropanol 230 parts, and then heated while stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system. Subsequently, 10 parts of a non-volatile content 60% solution of the product (B1) obtained in Production Example 11 [4 parts of the compound represented by the formula (P-XVII)] was added, and the mixture was stirred at 95 ° C. for 2 hours. Then, the dehydration condensation reaction was carried out, the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the mixture was further reacted for 1 hour with stirring. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent was replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a mixture of reactive particles and a compound represented by the formula (P-XVIII) having a nonvolatile content of 40%. It was. The ratio between the reactive particles calculated from the blending amount and the compound represented by the formula (P-XVIII) is as follows: reactive particles / compound represented by the formula (P-XVIII) = 100/2 (mass ratio) )Met. In addition, the mixture of the reactive particle obtained by this manufacture example and the compound represented by said Formula (P-XVIII) is called a product (B3).

(Production Example 14)
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica fine particles (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, Nissan Chemical Industries, Ltd.) 333 parts (silica fine particles: 100 parts), 3-methacryloyloxypropyltrimethoxysilane (6 parts), p-methoxyphenol (0.2 parts) and isopropanol (223 parts) were added, and the mixture was heated with stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system. Subsequently, 23 parts of a 60% non-volatile solution of the product (B1) obtained in Production Example 11 [8 parts of the compound represented by the formula (P-XVII)] was added and stirred at 95 ° C. for 2 hours. Then, the dehydration condensation reaction was carried out, the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the mixture was further reacted for 1 hour with stirring. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent was replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a mixture of reactive particles and a compound represented by the formula (P-XVIII) having a nonvolatile content of 40%. It was. The ratio between the reactive particles calculated from the blending amount and the compound represented by the formula (P-XVIII) is: reactive particles / compound represented by the formula (P-XVIII) = 100/5 (mass ratio) )Met. In addition, the mixture of the reactive particle obtained by this manufacture example and the compound represented by said Formula (P-XVIII) is called a product (B4).

(Production Example 15)
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica fine particles (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, Nissan Chemical Industries, Ltd.) 333 parts (silica fine particle: 100 parts), 3-methacryloyloxypropyltrimethoxysilane (3 parts), p-methoxyphenol (0.2 parts) and isopropanol (232 parts) were added, and the mixture was heated with stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system. Subsequently, 4 parts of a 60% nonvolatile solution of the product (B1) obtained in Production Example 11 [2 parts of the compound represented by the above formula (P-XVII)] were added, and the mixture was stirred at 95 ° C. for 2 hours. Then, the dehydration condensation reaction was carried out, the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the mixture was further reacted for 1 hour with stirring. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent was replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a mixture of reactive particles and a compound represented by the formula (P-XVIII) having a nonvolatile content of 40%. It was. The ratio of the reactive particles calculated from the blending amount to the compound represented by the formula (P-XVIII) is as follows: reactive particles / compound represented by the formula (P-XVIII) = 100/1 (mass ratio) )Met. In addition, the mixture of the reactive particle obtained by this manufacture example and the compound represented by said Formula (P-XVIII) is called a product (B5).

(Production Example 16)
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica fine particles (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, Nissan Chemical Industries, Ltd.) Manufactured) 333 parts (silica fine particles 100 parts), 3-methacryloyloxypropyltrimethoxysilane 20 parts, p-methoxyphenol 0.2 parts and isopropanol 220 parts, and then heated while stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system. Subsequently, 33 parts of a 60% nonvolatile solution of the product (B1) obtained in Production Example 11 [12 parts of the compound represented by the formula (P-XVII)] were added, and the mixture was stirred at 95 ° C. for 2 hours. Then, the dehydration condensation reaction was carried out, the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the mixture was further reacted for 1 hour with stirring. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent was replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a mixture of reactive particles and a compound represented by the formula (P-XVIII) having a nonvolatile content of 40%. It was. The ratio of the reactive particles calculated from the blending amount to the compound represented by the formula (P-XVIII) is as follows: reactive particles / compound represented by the formula (P-XVIII) = 100/6 (mass ratio) )Met. In addition, the mixture of the reactive particle obtained by this manufacture example and the compound represented by said Formula (P-XVIII) is called a product (B6).

(Production Example 17)
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica fine particles (dispersion medium: water, silica concentration: 40% by mass, average primary particle size: 20 nm, trade name: SNOWTEX O-40, Nissan Chemical Co., Ltd.) 250 parts (manufactured by Kogyo Co., Ltd.) (100 parts of silica fine particles), 10 parts of 3-methacryloyloxypropyltrimethoxysilane, 0.2 part of p-methoxyphenol and 143 parts of isopropanol were added, and the temperature was increased while stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system. Subsequently, 17 parts of a non-volatile content 60% solution of the product (B1) obtained in Production Example 11 [6 parts of the compound represented by the formula (P-XVII)] was added and stirred at 95 ° C. for 2 hours. Then, the dehydration condensation reaction was carried out, the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the mixture was further reacted for 1 hour with stirring. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent was replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a mixture of reactive particles and a compound represented by the formula (P-XVIII) having a nonvolatile content of 40%. It was. The ratio between the reactive particles calculated from the blending amount and the compound represented by the formula (P-XVIII) is as follows: reactive particles / compound represented by the formula (P-XVIII) = 100/3 (mass ratio) )Met. In addition, the mixture of the reactive particle obtained by this manufacture example and the compound represented by said Formula (P-XVIII) is called a product (B7).

(Production Example 18)
A separable flask equipped with a reflux condenser, a thermometer and a stirrer was charged with 100 parts of 3-isocyanatopropyltriethoxysilane, 47 parts of 2-hydroxyethyl acrylate, and 0.1 part of p-methoxyphenol, while blowing dry air. The mixture was reacted at 100 ° C. for 12 hours to obtain a product (B8).

(Production Example 19)
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica fine particles (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, Nissan Chemical Industries, Ltd.) 333 parts (silica fine particle is 100 parts), 10 parts of the product (B8) obtained in Production Example 18, 0.2 part of p-methoxyphenol and 227 parts of isopropanol were added, and the temperature was increased while stirring. . When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system. Subsequently, 17 parts of a non-volatile content 60% solution of the product (B1) obtained in Production Example 11 [6 parts of the compound represented by the formula (P-XVII)] was added and stirred at 95 ° C. for 2 hours. Then, the dehydration condensation reaction was carried out, the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the mixture was further reacted for 1 hour with stirring. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent was replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a mixture of reactive particles and a compound represented by the formula (P-XVIII) having a nonvolatile content of 40%. It was. The ratio between the reactive particles calculated from the blending amount and the compound represented by the formula (P-XVIII) is as follows: reactive particles / compound represented by the formula (P-XVIII) = 100/3 (mass ratio) )Met. In addition, the mixture of the reactive particle obtained by this manufacture example and the compound represented by said Formula (P-XVIII) is called a product (B9).

(Production Example 20)
In a four-necked flask equipped with a reflux condenser, a thermometer, an air introduction tube and a stirrer, 179 parts of Sumidur N3300 (manufactured by Sumika Bayer Urethane Co., Ltd.), 108 parts of 4-hydroxybutyl acrylate, 205 parts of isobutyl acetate and p-methoxy 1 part of phenol was blended and stirred. While blowing air, the temperature was raised to 100 ° C., and the reaction was carried out at 100 ° C. for 8 hours. After the reaction, the mixture was cooled to 5 ° C., and 41 parts of 3-aminopropyltriethoxysilane was added dropwise over 1 hour. At this time, the temperature of the reaction product in the flask was controlled so as not to exceed 20 ° C. Subsequently, 219 parts of ethylene glycol monobutyl ether was added, the temperature was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 1 hour, then isobutyl acetate was removed by distillation under reduced pressure, and a 60% non-volatile solution of the product (B10) Got.

The obtained product (B10) had an NCO value = 0 mgNCO / g and an amine value = 0 mgKOH / g. As a result of ¹ H-NMR analysis of the product (B10), the molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy group to the methylene group bonded to Si of the product (B10) was 4.0. It was. Further, as a result of ²⁹ Si-NMR analysis of the product (B10), hydrolysis of the ethoxysilyl group in the product (B10) was not confirmed.

  From the above results, the product (B10) is a mixture of a compound represented by the following formula (P-XIX) and a compound represented by the following formula (P-XX),

The ratio was the compound represented by the formula (P-XIX) / the compound represented by the formula (P-XX) = 60/40 (molar ratio).

(Production Example 21)
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica fine particles (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, Nissan Chemical Industries, Ltd.) 333 parts (silica fine particles: 100 parts), 3-methacryloyloxypropyltrimethoxysilane (10 parts), p-methoxyphenol (0.2 parts) and isopropanol (227 parts) were added, and the mixture was heated with stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system. Subsequently, 17 parts of a 60% non-volatile solution of the product (B10) obtained in Production Example 20 [6 parts of the compound represented by the formula (P-XIX)] was added, and the mixture was stirred at 95 ° C. for 2 hours. Then, the dehydration condensation reaction was carried out, the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the mixture was further reacted for 1 hour with stirring. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent was replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a mixture of reactive particles and the compound represented by the formula (P-XX) having a nonvolatile content of 40%. It was. The ratio between the reactive particles calculated from the blending amount and the compound represented by the formula (P-XX) is as follows: reactive particles / compound represented by the formula (P-XX) = 100/3 (mass ratio) )Met. In addition, the mixture of the reactive particle obtained by this manufacture example and the compound represented by said Formula (P-XX) is called a product (B11).

(Production Example 22)
In a four-necked flask equipped with a reflux condenser, thermometer, air inlet tube and stirrer, 179 parts of Sumidur N3300 (manufactured by Sumika Bayer Urethane Co., Ltd.), Plaxel FA-2D (trade name, ε-caprolactone modified 2-hydroxyethyl) Acrylate, manufactured by Daicel Chemical Industries, Ltd.) 258 parts, isobutyl acetate 319 parts and p-methoxyphenol 1 part were blended and stirred. While blowing air, the temperature was raised to 100 ° C., and the reaction was carried out at 100 ° C. for 8 hours. After the reaction, the mixture was cooled to 5 ° C., and 41 parts of 3-aminopropyltriethoxysilane was added dropwise over 1 hour. At this time, the temperature of the reaction product in the flask was controlled so as not to exceed 20 ° C. Subsequently, 319 parts of ethylene glycol monobutyl ether was added, the temperature was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 1 hour. Then, isobutyl acetate was removed by distillation under reduced pressure, and a 60% nonvolatile solution of the product (B12) Got.

The obtained product (B12) had an NCO value = 0 mgNCO / g and an amine value = 0 mgKOH / g. As a result of ¹ H-NMR analysis of the product (B12), the molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy group to the methylene group bonded to Si of the product (B12) was 4.0. It was. Further, as a result of ²⁹ Si-NMR analysis of the product (B12), hydrolysis of the ethoxysilyl group in the product (B12) was not confirmed.

  From the above results, the product (B12) is a mixture of a compound represented by the following formula (P-XXI) and a compound represented by the following formula (P-XXII),

The ratio was the compound represented by the formula (P-XXI) / the compound represented by the formula (P-XXII) = 60/40 (molar ratio).

(Production Example 23)
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica fine particles (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, Nissan Chemical Industries, Ltd.) 333 parts (silica fine particles: 100 parts), 3-methacryloyloxypropyltrimethoxysilane (10 parts), p-methoxyphenol (0.2 parts) and isopropanol (227 parts) were added, and the mixture was heated with stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system. Subsequently, 17 parts of a non-volatile content 60% solution of the product (B12) obtained in Production Example 22 [6 parts of the compound represented by the formula (P-XXI)] was added and stirred at 95 ° C. for 2 hours. Then, the dehydration condensation reaction was carried out, the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the mixture was further reacted for 1 hour with stirring. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent was replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a mixed solution of reactive particles and the compound represented by the formula (P-XXII) having a nonvolatile content of 40%. It was. The ratio of the reactive particles calculated from the blending amount to the compound represented by the formula (P-XXII) is as follows: reactive particles / compound represented by the formula (P-XXII) = 100/4 (mass ratio) )Met. In addition, the mixture of the reactive particle obtained by this manufacture example and the compound represented by said Formula (P-XXII) is called a product (B13).

(Production Example 24)
A four-necked flask equipped with a reflux condenser, a thermometer, an air introduction tube, and a stirrer was added to 179 parts of Aronix M-313 (manufactured by Toagosei Co., Ltd., isocyanuric acid EO-modified di- and triacrylate), 3-isocyanatopropyltriethoxysilane 38 Parts, 145 parts of isobutyl acetate and 1 part of p-methoxyphenol were mixed and stirred. While blowing air, the temperature was raised to 100 ° C., and the reaction was carried out at 100 ° C. for 8 hours. After the reaction, 145 parts of ethylene glycol monobutyl ether was added, the temperature was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 1 hour. Then, isobutyl acetate was removed by distillation under reduced pressure, and a 60% nonvolatile solution of the product (B14) Got.

The obtained product (B14) had an NCO value of 0 mg NCO / g. As a result of ¹ H-NMR analysis of the product (B14), the molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy group to the methylene group bonded to Si of the product (B14) was 7.7. It was. Further, as a result of ²⁹ Si-NMR analysis of the product (B14), hydrolysis of the ethoxysilyl group in the product (B14) was not confirmed.

  From the above results, the product (B14) is a mixture of a compound represented by the following formula (P-XXIII) and a compound represented by the following formula (P-XXIV),

The ratio was the compound represented by the formula (P-XXIII) / the compound represented by the formula (P-XXIV) = 35/65 (molar ratio).

(Production Example 25)
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica fine particles (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, Nissan Chemical Industries, Ltd.) 333 parts (silica fine particles: 100 parts), 3-methacryloyloxypropyltrimethoxysilane (10 parts), p-methoxyphenol (0.2 parts) and isopropanol (227 parts) were added, and the mixture was heated with stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system. Subsequently, 17 parts of a non-volatile content 60% solution of the product (B14) obtained in Production Example 24 [4 parts of the compound represented by the formula (P-XXIII)] was added and stirred at 95 ° C. for 2 hours. Then, the dehydration condensation reaction was carried out, the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the mixture was further reacted for 1 hour with stirring. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The solvent was replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a mixed solution of reactive particles and the compound represented by the formula (P-XXIV) having a nonvolatile content of 40%. It was. The ratio between the reactive particles calculated from the blending amount and the compound represented by the formula (P-XXIV) is: reactive particles / compound represented by the formula (P-XXIV) = 100/3 (mass ratio) )Met. In addition, the mixture of the reactive particle obtained by this manufacture example and the compound represented by said Formula (P-XXIV) is called a product (B15).

(Production Example 26)
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica fine particles (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, Nissan Chemical Industries, Ltd.) Manufactured) 333 parts (silica fine particles 100 parts), 3-methacryloyloxypropyltrimethoxysilane 10 parts, p-methoxyphenol 0.2 parts and isopropanol 233 parts, and then heated while stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system. Subsequently, after performing a dehydration condensation reaction with stirring at 95 ° C. for 2 hours, the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the mixture was further reacted with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The operation of adding propylene glycol monomethyl ether and performing azeotropic distillation was performed several times to replace the solvent, thereby obtaining a 40% non-volatile dispersion of reactive particles. In addition, the reactive particle obtained by this manufacture example is called a product (B16).

(Production Example 27)
In a four-necked flask equipped with a reflux condenser, thermometer, air inlet tube and stirrer, 179 parts of Sumidur N3300 (manufactured by Sumika Bayer Urethane Co., Ltd.), 109 parts of 2-hydroxyethyl acrylate, 192 parts of isobutyl acetate and p-methoxy 1 part of phenol was blended and stirred. While blowing air, the temperature was raised to 100 ° C., and the reaction was carried out at 100 ° C. for 8 hours. After the reaction, 192 parts of ethylene glycol monobutyl ether was added, the temperature was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 1 hour. Then, isobutyl acetate was removed by distillation under reduced pressure, and a 60% nonvolatile solution of the product (D1) Got.

  The obtained product (D1) had an NCO value = 0 mg NCO / g. From the above results, the product (D1) was a compound represented by the following formula (P-XXV).

(Production Example 28)
A mixture of 50 parts Desmodur XP2410 (manufactured by Bayer MaterialScience), 0.02 part dibutyltin dilaurate, and 0.1 part hydroquinone monomethyl ether in a four-necked flask equipped with a reflux condenser, thermometer, air inlet tube and stirrer Was charged. The mixture was heated to 80 ° C. with stirring. Subsequently, 32.9 parts of 2-hydroxyethyl acrylate was added dropwise over 2 hours while keeping the temperature of the mixture not exceeding 90 ° C., and the mixture was stirred at 80 ° C. for further 4 hours, 20.7 parts of propanol was added to obtain an 80% non-volatile solution of the product (D2). The obtained product (D2) had an NCO value of 0 mg NCO / g.

Example 1
100.0 parts of a 50% nonvolatile solution of the product (A2) obtained in Production Example 2, 75.0 parts of a 40% nonvolatile solution of the product (B2) obtained in Production Example 12, Aronix M-315 (Trade name, manufactured by Toagosei Co., Ltd., isocyanuric acid EO-modified di- and triacrylate) 20.0 parts, 1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator) 3.0 parts, and 2,4,6- 0.5 parts of trimethylbenzoyl-diphenyl-phosphine oxide (photopolymerization initiator) was added, diluted with ethyl acetate to a non-volatile content of 30%, stirred, and then the active energy ray-curable composition No. 1 was produced. Table 1 shows active energy ray-curable composition No. The mass part of (A) component, (B) component, and (D) component with respect to 100 mass parts of nonvolatile content in 1 was shown. In addition, the compounding quantity of Table 1 shows the mass part of a non volatile matter.

Next, the active energy ray-curable composition was applied on an ABS substrate (acrylonitrile-butadiene-styrene terpolymer resin substrate) degreased with isopropanol under the condition that the dry film thickness was 10 μm with an applicator, and at 80 ° C. After removing the solvent by drying for 10 minutes, a cured coating film is formed by irradiating ultraviolet rays (peak top wavelength 365 nm) with a high pressure mercury lamp (80 W / cm) at a dose of 20,000 J / m ² in a nitrogen atmosphere. A test plate was obtained. The obtained test plate was subjected to the following evaluation test. The evaluation results are shown in Table 1.

(Examples 2 to 26, Comparative Examples 1 to 5)
In Example 1, the active energy ray curing of Examples 2 to 26 and Comparative Examples 1 to 5 was performed in the same manner as in Example 1 except that the respective components and blending amounts were changed to the respective components and blending amounts described in Table 1. Composition No. 2-31 were produced.

  Next, a cured coating film was formed by the same method as described in Example 1 to obtain a test plate. The obtained test plate was subjected to the following evaluation test. The evaluation results are shown in Table 1.

(Note 1) EBECRYL 1290: manufactured by Daicel Cytec, 6-functional urethane acrylate (Note 2) In Comparative Examples 2 and 4, “-” indicates that the compatibility between the product P16 and the polymerizable unsaturated compound is poor, and the coating film is considerably cloudy. Indicates that the evaluation was not possible.

<Adhesiveness>
Make a cut line with a cutter to reach the object to be coated, make 100 squares with a size of 2 mm x 2 mm, stick adhesive cellophane tape (registered trademark) on the surface, and peel it off rapidly at 20 ° C The number of the remaining coatings after the check was examined and evaluated according to the following criteria.
A: 100 (no peeling)
○: 90 to 99 Δ: 89 to 50 ×: 49 or less.

<Abrasion resistance>
In accordance with ASTM D-1044, a wear test was performed under the conditions of a wear wheel CS-10F, a load of 500 g, and a rotation speed of 500 cycles. After the test, the sample was washed with a neutral detergent, and the haze value was measured with a haze meter. [Haze value after test-haze value before test] was calculated and evaluated. The smaller the value, the better the scratch resistance.

<Weather resistance>
About each obtained test board, after performing the test for 1000 hours using a sunshine weatherometer, the coating film was observed visually and evaluated according to the following reference | standard.
○: No abnormality, or slight swelling, discoloration, gloss change, peeling, etc. are observed, but there is no practical problem.
(Triangle | delta): A blister, discoloration, gloss change, peeling, etc. are recognized.
X: Remarkable blistering, discoloration, gloss change, peeling, etc.

<Transparency>
A test plate was prepared in the same manner as the test plate preparation method described above except that the article to be coated was changed from the ABS substrate to the glass plate. The appearance of the prepared test plate was visually observed and evaluated according to the following criteria.
○: Transparent and good.
Δ: Slightly cloudy.
X: It is very muddy.

Claims (4)

An organic group directly bonded to a silicon atom, and part or all of the organic groups directly bonded to the silicon atom are at least one (meth) acryloyloxy group and at least one isocyanurate ring structure; The silsesquioxane compound (A), which is an organic group having both of the above, and silica fine particles (b-1) are reacted with hydrolyzable silane (b-2) having a (meth) acryloyloxy group in the molecule. An active energy ray-curable composition containing the reactive particles (B) obtained by the process , wherein the organic group having both the at least one (meth) acryloyloxy group and at least one isocyanurate ring structure The following general formula (AI)

[In formula (AI), R ¹ is the same or different and represents a hydrogen atom or a methyl group. R ² is the same or different and represents a divalent organic group. R ³ represents a divalent organic group. ] The active energy ray-curable composition characterized by the above-mentioned.

The active energy ray-curable composition according to claim 1, comprising a photopolymerization initiator (C). The active energy ray-curable composition according to claim 1 or 2, comprising a polymerizable unsaturated compound (D) other than the component (A) and the component (B). A coated article obtained by coating the active energy ray-curable composition according to any one of claims 1 to 3 on an object to be coated.