WO2011086957A1

WO2011086957A1 - Active energy ray-curable composition, and coated article

Info

Publication number: WO2011086957A1
Application number: PCT/JP2011/050064
Authority: WO
Inventors: 良成松浦; 彰典永井; 敦也加藤
Original assignee: 関西ペイント株式会社
Priority date: 2010-01-15
Filing date: 2011-01-05
Publication date: 2011-07-21
Also published as: TW201139573A; TWI439520B; JP5656877B2; JPWO2011086957A1

Abstract

Disclosed is an active energy ray-curable composition which is capable of providing a cured coating film that has high abrasion resistance and excellent transparency. Specifically disclosed is an active energy ray-curable composition which contains (A) a silsesquioxane compound and (B) reactive particles. The active energy ray-curable composition is characterized in that: the silsesquioxane compound (A) has organic groups that are directly bonded to silicon atoms in the silsesquioxane compound (A), and at least one of the organic groups has both (a-1) at least one member selected from the group consisting of a secondary hydroxyl group, an urethane bond and a urea bond and (a-2) at least one (meth)acryloyloxy group; and the reactive particles (B) are obtained by having (b-1) fine silica particles and (b-2) a hydrolyzable silane, which has a (meth)acryloyloxy group in each molecule, react with each other.

Description

Active energy ray-curable composition and coated article

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 outdoors increases, 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. Disclosed is a wear-resistant coating-forming composition containing a urethane (meth) acrylate having a group and an alicyclic skeleton, and a photopolymerization initiator. The scratch resistance of the coating film obtained using this abrasion-resistant coating forming composition 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 the 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 to an organic compound having a polymerizable unsaturated group and a hydrolyzable silyl group, and an organic compound having two or more polymerizable unsaturated groups. Disclosed is a curable composition containing a compound and a both-end reactive polydimethylsiloxane compound. The scratch resistance of the coating film obtained by using this curable composition is not yet sufficient for the high scratch resistance requirement recently required. In this curable composition, the both-end reactive polysiloxane compound is a component that imparts slipperiness to the cured coating film, and the scratch resistance is high even when the blending amount of the both-end reactive polysiloxane compound is increased. On the other hand, when the blending amount of the both-end reactive polysiloxane compound is increased, the transparency of the resulting cured coating film is lowered.

Japanese Patent Laid-Open No. 5-230397 JP-A-6-128502 International Publication 97/011129 Japanese Patent Laid-Open No. 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. Silsesquioxane compound (A) and reactive particles (B)
An active energy ray-curable composition containing
The silsesquioxane compound (A) has an organic group directly bonded to a silicon atom in the silsesquioxane compound (A),
At least one of the organic groups has both (a-1) at least one selected from the group consisting of a secondary hydroxyl group, a urethane bond and a urea bond, and (a-2) at least one (meth) acryloyloxy group. And 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. ,
Active energy ray-curable composition,
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. 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.

The cured film with high scratch resistance and excellent transparency can be obtained by the active energy ray-curable composition of the present invention.

The active energy ray-curable composition of the present invention is the silsesquioxane compound (A),
The silsesquioxane compound (A) has an organic group directly bonded to a silicon atom, and at least one of the organic groups directly bonded to the silicon atom is a secondary hydroxyl group, a urethane bond or a urea bond. Having at least one selected from the group consisting of at least one (meth) acryloyloxy group,
Silsesquioxane compound (A) [hereinafter referred to as “component (A)” or “silsesquioxane compound as component (A)”. ], 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 “( B) may be abbreviated as “component” or “reactive particle (B)”. ]
Containing.

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 of the Si—OH group (hydroxysilyl group) is hydrolytically condensed, but the Si—OH group remains. It is also possible to include a silsesquioxane compound having a ladder structure, an incomplete cage structure, or a random condensate.

In the silsesquioxane compound as the component (A), the ratio of the silsesquioxane compound having a structure in which all 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 the silicon atom in the silsesquioxane compound (A). Typically, in the present invention, the silsesquioxane compound (A) contains at least 1 or all of silicon atoms (for example, 90 to 100 mol% with respect to all silicon atoms in component (A)). One (usually one) organic group. At least one of the organic groups directly bonded to the silicon atom is (a-1) at least one selected from the group consisting of a secondary hydroxyl group, a urethane bond and a urea bond, and (a-2) at least one (meth) acryloyl. It has both an oxy group. The ratio of the number of organic groups having the above (a-1) and (a-2) among the number of the organic groups is, for example, 90 to 100% or the total number of the organic groups. The total number of groups may be sufficient. The silsesquioxane compound as the component (A) is excellent in compatibility with the reactive particles (B) and various polymerizable unsaturated compounds by having the organic group, and is a photopolymerizable initiator. It is cured by irradiation with active energy rays in the presence. Therefore, the cured coating film obtained by the active energy ray-curable composition of the present invention is excellent in transparency and scratch resistance. The silsesquioxane compound as the component (A) is excellent in compatibility with various polymerizable unsaturated compounds such as the reactive particles (B) because the silsesquioxane compound as the component (A) is 2 This is presumed to have a functional group or bond having at least one polarity selected from the group consisting of a primary hydroxyl group, a urethane bond and a urea bond.

In this specification, “(meth) acryloyloxy group” means “acryloyloxy group or methacryloyloxy group”. Further, “(meth) acryloyl group” means “acryloyl group or methacryloyl group”. “(Meth) acrylate” means “acrylate or methacrylate”. Further, “(meth) acryloyloxy” means “acryloyloxy or methacryloyloxy”. “(Meth) acrylic acid” means “acrylic acid or methacrylic acid”. “(Meth) acrylamide” means “acrylamide or methacrylamide”.

In the present specification, the secondary hydroxyl group means a hydroxyl group in which two carbon atoms are bonded to the carbon atom to which the hydroxyl group is bonded.

Examples of the silsesquioxane compound as the component (A) include the silsesquioxane compounds represented by the following (A1) and (A2).

(A1): a silsesquioxane compound having an organic group directly bonded to a silicon atom, wherein at least one of the organic groups directly bonded to the silicon atom is at least one secondary hydroxyl group and at least one ( A silsesquioxane compound which is an organic group having both a (meth) acryloyloxy group [hereinafter, abbreviated as “silsesquioxane compound represented by (A1)”. ].

(A2): a silsesquioxane compound having an organic group directly bonded to a silicon atom, wherein at least one of the organic groups directly bonded to the silicon atom is at least one urethane bond and / or urea bond A silsesquioxane compound which is an organic group having both of at least one (meth) acryloyloxy group [hereinafter, abbreviated as “silsesquioxane compound represented by (A2)”. ].

As the silsesquioxane compound which is the component (A), a silsesquioxane compound represented by (A2) is preferable. Since the silsesquioxane compound represented by (A2) is particularly excellent in compatibility with the reactive particles (B) and various polymerizable unsaturated compounds, the silsesquioxane compound represented by (A2) The cured coating film obtained from the active energy ray-curable composition of the present invention using the above has particularly excellent transparency.

Specific examples of the silsesquioxane compound represented by (A2) include silsesquioxane compounds represented by the following (A21) to (A23).

(A21): a silsesquioxane compound having an organic group directly bonded to a silicon atom, wherein at least one of the organic groups directly bonded to the silicon atom is at least one urethane bond and one (meth) A silsesquioxane compound which is an organic group having both an acryloyloxy group and abbreviated as “silsesquioxane compound represented by (A21)”. ].

(A22): a silsesquioxane compound having an organic group directly bonded to a silicon atom, wherein at least one of the organic groups directly bonded to the silicon atom has at least one urea bond and one (meth) A silsesquioxane compound which is an organic group having both an acryloyloxy group [hereinafter, abbreviated as “silsesquioxane compound represented by (A22)”. ].

(A23): a silsesquioxane compound having an organic group directly bonded to a silicon atom, wherein at least one of the organic groups directly bonded to the silicon atom is at least one urethane bond and / or urea bond. A silsesquioxane compound which is an organic group having both of two or more (meth) acryloyloxy groups [hereinafter, abbreviated as “silsesquioxane compound represented by (A23)”. ].

Subsequently, the silsesquioxane compound represented by (A1), the silsesquioxane compound represented by (A21), the silsesquioxane compound represented by (A22), and (A23). The silsesquioxane compound will be described in detail.

First, the silsesquioxane compound represented by (A1) will be described. The silsesquioxane compound represented by the above (A1) has an organic group directly bonded to a silicon atom. At least one of the organic groups directly bonded to the silicon atom is an organic group having both at least one secondary hydroxyl group and at least one (meth) acryloyloxy group.

Examples of the organic group having at least one secondary hydroxyl group and at least one (meth) acryloyloxy group include an organic group represented by the following general formula (A1-I) and the following general formula (A1-II). ). An organic group represented by

[In the formula (A1-I), R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent hydrocarbon group having 1 to 10 carbon atoms. In formula (A1-II), R ¹ and R ² are the same as described above. ].

R ² is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specific examples include alkylene groups such as methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and decanylene group. A cycloalkylene group such as a cyclohexylene group; an arylene group such as a phenylene group or a xylylene group; Among them, a divalent hydrocarbon group having 1 to 6 carbon atoms (more preferably 1 to 3 carbon atoms), particularly an ethylene group or a 1,3-propylene group, has a high scratch resistance and high polarity. It is preferable from the viewpoint that the compatibility with the polymerizable unsaturated compound is more excellent.

The organic group represented by the general formula (A1-I) 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 ¹ is a hydrogen atom and R ² is a 1,3-propylene group is preferable.

The organic group represented by the general formula (A1-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 ¹ is a hydrogen atom and R ² is an ethylene group is preferable.

Next, the silsesquioxane compound represented by (A21) will be described. The silsesquioxane compound represented by the above (A21) has an organic group directly bonded to a silicon atom. At least one of the organic groups directly bonded to the silicon atom is an organic group having both at least one urethane bond and one (meth) acryloyloxy group.

Examples of the organic group having both at least one urethane bond and one (meth) acryloyloxy group include an organic group represented by the following general formula (A21-I).

[In the formula (A21-I), R ³ represents a hydrogen atom or a methyl group. R ⁴ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. R ⁵ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. X ¹ is

(Wherein R ⁴ is the same as defined above, m represents an integer of 0 to 9),

(Wherein R ⁶ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms) or

(Wherein R ⁶ is the same as defined above). ].

Here, the silsesquioxane compound represented by (A21) has one or more types of organic groups among the organic groups represented by the general formula (A21-I). You may do it.

In other words, as the silsesquioxane compound represented by (A21), for example, an organic group having both the at least one urethane bond and one (meth) acryloyloxy group is represented by the following general formula (A21- Examples thereof include silsesquioxane compounds which are at least one selected from the group consisting of organic groups represented by II) to (A21-IV).

[In the formula (A21-II), R ³ represents a hydrogen atom or a methyl group. R ⁴ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. R ⁵ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. m represents an integer of 0 to 9. ]

[In the formula (A21-III), R ³ , R ⁴ , R ⁵ and R ⁶ are the same as defined above. ]

[In the formula (A21-IV), R ³ , R ⁴ , R ⁵ and R ⁶ are the same as defined above. ].

R ⁴ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specific examples include alkylene groups such as methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and decanylene group. A cycloalkylene group such as a cyclohexylene group; an arylene group such as a phenylene group or a xylylene group; Among them, a divalent hydrocarbon group having 1 to 6 carbon atoms, particularly an ethylene group, a 1,2-propylene group, or a 1,4-butylene group, is a polymerizable unsaturated compound having high scratch resistance and high polarity. It is preferable from the viewpoint of more excellent compatibility.

R ⁵ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specific examples include alkylene groups such as methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and decanylene group. A cycloalkylene group such as a cyclohexylene group; an arylene group such as a phenylene group or a xylylene group; Among these, a divalent hydrocarbon group having 1 to 6 carbon atoms (more preferably 1 to 3 carbon atoms), particularly an ethylene group or a 1,3-propylene group, has excellent scratch resistance and high polarizability. It is preferable from the viewpoint of better compatibility with unsaturated compounds.

The m is not particularly limited as long as it is an integer of 0 to 9. m is preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and particularly preferably 0 or 1.

R ⁶ is not particularly limited as long as it is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, neopentyl group, cyclopentyl A non-cyclic aliphatic monovalent hydrocarbon group or a cyclic aliphatic monovalent hydrocarbon group such as a straight chain or branched alkyl group such as a group, n-hexyl group, isohexyl group, cyclohexyl group; trifluoromethyl group, 3, And fluorine-containing alkyl groups such as 3,3-trifluoro-n-propyl group. In particular, a methyl group is preferable from the viewpoint of better compatibility with a highly polar polymerizable unsaturated compound.

The organic group represented by the general formula (A21-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. In view of this, an organic group in which R ³ is a hydrogen atom, R ⁴ is an ethylene group or a 1,4-butylene group, R ⁵ is an ethylene group or a 1,3-propylene group, and m is 0 preferable.

The organic group represented by the general formula (A21-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 ³ is a hydrogen atom, R ⁴ is an ethylene group, R ⁵ is an ethylene group or a 1,3-propylene group, and R ⁶ is a methyl group is preferable.

The organic group represented by the general formula (A21-IV) 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 ³ is a hydrogen atom, R ⁴ is an ethylene group, R ⁵ is an ethylene group or a 1,3-propylene group, and R ⁶ is a methyl group is preferable.

Next, the silsesquioxane compound represented by (A22) will be described. The silsesquioxane compound represented by (A22) has an organic group directly bonded to a silicon atom. At least one of the organic groups directly bonded to the silicon atom is an organic group having both at least one urea bond and one (meth) acryloyloxy group.

As an organic group having both at least one urea bond and one (meth) acryloyloxy group, for example, the following general formula (A22-I)

[In the formula (A22-I), R ⁷ represents a hydrogen atom or a methyl group. X ² represents a divalent organic group having a urea bond. ]
The organic group represented by these is mentioned.

Specific examples of the organic group represented by the general formula (A22-I) include an organic group represented by the following general formula (A22-II).

{In Formula (A22-II), R ⁷ is the same as defined above. R ⁸ is a divalent hydrocarbon group having 1 to 10 carbon atoms or the following general formula (A22-III)

[In the formula (A22-III), R ¹⁰ represents a divalent hydrocarbon group having 2 to 4 carbon atoms. R ¹¹ represents a diisocyanate residue. ]
R ⁹ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. }.

R ⁸ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent group represented by the general formula (A22-III). Specific examples of the divalent hydrocarbon group having 1 to 10 carbon atoms include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1, Examples thereof include alkylene groups such as 4-butylene group, hexylene group and decanylene group; cycloalkylene groups such as cyclohexylene group; arylene groups such as phenylene group and xylylene group. Among these, a divalent hydrocarbon group having 1 to 6 carbon atoms (more preferably 1 to 3 carbon atoms), particularly an ethylene group or a 1,3-propylene group, has excellent scratch resistance and high polarizability. It is preferable from the viewpoint of better compatibility with unsaturated compounds.

R ⁹ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specific examples include alkylene groups such as methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and decanylene group. A cycloalkylene group such as a cyclohexylene group; an arylene group such as a phenylene group or a xylylene group; Among these, a divalent hydrocarbon group having 1 to 6 carbon atoms (more preferably 1 to 3 carbon atoms), particularly an ethylene group or a 1,3-propylene group, has excellent scratch resistance and high polarizability. It is preferable from the viewpoint of better compatibility with unsaturated compounds.

R ¹⁰ is not particularly limited as long as it is a divalent hydrocarbon group having 2 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.

R ¹¹ represents a diisocyanate residue. The diisocyanate residue is a remaining portion obtained by removing two isocyanate groups (NCO) from a diisocyanate compound. Specific examples of the diisocyanate compound include m-phenylene diisocyanate, p-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1, Aromatic diisocyanate compounds such as 5-naphthalene diisocyanate, diphenylmethane-4,4′-diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate; ethane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate , Hexane diisocyanate, heptane diisocyanate, octane diisocyanate, nonane diisocyanate, decane diisocyanate, dicyclohexylmethane diisocyanate, Aliphatic diisocyanate compounds such as isophorone diisocyanate. Of these, aliphatic diisocyanate compounds, particularly isophorone diisocyanate, are preferred from the viewpoint of excellent weather resistance. Further, as the diisocyanate compound, a diisocyanate compound having a molecular weight of 300 or less is preferable from the viewpoint of better scratch resistance and curability of active energy rays in the presence of a photopolymerization initiator.

As the organic group represented by the general formula (A22-II), scratch resistance, compatibility with a highly polar polymerizable unsaturated compound, and active energy ray curability in the presence of a photopolymerization initiator are more excellent. From the viewpoint, an organic group in which R ⁷ is a hydrogen atom, R ⁸ is an ethylene group, and R ⁹ is an ethylene group or a 1,3-propylene group is preferable. Further, R ⁷ is a hydrogen atom, R ⁸ is a divalent group represented by the general formula (A22-III), R ¹⁰ is an ethylene group, and R ¹¹ is an isophorone diisocyanate residue. And an organic group in which R ⁹ is an ethylene group or a 1,3-propylene group.

Next, the silsesquioxane compound represented by (A23) will be described. The silsesquioxane compound represented by the above (A23) has an organic group directly bonded to a silicon atom. At least one of the organic groups directly bonded to the silicon atom is an organic group having both at least one urethane bond and / or urea bond and two or more (meth) acryloyloxy groups.

As the organic group having both at least one urethane bond and / or urea bond and two or more (meth) acryloyloxy groups, for example, the following general formula (A23-I)

[In the formula (A23-I), R ¹² represents a hydrogen atom or a methyl group. n represents an integer of 2 to 5. X ³ represents an (n + 1) -valent organic group having a urethane bond and / or a urea bond. ]
The organic group represented by these is mentioned.

Specific examples of the organic group represented by the general formula (A23-I) include organic groups represented by the following general formula (A23-II) to general formula (A23-V).

{In Formula (A23-II), R ¹² is the same as defined above, and R ¹² may be the same as or different from each other. R ¹³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. R ¹⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms or the following general formula (A23-VI)

[In the formula (A23-VI), R ¹⁶ represents a divalent hydrocarbon group having 2 to 4 carbon atoms, and R ¹⁷ represents a diisocyanate residue. ]
The bivalent group represented by these is shown. In formula (A23-III), R ¹² is the same as defined above, and R ¹² may be the same or different. R ¹³ is the same as described above. R ¹⁴ is the same as described above. In formula (A23-IV), R ¹² is the same as defined above, and R ¹² may be the same or different. R ¹³ is the same as described above. R ¹⁴ is the same as above, and each R ¹⁴ may be the same or different. In the formula (A23-V), p represents an integer of 1 to 3. R ¹² is the same as described above, and R ¹² may be the same or different. R ¹³ is the same as described above. R ¹⁴ is the same as above, and each R ¹⁴ may be the same or different. R ¹⁵ represents a (p + 1) -valent hydrocarbon group having 1 to 10 carbon atoms. }.

R ¹³ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specific examples include alkylene groups such as methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and decanylene group. A cycloalkylene group such as a cyclohexylene group; an arylene group such as a phenylene group or a xylylene group; Among these, a divalent hydrocarbon group having 1 to 6 carbon atoms (more preferably 1 to 3 carbon atoms), particularly an ethylene group or a 1,3-propylene group, has excellent scratch resistance and high polarizability. It is preferable from the viewpoint of better compatibility with unsaturated compounds.

R ¹⁴ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent group represented by the general formula (A23-VI). Specific examples of the divalent hydrocarbon group having 1 to 10 carbon atoms include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1, Examples thereof include alkylene groups such as 4-butylene group, hexylene group and decanylene group; cycloalkylene groups such as cyclohexylene group; arylene groups such as phenylene group and xylylene group. Among these, a divalent hydrocarbon group having 1 to 6 carbon atoms (more preferably 1 to 3 carbon atoms), particularly an ethylene group or a 1,3-propylene group, has excellent scratch resistance and high polarizability. It is preferable from the viewpoint of better compatibility with unsaturated compounds.

R ¹⁶ is not particularly limited as long as it is a divalent hydrocarbon group having 2 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.

R ¹⁷ represents a diisocyanate residue. The diisocyanate residue is a remaining portion obtained by removing two isocyanate groups (NCO) from a diisocyanate compound. Specific examples of the diisocyanate compound include m-phenylene diisocyanate, p-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1, Aromatic diisocyanate compounds such as 5-naphthalene diisocyanate, diphenylmethane-4,4′-diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate; ethane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, Heptane diisocyanate, octane diisocyanate, nonane diisocyanate, decane diisocyanate, dicyclohexylmethane diisocyanate, Aliphatic diisocyanate compounds such as isophorone diisocyanate. Of these, aliphatic diisocyanate compounds, particularly isophorone diisocyanate, are preferred from the viewpoint of excellent weather resistance. Moreover, as a diisocyanate compound, the diisocyanate compound of molecular weight 300 or less is preferable from the point which is more excellent in abrasion resistance and active energy ray curability.

R ¹⁵ is not particularly limited as long as it is a (p + 1) -valent hydrocarbon group having 1 to 10 carbon atoms. The (p + 1) -valent hydrocarbon group for R ¹⁵ is a hydroxymonocarboxylic acid residue. The hydroxy monocarboxylic acid residue is the remaining part obtained by removing the hydroxyl group and the carboxyl group from the hydroxy monocarboxylic acid. Specific examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a 1,2-butylene group, and a 1,4-butylene group. And alkylene groups such as xylene group and decanylene group; cycloalkylene groups such as cyclohexylene group; and arylene groups such as phenylene group and xylylene group. Specific examples of the hydroxy monocarboxylic acid include hydroxypivalic acid, glycolic acid, lactic acid, 3-hydroxypropionic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyisobutyric acid, 2 -Hydroxy-2-methylpropionic acid, 3-hydroxyvaleric acid, 5-hydroxyvaleric acid, 2-hydroxycyclohexanecarboxylic acid, dimethylolpropionic acid, dimethylolbutanoic acid, o-hydroxybenzoic acid, m-hydroxybenzoic acid, Examples thereof include p-hydroxybenzoic acid. Of these, dimethylolpropionic acid and dimethylolbutanoic acid are preferred from the viewpoint of better scratch resistance and active energy ray curability.

The organic group represented by the general formula (A23-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 ¹² is a hydrogen atom, R ¹³ is an ethylene group or a 1,3-propylene group, and R ¹⁴ is an ethylene group is preferable. R ¹² is a hydrogen atom, R ¹³ is an ethylene group or a 1,3-propylene group, R ¹⁴ is a divalent group represented by the general formula (A23-VI), and R ¹⁶ An organic group in which is a divalent group in which is an ethylene group and R ¹⁷ is an isophorone diisocyanate residue is preferred.

The organic group represented by the general formula (A23-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 ¹² is a hydrogen atom, R ¹³ is an ethylene group or a 1,3-propylene group, and R ¹⁴ is an ethylene group is preferable. R ¹² is a hydrogen atom, R ¹³ is an ethylene group or a 1,3-propylene group, R ¹⁴ is a divalent group represented by the general formula (A23-VI), and R ¹⁶ An organic group in which is a divalent group in which is an ethylene group and R ¹⁷ is an isophorone diisocyanate residue is preferred.

The organic group represented by the general formula (A23-IV) 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 ¹² is a hydrogen atom, R ¹³ is an ethylene group or a 1,3-propylene group, and R ¹⁴ is an ethylene group is preferable. R ¹² is a hydrogen atom, R ¹³ is an ethylene group or a 1,3-propylene group, R ¹⁴ is a divalent group represented by the general formula (A23-VI), and R ¹⁶ An organic group in which is a divalent group in which is an ethylene group and R ¹⁷ is an isophorone diisocyanate residue is preferred.

The organic group represented by the general formula (A23-V) 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. In view of this, p is 2, R ¹² is a hydrogen atom, R ¹³ is an ethylene group or a 1,3-propylene group, R ¹⁴ is an ethylene group, and R ¹⁵ is a dimethylolpropionic acid residue. Certain organic groups are preferred. In addition, p is 2, R ¹² is a hydrogen atom, R ¹³ is an ethylene group or a 1,3-propylene group, and R ¹⁴ is a divalent group represented by the general formula (A23-VI). And an organic group in which R ¹⁶ is an ethylene group, R ¹⁷ is a divalent group that is an isophorone diisocyanate residue, and R ¹⁵ is a dimethylolpropionic acid residue.

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 the weight average molecular weight is 1,000 to 10,000. These ranges are significant in terms of the viscosity and paintability of the active energy ray-curable composition of the present invention.

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 mass%. . The weight average molecular weight was determined by measuring the light scattering intensity of these 10 samples.

Production method of silsesquioxane compound as component (A) The silsesquioxane compound as component (A) can be produced by various methods. An example is shown below.

Manufacturing method a
Production method a is a hydrolyzable silane having an organic group directly bonded to a silicon atom, and the organic group is at least one selected from the group consisting of a secondary hydroxyl group, a urethane bond, and a urea bond. And a production method using a starting material containing a hydrolyzable silane having both one and at least one (meth) acryloyloxy group.

Manufacturing method b
The production method b includes a step of producing a silsesquioxane compound having a functional group using a hydrolyzable silane having a functional group such as an epoxy group, an amino group, an isocyanate group, and the silyl obtained by the step. The manufacturing method which has the process of reacting a sesquioxane compound, the compound which has a (meth) acryloyl group and a functional group, and manufacturing the silsesquioxane compound which has a desired organic group is mentioned.

Moreover, as another example of the manufacturing method b, the process (i) which manufactures the silsesquioxane compound which has a functional group using hydrolyzable silane which has functional groups, such as an epoxy group, an amino group, and an isocyanate group, If necessary, the silsesquioxane compound obtained in this step and the compound having a functional group are reacted to generate a new functional group (ii) and the silsesquioxane obtained in step (i). Silsesquioxane compound having a desired organic group by reacting a functional group of an oxan compound or a functional group newly generated by the step (ii) with a functional group of a compound having a (meth) acryloyl group and a functional group The manufacturing method which has the process (iii) which manufactures is mentioned.

These manufacturing methods will be described in detail with specific examples.

First, a silsesquioxane compound as component (A), wherein at least one of organic groups directly bonded to a silicon atom has an organic group represented by the following general formula (A1-I) Compound [hereinafter sometimes referred to as “silsesquioxane compound having an organic group represented by the general formula (A1-I)”. ] Is exemplified.

[In the formula (A1-I), R ¹ and R ² are the same as defined above. ].

The following manufacturing method corresponds to the manufacturing method b. In this production method, the following general formula (A1-I-1) is used as a starting material.

[In the formula (A1-I-1), R ² is the same as defined above. Y is chlorine or an alkoxy group having 1 to 6 carbon atoms, and Y may be the same or different. ]
Is hydrolyzed and condensed in the presence of a catalyst using a hydrolyzable silane represented by the following general formula (A1-I-2)

[In the formula (A1-I-2), R ² is the same as defined above. ]
The silsesquioxane compound which has an organic group represented by these is manufactured.

Specific examples of Y in the general formula (A1-I-1) include chlorine, methoxy group, ethoxy group, propoxy group, butoxy group and the like.

Specific examples of the hydrolyzable silane represented by the general formula (A1-I-1) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like. .

In order to obtain a silsesquioxane compound having an organic group represented by the general formula (A1-I-2), specifically,
[1] Hydrolytic condensation using the hydrolyzable silane represented by the general formula (A1-I-1) as a starting material in the presence of a catalyst, or
[2] Hydrolysis in the presence of a catalyst using a hydrolyzable silane represented by the general formula (A1-I-1) and a hydrolyzable silane other than a hydrolyzable silane having an epoxy group as a starting material Condensing.

As the hydrolyzable silane other than the hydrolyzable silane having an epoxy group, a silsesquioxane compound is produced by hydrolytic condensation together with the hydrolyzable silane represented by the general formula (A1-I-1). There is no particular limitation as long as it is possible. 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.

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. However, if the amount is too large, there are problems such as high cost and difficulty in removal. On the other hand, if the amount is too small, the reaction becomes slow. Therefore, the amount of the catalyst used is preferably in the range of 0.0001 to 1.0 mol, more preferably 0.0005 to 0.1 mol, relative to 1 mol of hydrolyzable silane.

When hydrolytic condensation is performed (in the case of [1] or [2] above), water is used. The quantity ratio of hydrolyzable silane and water is not particularly limited. The amount of water used is preferably a ratio of 0.1 to 100 mol, more preferably 0.5 to 3 mol, of water relative to 1 mol of hydrolyzable silane. If the amount of water is too small, the reaction may be slowed and the yield of the desired silsesquioxane may be reduced. If the amount of water is too large, the molecular weight will increase and the product of the desired structure will decrease. There is a risk. 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 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, a lower alcohol solvent such as methanol, ethanol and 2-propanol, a ketone solvent such as acetone and methyl isobutyl ketone, and an ether solvent such as tetrahydrofuran are used. Particularly, acetone and tetrahydrofuran have a low boiling point. Is preferable because it becomes 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.

The reaction temperature during the hydrolysis condensation is 0 to 200 ° C., preferably 10 to 200 ° C., more preferably 10 to 120 ° C. The reaction is usually completed in about 1 to 12 hours.

In the hydrolysis-condensation reaction, the condensation reaction proceeds together with the hydrolysis, and most of the hydrolyzable group of the hydrolyzable silane [specifically, for example, most of Y in the general formula (A1-I-1)], preferably 100% is hydrolyzed to hydroxyl groups (OH groups), and most of the OH groups, preferably 80% or more, more preferably 90% or more, particularly preferably 100% is condensed to be liquid stable. It is preferable from the point.

Specific examples of the silsesquioxane compound having an organic group represented by the general formula (A1-I-2) include Glycylyl POSS cage mixture (trade name, Hybrid Plastics).

Subsequently, the silsesquioxane compound having an organic group represented by the general formula (A1-I-2) produced above is added to the following general formula (A1-I-3).

[In the formula (A1-I-3), R ¹ is the same as defined above. ]
To produce a silsesquioxane compound having an organic group represented by the general formula (A1-I).

Examples of the compound represented by the general formula (A1-I-3) include acrylic acid and methacrylic acid.

The reaction can be performed according to a conventional method in which an epoxy group and a carboxyl group are reacted. The reaction temperature is, for example, 0 to 200 ° C, preferably 20 to 200 ° C, more preferably 20 to 120 ° C. The reaction is usually completed in about 10 to 24 hours.

The ratio of the silsesquioxane compound having an organic group represented by the general formula (A1-I-2) and the compound represented by the general formula (A1-I-3) in the reaction is as follows. The compound represented by the general formula (A1-I-3) is usually used in an amount of 0.80 to 1.20 mol per 1 mol of the organic group represented by the general formula (A1-I-2) of the oxan compound. About 0.90 to 1.10 mol.

In the above reaction, a catalyst may be used as appropriate. Specific examples of the catalyst include tertiary amines such as triethylamine and benzyldimethylamine; quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium bromide and tetrabutylammonium bromide; acetates and formates such as diethylamine Secondary amine salts of sodium hydroxide, alkali metal hydroxides such as sodium hydroxide and calcium hydroxide; alkali metal and alkaline earth metal salts such as sodium acetate and calcium acetate; imidazole compounds; diaza Examples thereof include cyclic nitrogen-containing compounds such as bicycloundecene and phosphorus compounds such as triphenylphosphine and tributylphosphine. The amount of the catalyst used is not particularly limited, but is 0.01 to 5% by mass with respect to the reaction raw material.

In the above reaction, a solvent may be appropriately used. The solvent is not particularly limited. Specifically, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, ethyl isoamyl ketone, diisobutyl ketone, methyl hexyl ketone; ethyl acetate, butyl acetate, methyl benzoate, methyl propionate, etc. Ester solvents such as tetrahydrofuran, dioxane and dimethoxyethane; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; Aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents and the like can be mentioned.

The silsesquioxane compound having an organic group represented by the general formula (A1-I) is produced by the above production method.

The target compound obtained by the above reactions can be separated from the reaction system by ordinary separation means and further purified. As this separation and purification means, for example, distillation method, solvent extraction method, dilution method, recrystallization method, column chromatography, ion exchange chromatography, gel chromatography, affinity chromatography and the like can be used.

Here, when 100% condensation is not performed in the hydrolysis condensation, the product obtained by this production method includes a silsesquioxane compound having a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed. In addition, there may be included a ladder structure in which a Si—OH group remains, an incomplete cage structure, and / or a silsesquioxane compound of a random condensate, but the general formula (A1-I) obtained by this production method may be included. The silsesquioxane compound having an organic group represented by (II) may contain a ladder structure, an incomplete cage structure and / or a random condensate. The silsesquioxane compound having an organic group represented by the general formula (A1-I) obtained by this production method is a ratio of the silsesquioxane compound having a structure in which all Si—OH groups are hydrolyzed and condensed. However, it is preferably 80% by mass or more, more preferably 90% by mass or more from the viewpoint of liquid stability.

Next, a silsesquioxane compound (A) is a silsesquioxane compound in which at least one of organic groups directly bonded to a silicon atom has an organic group represented by the following general formula (A21-II) Sun compound [hereinafter sometimes abbreviated as “silsesquioxane compound having an organic group represented by formula (A21-II)”. ] Is exemplified.

[In the formula (A21-II), R ³ , R ⁴ , R ⁵ and m are the same as defined above. ].

The following manufacturing method corresponds to the manufacturing method a. In this production method, the following general formula (A21-II-1) is used as a starting material.

[In the formula (A21-II-1), R ³ , R ⁴ , R ⁵ , m and Y are the same as defined above. Y may be the same or different. ]
And hydrolyzable silane other than the hydrolyzable silane represented by the general formula (A21-II-1), if necessary, in the presence of a catalyst. And a silsesquioxane compound having an organic group represented by the general formula (A21-II) is produced.

The hydrolyzable silane other than the hydrolyzable silane represented by the general formula (A21-II-1) is hydrolyzed and condensed together with the hydrolyzable silane represented by the general formula (A21-II-1). If it can manufacture a silsesquioxane compound by this, it will not specifically limit. 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.

Examples of the hydrolyzable silane represented by the general formula (A21-II-1) include a hydrolyzable silane represented by the following general formula (A21-II-2) and a general formula (A21-II- It can be obtained by reacting with the compound represented by 3).

[In the formula (A21-II-2), R ⁵ and Y are the same as defined above. Y may be the same or different. ].

[In the formula (A21-II-3), R ³ , R ⁴ and m are the same as defined above. ].

Examples of the compound represented by the general formula (A21-II-2) include 3-isocyanatopropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane.

Examples of the compound represented by the general formula (A21-II-3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy Examples include butyl (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 (A21-II-2) and the compound represented by the general formula (A21-II-3) is performed according to a conventional method in which an isocyanate group and a hydroxyl group are reacted. It can be carried out.

The proportion of the hydrolyzable silane represented by the general formula (A21-II-2) and the compound represented by the general formula (A21-II-3) in the reaction is usually the latter with respect to 1 mol of the former. The amount may be about 0.90 to 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. This reaction can be carried out regardless of pressure, but a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferred. The reaction is usually completed in about 2 to 10 hours.

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

In the above reaction, a solvent may be appropriately used. Specific examples of the solvent include ketone solvents 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, Ester solvents such as methyl propionate; Ether solvents such as tetrahydrofuran, dioxane and dimethoxyethane; Glycol ether solvents such as propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; Aromatic hydrocarbon solvents such as toluene and xylene And aliphatic hydrocarbon solvents.

In this production method, in order to obtain a silsesquioxane compound having an organic group represented by the general formula (A21-II), specifically,
[3] Hydrolytic condensation using the hydrolyzable silane represented by the general formula (A21-II-1) as a starting material in the presence of a catalyst, or [4] the general formula (A21-II-1 ) And a hydrolyzable silane other than the hydrolyzable silane represented by the general formula (A21-II-1) as a starting material, and hydrolytic condensation in the presence of a catalyst. Can be mentioned.

In this hydrolysis condensation, the catalyst, the amount of catalyst used, the amount of water used, the type of organic solvent in the case of using an organic solvent, the reaction temperature and reaction time during the hydrolysis condensation are the above-mentioned general formulas (A1-I). The same conditions as those used in the production of the silsesquioxane compound having an organic group represented by -2) can be applied.

In the hydrolysis-condensation reaction, the condensation reaction proceeds together with the hydrolysis, and most of the hydrolyzable group of the hydrolyzable silane [specifically, for example, most of Y in the general formula (A21-II-1)], preferably 100% is hydrolyzed to hydroxyl groups (OH groups), and most of the OH groups, preferably 80% or more, more preferably 90% or more, particularly preferably 100% is condensed to be liquid stable. It is preferable from the point.

The silsesquioxane compound having an organic group represented by the general formula (A21-II) is produced by the above production method.

Here, when 100% condensation is not performed in the hydrolysis condensation, the product obtained by this production method includes a silsesquioxane compound having a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed. In addition, there may be included a ladder structure in which Si—OH groups remain, an incomplete cage structure, and / or a silsesquioxane compound of a random condensate, but the general formula (A21-II) obtained by this production method may be included. The silsesquioxane compound having an organic group represented by (II) may contain a ladder structure, an incomplete cage structure and / or a random condensate. The silsesquioxane compound having an organic group represented by the general formula (A21-II) obtained by this production method is a ratio of the silsesquioxane compound having a structure in which all Si—OH groups are hydrolyzed and condensed. However, it is preferably 80% by mass or more, more preferably 90% by mass or more from the viewpoint of liquid stability.

Next, a silsesquioxane compound (A), which is a silsesquioxane compound in which at least one of organic groups directly bonded to a silicon atom has an organic group represented by the following general formula (A22-II): Sun compound [hereinafter sometimes referred to as “silsesquioxane compound having an organic group represented by the general formula (A22-II)”. ] Is exemplified.

[In the formula (A22-II), R ⁷ , R ⁸ and R ⁹ are the same as defined above. ].

The following manufacturing method corresponds to the manufacturing method b. In this production method, the following general formula (A22-II-1) is used as a starting material.

[In the formula (A22-II-1), R ⁹ and Y are the same as defined above. Y may be the same or different. ]
The following general formula (A22-II-2) is obtained by performing hydrolytic condensation in the presence of a catalyst using a hydrolyzable silane represented by

[In the formula (A22-II-2), R ⁹ is the same as defined above. ]
The silsesquioxane compound which has an organic group represented by these is manufactured.

Specific examples of the hydrolyzable silane represented by the general formula (A22-II-1) include aminomethyltrimethoxysilane, aminomethyltriethoxysilane, 2-aminoethyltrimethoxysilane, and 2-amino. Examples include ethyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane.

In order to obtain a silsesquioxane compound having an organic group represented by the general formula (A22-II-2), specifically,
[5] Hydrolytic condensation using the hydrolyzable silane represented by the general formula (A22-II-1) as a starting material in the presence of a catalyst, or
[6] Hydrolysis in the presence of a catalyst using a hydrolyzable silane represented by the general formula (A22-II-1) and a hydrolyzable silane other than a hydrolyzable silane having an amino group as a starting material. Condensing.

The hydrolyzable silane other than the hydrolyzable silane having an amino group is particularly limited as long as it can produce a silsesquioxane compound by hydrolytic condensation together with the hydrolyzable silane having the amino group. It is not a thing. 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.

In the hydrolysis-condensation reaction, the condensation reaction proceeds together with the hydrolysis, and a hydrolyzable group of the hydrolyzable silane [specifically, for example, most of Y in the general formula (A22-II-1)], preferably 100% is hydrolyzed to hydroxyl groups (OH groups), and most of the OH groups, preferably 80% or more, more preferably 90% or more, particularly preferably 100% is condensed to be liquid stable. It is preferable from the point.

Subsequently, the amino group of the silsesquioxane compound having the organic group represented by the general formula (A22-II-2) produced above is represented by the following general formula (A22-II-3). The isocyanate group of the compound is reacted to produce a silsesquioxane compound having an organic group represented by the general formula (A22-II).

[In the formula (A22-II-3), R ⁷ and R ⁸ are the same as defined above. ].

Specific examples of the compound represented by the general formula (A22-II-3) include, for example, isocyanate methyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, and isocyanate. Examples include octyl (meth) acrylate. Moreover, the adduct of a hydroxyl group containing (meth) acrylate and a diisocyanate compound is mentioned. Specific examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth). An acrylate etc. are mentioned. Specific examples of the diisocyanate compound include m-phenylene diisocyanate, p-phenylene diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1, Aromatic diisocyanate compounds such as 5-naphthalene diisocyanate, diphenylmethane-4,4′-diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate; ethane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, Heptane diisocyanate, octane diisocyanate, nonane diisocyanate, decane diisocyanate, dicyclohexylmethane diisocyanate , Aliphatic diisocyanate compounds such as isophorone diisocyanate.

The reaction is usually performed using 1 mol or more of the compound represented by the general formula (A22-II-3) per 1 mol of the organic group represented by the general formula (A22-II-2). Is called.

The 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. This reaction can be carried out regardless of pressure, but a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferred. The reaction is very fast and usually completes when the dropping is completed.

In the above reaction, a solvent may be appropriately used. Specific examples of the solvent include ester solvents such as ethyl acetate, butyl acetate, methyl benzoate and methyl propionate; ether solvents such as tetrahydrofuran, dioxane and dimethoxyethane; propylene glycol monomethyl ether and propylene glycol monomethyl ether. Examples thereof include glycol ether solvents such as acetate and 3-methoxybutyl acetate; alcohol solvents such as methanol, ethanol and propanol, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents and the like.

The silsesquioxane compound having an organic group represented by the general formula (A22-II) is produced by the above production method.

Here, when 100% condensation is not performed in the hydrolysis condensation, the product obtained by this production method includes a silsesquioxane compound having a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed. In addition, there may be included a ladder structure in which Si—OH groups remain, an incomplete cage structure and / or a silsesquioxane compound of a random condensate, but the general formula (A22-II) obtained by this production method may be included. The silsesquioxane compound having an organic group represented by (II) may contain a ladder structure, an incomplete cage structure and / or a random condensate. The silsesquioxane compound having an organic group represented by the general formula (A22-II) obtained by this production method is a ratio of the silsesquioxane compound having a structure in which all Si—OH groups are hydrolyzed and condensed. However, it is preferably 80% by mass or more, more preferably 90% by mass or more from the viewpoint of liquid stability.

Next, a silsesquioxane compound (A), which is a silsesquioxane compound in which at least one organic group directly bonded to a silicon atom has an organic group represented by the following general formula (A23-II): Sun compound [hereinafter sometimes referred to as “silsesquioxane compound having an organic group represented by formula (A23-II)”. ] Is exemplified.

[In the formula (A23-II), R ¹² , R ¹³ and R ¹⁴ are the same as defined above. ].

The following manufacturing method corresponds to the manufacturing method b. In this production method, the following general formula (A23-II-1) is used as a starting material.

[In the formula (A23-II-1), R ¹³ and Y are the same as defined above. Y may be the same or different. ]
And hydrolyzable silane other than the hydrolyzable silane represented by the general formula (A23-II-1), if necessary, in the presence of a catalyst. The following general formula (A22-II-2)

[In the formula (A23-II-2), R ¹³ is the same as defined above. ]
The silsesquioxane compound which has an organic group represented by these is manufactured.

Specific examples of the hydrolyzable silane represented by the general formula (A23-II-1) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like. .

In order to obtain a silsesquioxane compound having an organic group represented by the general formula (A23-II-2), specifically,
[7] The hydrolyzable silane represented by the general formula (A23-II-1) is used as a starting material for hydrolysis condensation in the presence of a catalyst, or
[8] Hydrolysis in the presence of a catalyst using a hydrolyzable silane represented by the general formula (A23-II-1) and a hydrolyzable silane other than a hydrolyzable silane having an epoxy group as a starting material Condensing.

As the hydrolyzable silane other than the hydrolyzable silane having an epoxy group, a silsesquioxane compound is produced by hydrolytic condensation together with the hydrolyzable silane represented by the general formula (A23-II-1). There is no particular limitation as long as it is possible. 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.

In the hydrolysis-condensation reaction, the condensation reaction proceeds together with the hydrolysis, and a hydrolyzable group of the hydrolyzable silane [specifically, for example, most of Y in the general formula (A23-II-1)], preferably 100% is hydrolyzed to hydroxyl groups (OH groups), and most of the OH groups, preferably 80% or more, more preferably 90% or more, particularly preferably 100% is condensed to be liquid stable. It is preferable from the point.

Specific examples of the silsesquioxane compound having an organic group represented by the general formula (A23-II-2) include Glycylyl POSS cage mixture (trade name, Hybrid Plastics).

Subsequently, the silsesquioxane compound having an organic group represented by the general formula (A23-II-2) produced above is added to the following general formula (A23-II-3).

[In the formula (A23-II-3), R ¹² is the same as defined above. ]
And a compound represented by the following general formula (A23-II-4)

[In the formula (A23-II-4), R ¹² and R ¹³ are the same as defined above. ]
The silsesquioxane compound which has an organic group represented by these is manufactured.

Examples of the compound represented by the general formula (A23-II-3) include acrylic acid and methacrylic acid.

The reaction can be performed according to a conventional method in which an epoxy group and a carboxyl group are reacted. In this reaction, various reaction conditions such as a reaction temperature, a use ratio, a reaction time, a catalyst, and a solvent can be used for the silsesquioxane compound having an organic group represented by the general formula (A1-I-2). The same conditions as various reaction conditions for reacting the compound represented by the general formula (A1-I-3) can be applied.

Subsequently, the compound represented by the following general formula (A23-II-5) is added to the secondary hydroxyl group of the silsesquioxane compound having the organic group represented by (A23-II-4) produced above. The isocyanate group is reacted.

[In the formula (A23-II-5), R ¹² and R ¹⁴ are the same as defined above. ].

The reaction can be performed according to a conventional method in which a hydroxyl group and an isocyanate group are reacted. The reaction temperature is, for example, 0 to 200 ° C., preferably 10 to 200 ° C., more preferably 10 to 120 ° C. The reaction is usually completed in about 2 to 10 hours.

The ratio of the silsesquioxane compound having an organic group represented by the general formula (A23-II-4) and the compound represented by the general formula (A23-II-5) in the above reaction is as follows. The compound represented by the general formula (A23-II-5) is usually used in an amount of 0.90 to 1.10 mol per 1 mol of the organic group represented by the general formula (A23-II-4) of the oxan compound. About 0.95 to 1.05 mol.

The silsesquioxane compound having an organic group represented by the general formula (A23-II) is produced by the above production method.

Here, when 100% condensation is not performed in the hydrolysis condensation, the product obtained by this production method includes a silsesquioxane compound having a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed. May include a ladder structure in which Si—OH groups remain, an incomplete cage structure, and / or a silsesquioxane compound of a random condensate. The general formula (A23-II) obtained by this production method may be included. The silsesquioxane compound which has an organic group represented by these may contain those ladder structures, incomplete cage structures, and / or random condensates. The silsesquioxane compound having an organic group represented by the general formula (A23-II) obtained by this production method is a ratio of the silsesquioxane compound having a structure in which all Si—OH groups are hydrolyzed and condensed. However, it is preferably 80% by mass or more, more preferably 90% by 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 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 to 80 parts by mass, and particularly preferably 15 to 50 parts by mass.

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, diacetone alcohol; and monomer compounds 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.

Colloidal silica fine particles include 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 having (meth) acryloyloxy group in the molecule (b-2)
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. A halogen atom includes chlorine.

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 the formula (BI), Z represents a (meth) acryloyloxy group. R ¹⁸ 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) represented by the formula [hereinafter sometimes referred to as “compound (b-2-1)”. ].

R ¹⁸ 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, ethoxy group, propoxy group, butoxy group, 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, ethyl group, propyl group, butyl group, 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) ". ].

As the hydrolyzable silane having both a (meth) acryloyloxy group and a urethane bond in the molecule, for example, the following general formula (B-II)

[In the formula (B-II), R ¹⁹ represents a hydrogen atom or a methyl group. R ²⁰ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. R ²¹ 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. q represents an integer of 1 to 10. ]
The hydrolyzable silane represented by these is mentioned.

R ²⁰ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specifically, for example, an alkylene group such as methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group; cyclohexylene group And aralkylene groups such as a phenylene group and a xylylene group. Of these, a divalent hydrocarbon group having 1 to 6 carbon atoms, particularly an ethylene group, a 1,2-propylene group, and a 1,4-butylene group are preferable.

R ²¹ is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specifically, for example, an alkylene group such as methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group; cyclohexylene group And aralkylene groups such as a phenylene group and a xylylene group. Of these, a divalent hydrocarbon group having 1 to 6 carbon atoms, particularly an ethylene group and a 1,3-propylene group are preferable.

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

Examples of the hydrolyzable silane represented by the general formula (B-II) include 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 ²¹ , R ^a , R ^b and R ^c are the same as defined above. ]

[In the formula (B-IV), R ¹⁹ , R ²⁰ and q are the same as defined above. Examples of the hydrolyzable silane represented by the general formula (B-III) include 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.

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. .

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

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 having the formula [hereinafter sometimes referred to as “compound (b-2-3)”. ].

Examples of hydrolyzable silanes having both a (meth) acryloyloxy group and an isocyanurate ring structure in the molecule include, for example, the following general formula (BV)

[In the formula (BV), R ²² are the same or different and each represents a hydrogen atom or a methyl group. R ²³ is the same or different and represents a divalent organic group. R ²⁴ 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 hydrolyzable silane represented by these is mentioned.

R ²³ is not particularly limited as long as it is a divalent organic group. Examples of the divalent organic group include divalent organic groups having 1 to 100 carbon atoms. A divalent organic group having 1 to 30 carbon atoms is preferred. 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 ²⁴ is not particularly limited as long as it is a divalent organic group. Examples of the divalent organic group include divalent organic groups having 1 to 100 carbon atoms. A divalent organic group having 1 to 30 carbon atoms is preferred. 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.

Specific examples of the hydrolyzable silane represented by the general formula (BV) include hydrolyzable silanes represented by the following general formula (B-VI) and the following general formula (B-VII). ) Represented by a hydrolyzable silane.

[In the formula (B-VI), R ²⁵ are the same or different and each represents a hydrogen atom or a methyl group. R ²⁶ is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. R ²⁷ represents a divalent hydrocarbon group having 1 to 4 carbon atoms. r 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 ²⁸ are the same or different and each represents a hydrogen atom or a methyl group. R ²⁹ is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. R ³⁰ 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 ²⁶ 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. Among these, a divalent hydrocarbon group having 2 to 4 carbon atoms, particularly an ethylene group is preferable from the viewpoint of transparency of the resulting cured coating film.

R ²⁷ 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 ²⁵ 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 ²⁶ is an ethylene group, R ²⁷ is a 1,3-propylene group, and an organic group in which r is 0 is preferable.

R ²⁹ 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. Among these, a divalent hydrocarbon group having 2 to 4 carbon atoms, particularly an ethylene group is preferable from the viewpoint of transparency of the resulting cured coating film.

R ³⁰ 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 (B-VII) 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 ²⁸ is a hydrogen atom, R ²⁹ is an ethylene group, and R ³⁰ is a 1,3-propylene group is preferable.

An example of a method for producing a hydrolyzable silane represented by the above general formula (B-VI) 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.

In the general formula (B-VIII), R ²⁷ , R ^a , R ^b and R ^c are the same as described above.

In the general formula (B-IX), R ²⁵ , R ²⁶ and r 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 equimolar amounts 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. This reaction can be carried out regardless of pressure, but a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferred.

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

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). Obtainable.

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.), Duranate. Examples thereof include TPA100 (manufactured by Asahi Kasei Chemicals Corporation).

In the general formula (B-XI), R ²⁵ , R ²⁶ and r are the same as described above. Examples of the compound represented by the general formula (B-XI) include compounds in which r is 0, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl ( And (meth) acrylate and 4-hydroxybutyl (meth) acrylate. Examples of the compound in which r is 1 to 5 include caprolactone-modified hydroxyalkyl (meth) acrylate. Specifically, as product names, “Placcel FA-1”, “Placcel FA-2”, “Placcel FA-2D”, “Placcel FA-3”, “Placcel FA-4”, “Placcel FA-5” , “Placcel FM-1,” “Placcel FM-2,” “Placcel FM-2D,” “Placcel FM-3,” “Placcel FM-4,” “Placcel FM-5” (all manufactured by Daicel Chemical Industries, Ltd.) 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 carried out 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. This reaction can be carried out regardless of pressure, but a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferred. The reaction is usually completed in about 2 to 10 hours.

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 above general formula (B-IX). In addition to the compound represented by formula (B-XII)

[In the formula (B-XII), R ²⁵ , R ²⁶ and r are the same as defined above. ]
May be included.

Then, when producing the hydrolyzable silane represented by the general formula (B-VI), and using the hydrolyzable silane represented by the general formula (B-VI), the reactive particles (B) In production, there is no particular problem even if the compound represented by the general formula (B-XII) is contained in the raw material for the production.

Subsequently, a method for producing a hydrolyzable silane represented by the general formula (B-VII) will be exemplified. 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.

In the general formula (B-XIII), R ³⁰ , R ^a , R ^b and R ^c are the same as described above.

R ²⁸ and R ^{29 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. 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 an equimolar amount 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.

The compound represented by the general formula (B-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 (B-XV) such as acryloyloxyethyl) isocyanurate, tris (2-acryloyloxypropyl) isocyanurate

[In the formula (B-XV), R ²⁸ and R ²⁹ are the same as defined above. ]
It is sold as a mixture with a compound represented by

Then, when producing the hydrolyzable silane represented by the general formula (B-VII), and using the hydrolyzable silane represented by the general formula (B-VII), the reactive particles (B) In production, there is no particular problem even if the compound represented by the general formula (B-XV) is contained in the raw material for the production.

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-2-2) and the compound (b-2-3) are used in combination. It is preferable to use the compound (b-2-1) and the compound (b-2-3) 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) / compound (b-2-3) = 10/90 to 90/10 (mass ratio), preferably 20/80 to 50/50 (mass ratio). More preferred.

In addition to the compound (b-2), when obtaining the reactive particles (B), an alkoxysilane having an alkyl group having 1 or more carbon atoms is optionally added together with the compound (b-2) to silica fine particles (b- You may make it react with 1). By reacting the alkoxysilane having an alkyl group having 1 or more carbon atoms, the water resistance of the coating film obtained using the obtained reactive particles (B) may be improved. Examples of the alkoxysilane having an alkyl group having 1 or more carbon atoms include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, and dodecyltrimethoxy. Silane etc. are mentioned, The compound (for example, methyltriethoxysilane etc.) which substituted the methoxy group in these illustrated compounds by the ethoxy group is also mentioned.

The reactive particles (B) can be 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 compound (b-2) with silica fine particles (b-1) after hydrolyzing compound (b-2), [iii] silica fine particles (b-1) and compound ( and b-2) may be mixed in the presence of water, an organic solvent, and other components such as a polymerizable unsaturated compound, and hydrolytic 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 a 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 as the 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 carried out with stirring for 0.5 to 10 hours at a temperature of preferably 80 to 130 ° C. and usually 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 hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and cyclohexane; halogenated hydrocarbon solvents such as trichloroethylene and tetrachloroethylene; 1,4-dioxane, dibutyl ether Ether solvents such as methyl isobutyl ketone; ester solvents such as n-butyl acetate, isobutyl acetate, ethyl acetate, and ethyl propionate; polyhydric alcohol derivatives such as ethylene glycol monobutyl ether.

The non-volatile 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 molecule of the compound (b-2) 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) in 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 5 parts 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. The mixing 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 resulting reactive particles (B). More preferably, it is 10 to 98 parts by mass.

When an alkoxysilane having an alkyl group having 1 or more carbon atoms is used, the blending ratio is 2.5 to 100% by mass, preferably 25 to 50% by mass with respect to the compound (b-2). It is preferable from the point of the water resistance improvement of the coating film obtained.

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. Particularly preferred is 10 to 50 parts by mass.

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-diketone compounds such as benzyl and diacetyl; acyloin compounds such as benzoin; acyloin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2, Thioxanthone compounds such as 4-diethylthioxanthone, 2-isopropylthioxanthone, thioxanthone-4-sulfonic acid; benzophenone compounds such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; Michler's ketone compound; acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, α, α'-dimethoxyacetoxy Nzophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- Acetophenone compounds such as (4-morpholinophenyl) -butan-1-one, α-isohydroxyisobutylphenone, α, α'-dichloro-4-phenoxyacetophenone, 1-hydroxy-cyclohexyl-phenyl-ketone; 2,4 Acylphosphine oxide compounds such as 1,6-trimethylbenzoyldiphenylphosphine oxide and bis (acyl) phosphine oxide; quinone compounds such as anthraquinone and 1,4-naphthoquinone; phenacyl chloride, trihalomethylphenylsulfone, Scan (trihalomethyl) -s-halogen compounds such as triazine; peroxides such as di -t- butyl peroxide. 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 name IRGACURE), Darocur-1173, Darocur-1116, Darocur-2959, Darocur-1664, Darocur-4064 (Merck Japan, trade name, English name 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., LTD., Product name], TRIGONAL P1 [AKZO Co., LTD., Product name], SANDORAY 1000 [SANDOZ Co., LTD.] Product name], Deep (DEAP) (manufactured by APJOHN Co., LTD., Product name), CANTACURE-PDO, CANTACURE-ITX, CANTACURE-EPD [WARD BREKKINSOP Co., LTD.), Trade name, etc.

The photopolymerization initiator (C) is preferably one or a mixture of two or more of a thioxanthone compound, an acetophenone compound and an acylphosphine oxide compound from the viewpoint of photocurability, and among them, an acetophenone compound and an acylphosphine. Particularly preferred is a mixture with a fin oxide compound.

The amount of the photopolymerization initiator (C) used is not particularly limited, but is preferably 0.5 to 10 parts by weight, more preferably 100 parts by weight of the nonvolatile content of the active energy ray-curable composition. Is in the range of 1 to 5 parts by weight. 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 amide compounds such as dimethylaminoethyl (meth) acrylamide.

Examples of the polyfunctional polymerizable unsaturated compound include esterified products of 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, Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, Hexane dimethanol di (meth) acrylate, tricyclodencan dimethanol di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, hydrogenated bisphenol F di (meth) acrylate, hydrogenated hexafluorobisphenol A di (meth) Acrylate, bis (2- (meth) acryloyloxy) hexahydrophthalic acid, 5-ethyl-2- (2-hydroxy-1,1dimethylethyl) -5- (hydroxymethyl) -1,3-dioxanedi (meth) ) Di (meth) acrylate compounds such as acrylate; glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide Tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ε-caprolactone-modified tris (acryloxyethyl) isocyanurate and other tri (meth) acrylate compounds; pentaerythritol tetra (meth) acrylate and other tetra (meth) acrylates Compound; Other examples include 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 thereof include polymerizable unsaturated group-containing acrylic resins obtained by adding a compound having an isocyanate group and a polymerizable unsaturated group, such as 2-isocyanatoethyl (meth) acrylate, 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 a polymerizable unsaturated compound represented by the following general formula (D-II).

[In the formula (DI), R ³¹ are the same or different and each represents a hydrogen atom or a methyl group. R ³² is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. s is the same or different and represents an integer of 0 to 5. In formula (D-II), R ³³ are the same or different and each represents a hydrogen atom or a methyl group. R ³⁴ is the same or different and represents a divalent hydrocarbon group having 1 to 6 carbon atoms. R ³² 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. Among these, a divalent hydrocarbon group having 2 to 4 carbon atoms, particularly an ethylene group is preferable.

R ³⁴ 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. Among these, a divalent hydrocarbon group having 2 to 4 carbon atoms, particularly an ethylene group is preferable.

Examples of the polymerizable unsaturated compound represented by the general formula (DI) include isocyanurate cycloadducts of 1,6-hexamethylene diisocyanate, and hydroxyalkyl (meth) acrylate or caprolactone-modified hydroxyalkyl (meth). The acrylate can be obtained by heating at 60 to 70 ° C. for several hours 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 (B-XII) described in the method for producing the reactive particles (B) described above. The same compound. The polymerizable unsaturated compound represented by the general formula (D-II) is the same as the compound represented by the general formula (B-XV) described in the method for producing the reactive particles (B) described above. A compound. Therefore, when the reactive particles (B) are produced, the polymerizable unsaturated compound represented by the general formula (DI) or the polymerizable unsaturated compound represented by the general formula (D-II) In the present invention, the polymerizable unsaturated compound represented by the general formula (DI) and the polymerizable unsaturated compound represented by the general formula (D-II) are used in the present invention. And contained in the 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 carried out 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.

The blending ratio of the polymerizable unsaturated compound (D) in the active energy ray-curable composition of the present invention is not particularly limited. From the viewpoint of scratch resistance, transparency of the coating film, and adhesion, it is preferably 1 to 95 parts by mass, more preferably 10 to 80 parts per 100 parts by mass of the nonvolatile content of the active energy ray-curable composition. Part 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, etc., if necessary, and may be diluted with a solvent if 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 ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate, butyl acetate, methyl benzoate, and methyl propionate; ethers such as tetrahydrofuran, dioxane, and dimethoxyethane Solvents: Glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, etc. Is mentioned. These can be used in appropriate combination depending on the purpose such as adjustment of viscosity and adjustment of coating property.

As the ultraviolet absorber, conventionally known ones can be used, and for example, a benzotriazole-based absorbent, a triazine-based absorbent, a salicylic acid derivative-based absorbent, a benzophenone-based absorbent, and the like can be used.

Specific examples of the benzotriazole-based absorbent include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-amylphenyl) benzotriazole 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- {2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -te La hydro) -5'-methylphenyl} benzotriazole.

Specific examples of the triazine-based absorbent include 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -1,3,5-triazine, 2- [4 ((2-hydroxy-3-dodecyloxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [ 4-((2-hydroxy-3-tridecyloxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like.

Specific examples of the salicylic acid derivative-based absorbent include phenyl salicylate, p-octylphenyl salicylate, 4-tert-butylphenyl salicylate, and the like.

Specific examples of the benzophenone-based absorbent include 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-octadecyloxy Benzophenone, sodium 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5-chloro-2 -Hydroxy Benzophenone, resorcinol monobenzoate, 2,4-dibenzoyl resorcinol, 4,6-dibenzoyl resorcinol, hydroxy dodecyl benzophenone. Examples of the UV absorber include known polymerizable UV absorbers such as 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole, 2,2′-dihydroxy-4 (3- Methacryloxy-2-hydroxypropoxy) benzophenone or the like can also be used.

Examples of commercially available ultraviolet absorbers include TINUVIN900, TINUVIN928, TINUVIN348-2, TINUVIN479, TINUVIN405 (trade name, manufactured by Ciba Specialty Chemicals), and RUVA93 (trade name, manufactured by Otsuka Chemical Co., Ltd.).

The amount of the ultraviolet absorber used is not particularly limited, but is 0.1 to 10 parts by weight, preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the nonvolatile content of the active energy ray-curable composition. It is preferable that it is in the range of parts by mass.

On the other hand, the light stabilizer is used as a radical chain inhibitor that traps active radical species generated during the deterioration process of the film, and includes, for example, a hindered amine light stabilizer.

Among the light stabilizers, a hindered piperidine compound may be mentioned as a light stabilizer exhibiting an excellent light stabilizing action. Examples of the hindered piperidine compound include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis ( N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 4-benzoyloxy-2,2 ′, 6,6′-tetramethylpiperidine, bis (1,2,2,6, Monomer type such as 6-pentamethyl-4-piperidyl) {[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl} butyl malonate; poly {[6- (1,1 , 3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene Oligomer type such as (2,2,6,6-tetramethyl-4-piperidyl) iminol]}; 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and succinic acid Examples include polyester-bonded types such as polyesters, but are not limited thereto. A known polymerizable light stabilizer can also be used as the light stabilizer.

Commercially available products of the above light stabilizer include, for example, TINUVIN123, TINUVIN152, TINUVIN292 (Ciba Specialty Chemicals, trade name), HOSTAVIN 3058 (Clariant, trade name), ADK STAB LA-82 (trade name, manufactured by ADEKA Corporation) ) And the like.

The amount of the light stabilizer to be used is not particularly limited, but is 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the nonvolatile content of the active energy ray-curable composition. It is preferable that it is in the range of parts by mass.

The nonvolatile content of the active energy ray-curable composition of the present invention is not particularly limited. For example, the content is preferably 20 to 100% by mass, and more preferably 25 to 70% by 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.

There is no particular limitation on the object to be coated. Specifically, for example, metal materials such as iron, aluminum, brass, copper, stainless steel, tinplate, galvanized steel, alloyed zinc (Zn—Al, Zn—Ni, Zn—Fe, etc.) plated steel; polyethylene resin, Polypropylene resin, acrylonitrile-butadiene-styrene (ABS) resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin, epoxy resin, and various plastic materials such as FRP; glass, cement, concrete, etc. Inorganic materials; wood; fiber materials (paper, cloth, etc.) 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 active energy ray-curable composition, drying can be performed as necessary. The drying is not particularly limited as long as the solvent that is added can be removed. For example, the drying 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 is appropriately set according to the purpose. For example, the film thickness is preferably 1 to 100 μm, 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. The irradiation dose is, for example, preferably in the range of 5 to 20,000 J / m ² , more preferably 100 to 10,000 J / m ² .

The active energy ray irradiation may be performed in an air atmosphere or 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.

Further, after the active energy ray irradiation, the coating film may be heated as necessary. 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. The heating can usually be performed at an atmospheric 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)
A separable flask equipped with a reflux condenser, a thermometer, an air introduction tube and a stirrer was charged with 400 parts of Glycidyl POSS cage mixture (trade name, manufactured by Hybrid Plastics) and 600 parts of butyl acetate and dissolved while stirring at 60 ° C. I let you. Here, 190 parts of acrylic acid, 1.5 parts of methoquinone and 10 parts of tetrabutylammonium bromide were charged and reacted at 100 ° C. for 4 hours while blowing dry air to obtain a 50% non-volatile solution of the product (A1). .

Glycidyl POSS cage mixture used as a raw material was a 3-glycidoxypropyl group-containing cage-type polysilsesquioxane having a weight average molecular weight of 1,800 and an epoxy equivalent of 168 g / eq.

As a result of ²⁹ Si-NMR analysis of the product (A1), 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. The T1 and T2 structures indicating the presence of were not confirmed.

As a result of ¹ H-NMR analysis of the product (A1), a peak of 0.6 ppm derived from a methylene group bonded to Si was confirmed. In addition, 5.9 ppm, 6.1 ppm, and 6.4 ppm peaks derived from the carbon-carbon unsaturated bond of the acryloyloxy group were confirmed. The molar ratio between the carbon-carbon unsaturated bond of the acryloyloxy group and the methylene group bonded to Si calculated from the peak intensity ratio was 1.07. (The molar ratio exceeds 1.00 because the acrylic acid is added excessively in order to promote the addition reaction of acrylic acid.) In addition, no peak attributed to the epoxy group was confirmed. The epoxy equivalent was 10,000 g / eq or more.

Further, as a result of FT-IR analysis of the product (A1), a broad peak around 3500 cm ⁻¹ attributed to a hydroxyl group that was not confirmed in the raw material Glycidyl POSS cage mixture was confirmed.

The weight average molecular weight of the product (A1) was 2,700.

From the results of ²⁹ Si-NMR, ¹ H-NMR, FT-IR, weight average molecular weight and the like of the product (A1), all the organic groups in which the product (A1) was directly bonded to the silicon atom were Organic group represented by formula (PI)

It was confirmed to be a silsesquioxane compound having a weight average molecular weight of 2,700.

(Production Example 2)
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 methoquinone at 100 ° C. while blowing dry air. It was made to react for 12 hours and the product (A2) was obtained. Next, in a separable flask equipped with a reflux condenser, a thermometer and a stirrer, 300 parts of toluene, 30 parts of a 40% tetrabutylammonium hydroxide methanol solution and 12 parts of deionized water were placed. Cooled to ° C. A solution obtained by mixing 300 parts of tetrahydrofuran and 147 parts of the product (A2) was added thereto and reacted at 20 ° C. for 24 hours. After removing volatile components by distillation under reduced pressure, this was dissolved in 100 parts of propylene glycol monomethyl ether acetate to obtain a 50% non-volatile solution of the product (A3).

As a result of ²⁹ Si-NMR analysis of the product (A3), a peak around −70 ppm derived from the T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si, and one hydroxysilyl group were found. A -59 ppm peak derived from the T2 structure possessed was confirmed. The integrated intensity ratio of these peaks was: peak derived from the T3 structure / peak derived from the T2 structure = 90/10.

As a result of ¹ H-NMR analysis of the product (A3), a peak of 0.6 ppm derived from a methylene group bonded to Si was confirmed. In addition, 5.9 ppm, 6.1 ppm, and 6.4 ppm peaks derived from the carbon-carbon unsaturated bond of the acryloyloxy group were confirmed. The molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy group to the methylene group bonded to Si calculated from these peak intensity ratios was 1.01.

As a result of FT-IR analysis of the product (A3), a peak around 1540 cm ⁻¹ attributable to the urethane bond was confirmed.

The weight average molecular weight of the product (A3) was 2,500.

From the results of the ²⁹ Si-NMR, ¹ H-NMR, FT-IR, weight average molecular weight, etc. for the product (A3), all of the organic groups in which the product (A3) was directly bonded to the silicon atom were as follows: Organic group represented by formula (P-II)

It was confirmed that the compound was a silsesquioxane compound having a weight average molecular weight of 2,500.

(Production Example 3)
In a separable flask equipped with a reflux condenser, thermometer, air inlet tube and stirrer, 400 parts of 3-aminopropyltrimethoxysilane, 1,600 parts of 2-propyl alcohol, 2 parts of tetrabutylammonium fluoride, and deionized 60 parts of water was charged and reacted at 60 ° C. for 8 hours. After concentration by vacuum distillation until the nonvolatile content was 60%, 160 parts of butyl acetate was added and vacuum distillation was continued to obtain a 60% nonvolatile solution of the product (A4).

In a separable flask equipped with a reflux condenser, a thermometer, an air introduction tube and a stirrer, 400 parts of butyl acetate and 310 parts of 2-isocyanatoethyl acrylate were blended and cooled to 10 ° C. while stirring in an ice bath. 400 parts of a non-volatile content 60% solution of the product (A4) was added dropwise thereto while maintaining the reaction temperature at 20 ° C. or lower. After stirring at 60 ° C. for 1 hour, the mixture was filtered through a 300 mesh filter to obtain a 50% non-volatile solution of the product (A5).

As a result of ²⁹ Si-NMR analysis of the product (A4), a peak around −70 ppm derived from the T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si, and one hydroxysilyl group were found. A -59 ppm peak derived from the T2 structure possessed was confirmed. The integrated intensity ratio of these peaks was: peak derived from the T3 structure / peak derived from the T2 structure = 90/10. The total amine value was 508 mgKOH / g.

The weight average molecular weight of the product (A4) was 1,500.

As a result of ²⁹ Si-NMR analysis of the product (A5), a peak around −70 ppm derived from the T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si, and one hydroxysilyl group were found. A -59 ppm peak derived from the T2 structure possessed was confirmed. The integrated intensity ratio of these peaks was: peak derived from the T3 structure / peak derived from the T2 structure = 90/10. The total amine value was 0 mgKOH / g, and the NCO value was 0 mgNCO / g.

As a result of ¹ H-NMR analysis of the product (A5), a peak of 0.6 ppm derived from a methylene group bonded to Si was confirmed. In addition, 5.9 ppm, 6.1 ppm, and 6.4 ppm peaks derived from the carbon-carbon unsaturated bond of the acryloyloxy group were confirmed. The molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy group to the methylene group bonded to Si calculated from these peak intensity ratios was 1.01.

The weight average molecular weight of the product (A5) was 3,000.

From the results of ²⁹ Si-NMR, ¹ H-NMR, weight average molecular weight, etc. for the product (A5), almost all of the organic groups in which the product (A5) was directly bonded to the silicon atom were represented by the following formula (P Organic group represented by -III)

It was confirmed to be a silsesquioxane compound having a weight average molecular weight of 3,000.

(Production Example 4)
A separable flask equipped with a reflux condenser, a thermometer, an air introduction tube and a stirrer was charged with 400 parts of Glycidyl POSS cage mixture (trade name, manufactured by Hybrid Plastics) and 600 parts of butyl acetate and dissolved while stirring at 60 ° C. I let you. To this, 172 parts of acrylic acid, 1.5 parts of methoquinone and 10 parts of tetrabutylammonium bromide were charged and reacted at 100 ° C. for 24 hours while blowing dry air. Further, 338 parts of 2-isocyanate ethyl acrylate and 306 parts of butyl acetate were blended and reacted at 80 ° C. for 12 hours to obtain a 50% nonvolatile solution of the product (A6).

As a result of ²⁹ Si-NMR analysis of the product (A6), 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. The T1 and T2 structures indicating the presence of were not confirmed.

As a result of ¹ H-NMR analysis of the product (A6), a peak of 0.6 ppm derived from a methylene group bonded to Si was confirmed. In addition, 5.9 ppm, 6.1 ppm, and 6.4 ppm peaks derived from the carbon-carbon unsaturated bond of the acryloyloxy group were confirmed. The molar ratio of the carbon-carbon unsaturated bond of the acryloyloxy group to the methylene group bonded to Si calculated from these peak intensity ratios was 2.03. Moreover, the peak attributed to an epoxy group was not confirmed. The epoxy equivalent was 10,000 g / eq or more.

Further, as a result of FT-IR analysis of the product (A6), a peak around 1540 cm −1 attributed to a urethane bond that was not confirmed in the raw material Glycidyl POSS cage mixture was confirmed.

The NCO value of the product (A6) was 0 mg NCO / g.

The weight average molecular weight of the product (A6) was 5,000.

From the results of the ²⁹ Si-NMR, ¹ H-NMR, FT-IR, weight average molecular weight, etc. for the product (A6), almost all of the organic groups in which the product (A6) was directly bonded to the silicon atom were found. Organic group represented by the following formula (P-IV)

It was confirmed to be a silsesquioxane compound having a weight average molecular weight of 5,000.

(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.), 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. 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 (PV) and a compound represented by the following formula (P-VI),

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

(Production Example 6)
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 10 parts, p-methoxyphenol 0.2 part and isopropanol 227 parts were added, and the temperature was raised 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 (B1) obtained in Production Example 5 [6 parts of the compound represented by the above formula (PV)] were 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 a compound represented by the formula (P-VI) 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-VI) is: reactive particles / compound represented by the formula (P-VI) = 100/3 (mass ratio) )Met. The mixture of the reactive particles obtained in this production example and the compound represented by the formula (P-VI) is referred to as product (B2).

(Production Example 7)
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 (100 parts of silica fine particles), 14 parts of 3-methacryloyloxypropyltrimethoxysilane, 0.2 part of p-methoxyphenol and 230 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, 10 parts of a 60% non-volatile solution of the product (B1) obtained in Production Example 5 [4 parts of the compound represented by the above formula (PV)] 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 a compound represented by the formula (P-VI) 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-VI) is: reactive particles / compound represented by the formula (P-VI) = 100/2 (mass ratio) )Met. The mixture of the reactive particles obtained in this production example and the compound represented by the formula (P-VI) is referred to as product (B3).

(Production Example 8)
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 (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% nonvolatile solution of the product (B1) obtained in Production Example 5 [8 parts of the compound represented by the formula (PV)] 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 mixed solution of reactive particles and a compound represented by the formula (P-VI) 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-VI) is: reactive particles / compound represented by the formula (P-VI) = 100/5 (mass ratio) )Met. The mixture of the reactive particles obtained in this production example and the compound represented by the formula (P-VI) is referred to as product (B4).

(Production Example 9)
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 (100 parts of silica fine particles), 3 parts of 3-methacryloyloxypropyltrimethoxysilane, 0.2 part of p-methoxyphenol and 232 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, 4 parts of a 60% non-volatile solution of the product (B1) obtained in Production Example 5 [2 parts of the compound represented by the above formula (PV)] were 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 a compound represented by the formula (P-VI) 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-VI) is: reactive particles / compound represented by the formula (P-VI) = 100/1 (mass ratio) )Met. The mixture of the reactive particles obtained in this production example and the compound represented by the formula (P-VI) is referred to as product (B5).

(Production Example 10)
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 (100 parts of silica fine particles), 20 parts of 3-methacryloyloxypropyltrimethoxysilane, 0.2 part of p-methoxyphenol and 220 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, 33 parts of a 60% non-volatile solution of the product (B1) obtained in Production Example 5 [12 parts of the compound represented by the above formula (PV)] were 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 a compound represented by the formula (P-VI) 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-VI) is: reactive particles / compound represented by the formula (P-VI) = 100/6 (mass ratio) )Met. The mixture of the reactive particles obtained in this production example and the compound represented by the formula (P-VI) is referred to as product (B6).

(Production Example 11)
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 60% non-volatile solution of the product (B1) obtained in Production Example 5 [6 parts of the compound represented by the above formula (PV)] were 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 a compound represented by the formula (P-VI) 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-VI) is: reactive particles / compound represented by the formula (P-VI) = 100/3 (mass ratio) )Met. The mixture of the reactive particles obtained in this production example and the compound represented by the formula (P-VI) is referred to as product (B7).

(Production Example 12)
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 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.) 333 parts (silica fine particle: 100 parts), 10 parts of the product (B8) obtained in Production Example 12, 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 60% non-volatile solution of the product (B1) obtained in Production Example 5 [6 parts of the compound represented by the above formula (PV)] were 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 a compound represented by the formula (P-VI) 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-VI) is: reactive particles / compound represented by the formula (P-VI) = 100/3 (mass ratio) )Met. The mixture of the reactive particles obtained in this production example and the compound represented by the formula (P-VI) is referred to as product (B9).

(Production Example 14)
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-VII) and a compound represented by the following formula (P-VIII),

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

(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 10 parts, p-methoxyphenol 0.2 part and isopropanol 227 parts were added, and the temperature was raised 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 14 [6 parts of the compound represented by the above formula (P-VII)] were 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-VIII) 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-VIII) is: reactive particles / compound represented by the formula (P-VIII) = 100/3 (mass ratio) )Met. The mixture of the reactive particles obtained in this production example and the compound represented by the formula (P-VIII) is referred to as product (B11).

(Production Example 16)
A four-necked flask equipped with a reflux condenser, a thermometer, an air introduction tube and a stirrer was added to 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 (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. 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-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 17)
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 10 parts, p-methoxyphenol 0.2 part and isopropanol 227 parts were added, and the temperature was raised 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 (B12) obtained in Production Example 16 [6 parts of the compound represented by the formula (P-IX)] 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 an azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a mixture of reactive particles and a compound represented by the formula (PX) having a nonvolatile content of 40%. It was. The ratio of the reactive particles calculated from the blending amount and the compound represented by the formula (PX) is: reactive particles / compound represented by the formula (PX) = 100/4 (mass ratio) )Met. The mixture of the reactive particles obtained in this production example and the compound represented by the formula (PX) is referred to as a product (B13).

(Production Example 18)
A four-necked flask equipped with a reflux condenser, a thermometer, an air inlet tube and a stirrer was charged with 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-XI) and a compound represented by the following formula (P-XII).

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

(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: 100 parts), 3-methacryloyloxypropyltrimethoxysilane 10 parts, p-methoxyphenol 0.2 part and isopropanol 227 parts were added, and the temperature was raised 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 (B14) obtained in Production Example 18 [4 parts of the compound represented by the above formula (P-XI)] 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 an 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-XII) 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-XII) is as follows: reactive particles / compound represented by the formula (P-XII) = 100/3 (mass ratio) )Met. The mixture of the reactive particles obtained in this production example and the compound represented by the formula (P-XII) is referred to as a product (B15).

(Production Example 20)
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 (100 parts of silica fine particles), 10 parts of 3-methacryloyloxypropyltrimethoxysilane, 0.2 part of p-methoxyphenol and 233 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, 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 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 particle: 100 parts), 3-methacryloyloxypropyltrimethoxysilane 10 parts, p-methoxyphenol 0.2 part and isopropanol 227 parts were added, and the temperature was raised 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 (B1) obtained in Production Example 1 [6 parts of the compound represented by the formula (PV)] and 5 parts of decyltrimethoxysilane were added. The dehydration condensation reaction was carried out with stirring at 95 ° C. for 2 hours, then 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 solvent was replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times to obtain a mixed solution of reactive particles and a compound represented by the formula (P-VI) 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-VI) is: reactive particles / compound represented by the formula (P-VI) = 100/3 (mass ratio) )Met. The mixture of the reactive particles obtained in this production example and the compound represented by the formula (P-VI) is referred to as product (B17).

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

(Production Example 23)
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 to give 1-methoxy-2- 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% non-volatile solution of the product (A1) obtained in Production Example 1, 75.0 parts of a 40% non-volatile solution of the product (B2) obtained in Production Example 6, 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%, and stirred, and then the active energy ray-curable composition No. 1 was produced. In Table 1, 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 using an applicator at a dry film thickness of 10 μm, 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 24, Comparative Examples 1 to 5)
In Example 1, the active energy rays of Examples 2 to 24 and Comparative Examples 1 to 5 were the same as Example 1, except that the respective components and blending amounts were changed to the respective components and blending amounts described in Table 1. Curable composition No. 2 to 29 were produced.

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

(Examples 25 to 34)
In Example 1, the active energy ray-curable composition Nos. 25 to 34 of Examples 25 to 34 were used 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 shown in Table 2. 30-39 were produced.

Next, the active energy ray-curable composition was air spray-coated on a polycarbonate resin plate degreased with isopropanol so that the dry film thickness was 10 μm, dried at 80 ° C. for 10 minutes to remove the solvent, and then subjected to ultrahigh pressure. A cured coating film was formed by irradiating active energy rays at a dose of 3,000 mJ / cm ² using a mercury lamp to obtain each test plate. The obtained test plate was subjected to the following evaluation test. The evaluation results are shown in Table 2.

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

(Note 3) KAYARAD R-604: trade name, manufactured by Nippon Kayaku Co., Ltd., 5-ethyl-2- (2-hydroxy-1,1-dimethylethyl) -5- (hydroxymethyl) -1,3-dioxane Diacrylate.
(Note 4) TINUVIN 384-2: trade name, manufactured by Ciba Specialty Chemicals, Inc., UV absorber (Note 5) RUVA93: trade name, manufactured by Otsuka Chemical Co., Ltd., UV absorber (Note 6) TINUVIN 479: trade name, Ciba Specialty Chemicals Manufactured, UV absorber (Note 7) TINUVIN123: trade name, manufactured by Ciba Specialty Chemicals, Inc., light stabilizer (Note 8) HOSTAVIN 3058: trade name, manufactured by Clariant, Inc., light stabilizer (Note 9) ADK STAB LA82: trade name, stock A light stabilizer made by the company ADEKA.

<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.

AA: 100 (no peeling)
A: 90-99 pieces
B: 89-50 pieces,
C: 49 or less.

<Abrasion resistance>
In accordance with ASTM D-1044, a wear test was conducted under 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.

A: No abnormality, or slight swelling, discoloration, gloss change, peeling, etc. are recognized, but there is no practical problem.
B: Dandruff, discoloration, gloss change, peeling, etc. are observed,
C: 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.

A: Transparent and good,
B: Slightly cloudy,
C: It is very cloudy.

<Comprehensive evaluation>
In the field of painting such as daylighting materials for buildings to which the present invention belongs, vehicle windows, lamp lenses, instrument covers, etc., it is desirable that all of adhesion, scratch resistance, weather resistance and transparency are excellent. Therefore, a comprehensive evaluation was performed based on the following criteria:
AA: Adhesiveness is AA, scratch resistance is 7 or less, weather resistance is A, and transparency is A.
A: Adhesiveness is A, scratch resistance is 7 or less, weather resistance is A, and transparency is A.
B: Adhesiveness is AA, A or B, scratch resistance is 7 or less, weather resistance is A or B, transparency is A or B, and adhesiveness, scratch resistance and weather resistance At least one of which is B,
C: At least one of adhesion, scratch resistance and weather resistance is C or cannot be evaluated, or the scratch resistance exceeds 7.

Claims

Silsesquioxane compound (A) and reactive particles (B)
An active energy ray-curable composition containing
The silsesquioxane compound (A) has an organic group directly bonded to a silicon atom in the silsesquioxane compound (A),
At least one of the organic groups has both (a-1) at least one selected from the group consisting of a secondary hydroxyl group, a urethane bond and a urea bond, and (a-2) at least one (meth) acryloyloxy group. And 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. ,
An active energy ray-curable composition.
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 article to be coated.