JPWO2010067684A1 - Silsesquioxane compound having a polymerizable functional group - Google Patents

Abstract

This invention makes it a subject to provide the silsesquioxane compound which is excellent in the heat resistance of the obtained coating film, scratch resistance, and a weather resistance. Another object of the present invention is to provide a silsesquioxane compound that is not only excellent in compatibility with a general polymerizable unsaturated compound but also excellent in compatibility with a highly polar polymerizable unsaturated compound. . The present invention is 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 two or more (meth) acryloyloxy groups A silsesquioxane compound, which is a group. Furthermore, the organic group having two or more (meth) acryloyloxy groups is an organic group having two or more (meth) acryloyloxy groups and having a urethane bond and / or a urea bond. Oxane compounds are provided.

Description

  The present invention relates to a silsesquioxane compound having a polymerizable functional group.

Silsesquioxane is a generic name for a series of network-like polysiloxanes having a ladder-type, cage-type, and three-dimensional network-type (random type) structure. Since this silsesquioxane is soluble in a general organic solvent unlike silica, which is a complete inorganic substance represented by the general formula SiO ₂ , it is easy to handle, processability such as film formation, It is characterized by excellent moldability and the like.

  On the other hand, polyfunctional acrylates and unsaturated polyesters are widely studied as unsaturated compounds having radical polymerizability and are industrially used. Various studies have been made on these radically polymerizable unsaturated compounds for the purpose of imparting characteristics such as scratch resistance and stain resistance to the cured product. However, a composition obtained by mixing an organopolysiloxane compound such as silsesquioxane with a radically polymerizable unsaturated compound that has been widely used in the past has been obtained because it is difficult to form a uniform composition due to poor compatibility. There are problems such as the release of the organopolysiloxane compound from the cured product.

  Patent Documents 1 to 5 disclose inventions relating to silsesquioxane having a radical polymerizable functional group such as acryloyloxy group or methacryloyloxy group and an ultraviolet curable composition containing the silsesquioxane. . However, the cured product obtained from the ultraviolet curable composition containing these silsesquioxanes does not sufficiently satisfy the scratch resistance, and the silsesquioxane is another polymerizable unsaturated group compound. There is a problem in that the compatibility with the polymerizable unsaturated compound having a high polarity is not sufficient.

JP-A-3-281616 Japanese Patent Laid-Open No. 4-28722 JP 2002-167552 A JP 2002-363414 A International Publication WO04 / 85501

  The present invention has been made in view of the above circumstances. The first object of the present invention is to provide a silsesquioxane compound that is excellent in heat resistance and that can obtain a coating film sufficiently excellent in scratch resistance and weather resistance. Further, the second object of the present invention is that the obtained coating film is not only excellent in heat resistance, scratch resistance and weather resistance, but also excellent in compatibility with a general polymerizable unsaturated composition. Another object of the present invention is to provide a silsesquioxane compound that is excellent in compatibility with a highly polar polymerizable unsaturated compound.

  As a result of intensive studies in order to solve the above problems, the present inventors have determined that a specific organic group having two or more (meth) acryloyloxy groups as an organic group directly bonded to a silicon atom is silsesquioxane. It has been found that the above problems can be solved by introducing the compound into the compound, and the present invention has been completed.

That is, the present invention
1. 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 an organic group having two or more (meth) acryloyloxy groups. Silsesquioxane compound characterized by the above.

  2. The silsesquioxane according to 1, wherein the organic group having two or more (meth) acryloyloxy groups is an organic group having two or more (meth) acryloyloxy groups and having a urethane bond and / or a urea bond. Compound.

  3. The silsesquioxy according to 2, wherein the organic group having two or more (meth) acryloyloxy groups and having a urethane bond and / or a urea bond is an organic group represented by the following general formula (I-1): Sun compounds,

[In Formula (I-1), R ¹ represents a hydrogen atom or a methyl group, m represents an integer of 2 to 5, and Y represents a (m + 1) -valent organic group having a urethane bond and / or a urea bond. .
However, m H ₂ C═ (R ¹ ) COO— groups are each bonded to two or more different carbons constituting the organic group that is Y].

  4). The silyl according to 3, wherein the organic group represented by the general formula (I-1) is any one of organic groups represented by the following general formula (II-1) to general formula (V-1): Sesquioxane compounds,

{In Formula (II-1), R ² represents a hydrogen atom or a methyl group, R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ is a divalent hydrocarbon group having 1 to 10 carbon atoms or the following general formula (VI)

[In the formula (VI), R ¹⁷ represents a divalent hydrocarbon group having 2 to 4 carbon atoms, and R ¹⁸ represents a diisocyanate residue. ]
The bivalent group represented by these is shown. In formula (III-1), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁸ represents a hydrogen atom or a methyl group, R ⁹ Represents a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent group represented by the general formula (VI). In formula (IV-1), R ¹⁰ represents a hydrogen atom or a methyl group which may be the same or different, and R ¹¹ is a divalent carbon atom having 1 to 10 carbon atoms which may be the same or different. A hydrogen group or a divalent group represented by the general formula (VI) is shown, and R ¹² represents a C 1-10 divalent hydrocarbon group. In formula (V-1), n represents an integer of 1 to 3, R ¹³ represents a hydrogen atom or a methyl group which may be the same or different, and R ¹⁴ may be the same or different. A divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent group represented by the above general formula (VI); R ¹⁵ represents an (n + 1) valent hydrocarbon group having 1 to 10 carbon atoms; R ¹⁶ represents a divalent hydrocarbon group having 1 to 10 carbon atoms.
However, when n is 2 or 3, the H ₂ C═C (R ¹³ ) COOR ¹⁴ NHCOO— group is bonded to two or more different carbons constituting the hydrocarbon group of R ^15. }.

  5. The silsesquioxane compound of any one of 1-4 whose weight average molecular weights are 1,000-100,000.

  An active energy ray-curable composition comprising the silsesquioxane compound according to any one of 6.1 to 5 and a photopolymerization initiator.

  7). The active energy ray-curable composition according to 6, further comprising a polymerizable unsaturated compound other than the silsesquioxane compound.

  According to the silsesquioxane compound of the present invention, by introducing an organic group having two or more (meth) acryloyloxy groups into the silsesquioxane compound, an active energy using the silsesquioxane compound of the present invention. The heat resistance, scratch resistance and weather resistance of the coating film obtained from the linear curable composition can be improved. The silsesquioxane compound according to claim 2, wherein an organic group having two or more (meth) acryloyloxy groups and having a urethane bond and / or a urea bond is introduced among the silsesquioxane compounds of the present invention. In addition to being excellent in heat resistance, scratch resistance and weather resistance, the obtained coating film is not only excellent in compatibility with general polymerizable unsaturated compounds, but also highly polar polymerizable unsaturated Excellent compatibility with compounds.

  The silsesquioxane compound of the present invention is 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 a (meth) acryloyloxy group. It is a silsesquioxane compound (hereinafter, sometimes simply referred to as “silsesquioxane compound of the present invention”) which is an organic group having two or more. When at least one of the organic groups directly bonded to the silicon atom of the silsesquioxane compound of the present invention is an organic group having two or more (meth) acryloyloxy groups, the photocurability is excellent, and as a result The obtained coating film is excellent in heat resistance and sufficiently excellent in scratch resistance and weather resistance.

Silsesquioxane Compound of the Present Invention The silsesquioxane compound of the present invention is a silsesquioxane compound having an organic group directly bonded to a silicon atom, and at least of the organic groups directly bonded to the silicon atom. One is a silsesquioxane compound which is an organic group having two or more (meth) acryloyloxy groups.

  Here, in the present specification, the “silsesquioxane compound” does not mean only a silsesquioxane compound having a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed, but Si—OH A ladder structure in which groups remain, an incomplete cage structure, or a random condensate silsesquioxane compound may also be included.

  In the silsesquioxane compound of the present invention, the ratio of the silsesquioxane compound having a structure in which all Si—OH groups are hydrolytically condensed is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably. Is preferably 100% by mass from the viewpoint of liquid stability.

  In the present invention, the ratio of the organic group having two or more (meth) acryloyloxy groups among the organic groups directly bonded to the silicon atom is not particularly limited, and preferably at least 15 mol% or more. Preferably, it may be 50 mol% or more.

  As the silsesquioxane compound of the present invention, for example, the organic group having two or more (meth) acryloyloxy groups has two or more (meth) acryloyloxy groups and has a urethane bond and / or a urea bond. The silsesquioxane compound which is an organic group can be mentioned. The coating film obtained from this silsesquioxane compound not only has excellent heat resistance, scratch resistance and weather resistance, but also has excellent compatibility with general polymerizable unsaturated compounds, as well as polarity. Excellent compatibility with highly polymerizable unsaturated compounds.

  Examples of the organic group having two or more (meth) acryloyloxy groups and having a urethane bond and / or a urea bond include organic groups represented by the following general formula (I-1).

[In Formula (I-1), R ¹ represents a hydrogen atom or a methyl group, m represents an integer of 2 to 5, and Y represents a (m + 1) -valent organic group having a urethane bond and / or a urea bond. .

However, m H ₂ C═ (R ¹ ) COO— groups are each bonded to two or more different carbons constituting the organic group that is Y.
In formula (I-1), 2 to 5 R ^{1 s} may be the same or different.

  Specific examples of the organic group represented by the general formula (I-1) include organic groups represented by the following general formula (II-1) to general formula (V-1). .

{In Formula (II-1), R ² represents a hydrogen atom or a methyl group, R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ is a divalent hydrocarbon group having 1 to 10 carbon atoms or the following general formula (VI)

[In the formula (VI), R ¹⁷ represents a divalent hydrocarbon group having 2 to 4 carbon atoms, and R ¹⁸ represents a diisocyanate residue. ]
The bivalent group represented by these is shown. In formula (III-1), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁸ represents a hydrogen atom or a methyl group, R ⁹ Represents a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent group represented by the general formula (VI). In formula (IV-1), R ¹⁰ represents a hydrogen atom or a methyl group which may be the same or different, and R ¹¹ is a divalent carbon atom having 1 to 10 carbon atoms which may be the same or different. A hydrogen group or a divalent group represented by the general formula (VI) is shown, and R ¹² represents a C 1-10 divalent hydrocarbon group. In formula (V-1), n represents an integer of 1 to 3, R ¹³ represents a hydrogen atom or a methyl group which may be the same or different, and R ¹⁴ may be the same or different. A divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent group represented by the above general formula (VI); R ¹⁵ represents an (n + 1) valent hydrocarbon group having 1 to 10 carbon atoms; R ¹⁶ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. }

R ³ in the general formula (II-1) is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specifically, for example, 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, decanylene group; Examples thereof include cycloalkylene groups such as cyclohexylene group; arylene groups such as phenylene group and 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 excellent heat resistance, scratch resistance, and polarity. It is preferable from the viewpoint of more excellent compatibility with a highly polymerizable unsaturated compound.

R ⁵ in the general formula (II-1) 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 (VI). Absent. 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 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 excellent heat resistance, scratch resistance, and polarity. It is preferable from the viewpoint of more excellent compatibility with a highly polymerizable unsaturated compound. R ¹⁷ in the general formula (VI) 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 ¹⁸ in the general formula (VI) 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, iso Aliphatic diisocyanate compounds such Ron 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.

As the organic group represented by the general formula (II-1), R ² is preferable because it is more excellent in heat resistance, scratch resistance, compatibility with a highly polar polymerizable unsaturated compound, and active energy ray curability. Is an organic group in which is a hydrogen atom, R ³ is an ethylene group or a 1,3-propylene group, R ⁴ is a hydrogen atom, and R ⁵ is an ethylene group. R ² is a hydrogen atom, R ³ is an ethylene group or a 1,3-propylene group, R ⁴ is a hydrogen atom, and R ⁵ is a divalent group represented by the general formula (VI). And an organic group in which R ¹⁷ is an ethylene group and R ¹⁸ is a divalent group which is an isophorone diisocyanate residue.

R ⁷ in the general formula (III-1) is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specific examples thereof include the same groups as the divalent hydrocarbon group exemplified in the description of R ^{3 in} the general formula (II-1). 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 excellent heat resistance, scratch resistance, and polarity. It is preferable from the viewpoint of more excellent compatibility with a highly polymerizable unsaturated compound.

R ⁹ in the general formula (III-1) 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 (VI). Absent. Specific examples include the same groups as the divalent groups exemplified in the description of R ^{5 in} the general formula (II-1). 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 excellent heat resistance, scratch resistance, and polarity. It is preferable from the viewpoint of more excellent compatibility with a highly polymerizable unsaturated compound.

The organic group represented by the general formula (III-1) includes R ⁶ from the viewpoints of heat resistance, scratch resistance, compatibility with a highly polar polymerizable unsaturated compound, and active energy ray curability. Is an organic group in which is a hydrogen atom, R ⁷ is an ethylene group or a 1,3-propylene group, R ⁸ is a hydrogen atom, and R ⁹ is an ethylene group. In addition, R ⁶ is a hydrogen atom, R ⁷ is an ethylene group or a 1,3-propylene group, R ⁸ is a hydrogen atom, and R ⁹ is a divalent group represented by the general formula (VI). And an organic group in which R ¹⁷ is an ethylene group and R ¹⁸ is a divalent group which is an isophorone diisocyanate residue.

R ¹¹ in the general formula (IV-1) 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 (VI). Absent. Specific examples include the same groups as the divalent groups exemplified in the description of R ^{5 in} the general formula (II-1). 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 excellent heat resistance, scratch resistance, and polarity. It is preferable from the viewpoint of more excellent compatibility with a highly polymerizable unsaturated compound.

R ¹² in the general formula (IV-1) is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specific examples thereof include the same groups as the divalent hydrocarbon group exemplified in the description of R ^{3 in} the general formula (II-1). 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 excellent heat resistance, scratch resistance, and polarity. It is preferable from the viewpoint of more excellent compatibility with a highly polymerizable unsaturated compound.

As the organic group represented by the general formula (IV-1), R ¹⁰ from the viewpoint that heat resistance, scratch resistance, compatibility with a highly polar polymerizable unsaturated compound and active energy ray curability are more excellent. Is an organic group in which is a hydrogen atom, R ¹¹ is an ethylene group, and R ¹² is an ethylene group or a 1,3-propylene group. Further, R ¹⁰ is a hydrogen atom, R ¹¹ is a divalent group represented by the general formula (VI), R ¹⁷ is an ethylene group, and R ¹⁸ is an isophorone diisocyanate residue. An organic group in which R ¹² is an ethylene group or a 1,3-propylene group.

R ¹⁴ in the general formula (V-1) 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 (VI). Absent. Specific examples include the same groups as the divalent groups exemplified in the description of R ^{5 in} the general formula (II-1). 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 excellent heat resistance, scratch resistance, and polarity. It is preferable from the viewpoint of more excellent compatibility with a highly polymerizable unsaturated compound.

R ¹⁵ in the general formula (V-1) is not particularly limited as long as it is an (n + 1) -valent hydrocarbon group having 1 to 10 carbon atoms. The (n + 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. Specifically, for example, the divalent hydrocarbon group includes methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene. Group, alkylene group such as decanylene group; cycloalkylene group such as cyclohexylene group; arylene group 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, p-hydroxybenzoic acid etc. are mentioned. Of these, dimethylolpropionic acid and dimethylolbutanoic acid are preferred from the standpoint of better scratch resistance and active energy ray curability.

R ¹⁶ in the general formula (V-1) is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specific examples thereof include the same groups as the divalent hydrocarbon group exemplified in the description of R ^{3 in} the general formula (II-1). Among them, a divalent hydrocarbon group having 1 to 6 carbon atoms, particularly an ethylene group or a 1,3-propylene group, is compatible with heat-resistant, scratch-resistant and highly polar polymerizable unsaturated compounds. Is preferable from the viewpoint of more excellent.

As the organic group represented by the general formula (V-1), the heat resistance, the scratch resistance, the compatibility with the polymerizable unsaturated compound having a high polarity and the active energy ray curability are more excellent. 2, an organic group in which R ¹³ is a hydrogen atom, R ¹⁴ is an ethylene group, R ¹⁵ is a dimethylolpropionic acid residue, and R ¹⁶ is an ethylene group or a 1,3-propylene group is preferable. . N is 2, R ¹³ is a hydrogen atom, R ¹⁴ is a divalent group represented by the general formula (VI), R ¹⁷ is an ethylene group, and R ¹⁸ is an isophorone diisocyanate residue. An organic group which is a divalent group which is a group, R ¹⁵ is a dimethylolpropionic acid residue, and R ¹⁶ is an ethylene group or a 1,3-propylene group is preferable.

  The silsesquioxane compound of the present invention 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 of the present invention is not particularly limited. The weight average molecular weight is preferably 1,000 to 100,000, more preferably 1,000 to 10,000. These ranges are significant in terms of the heat resistance of the coating film obtained from the silsesquioxane compound of the present invention, the viscosity and paintability of the active energy ray-curable composition containing the silsesquioxane compound of the present invention, and the like. is there.

  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 are 10 samples having different concentrations in which the silsesquioxane compound of the present invention is dissolved in propylene glycol monomethyl ether and the concentration is 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 of the present invention The production method of the silsesquioxane compound of the present invention can use a production method conventionally used for production of general silsesquioxane, and is particularly limited. Is not to be done.
In addition, for example, it can also be produced using the following production method A, production method B or the like.

Manufacturing method A
Production method A includes a production method using a hydrolyzable silane in which an organic group having two or more (meth) acryloyloxy groups is directly bonded to a silicon atom as a starting material.

  Specifically, for example, a hydrolyzable silane represented by the following general formula (VII) and, if necessary, a hydrolyzable silane other than the hydrolyzable silane represented by the following general formula (VII) are used as a starting material. And a method for producing the silsesquioxane compound of the present invention by hydrolytic condensation in the presence of a catalyst.

R ¹⁹ SiX ₃ (VII)
R ¹⁹ in the general formula (VII) represents an organic group having two or more (meth) acryloyloxy groups. X is chlorine or a C1-C6 alkoxy group, and X may be the same or different.

As a C1-C6 alkoxy group, a C1-C6 (preferably C1-C4) linear or branched alkoxy group can be mentioned. More specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, 1-ethylpropoxy, isopentyloxy, neopentyloxy, n -Hexyloxy, 1,2,2-trimethylpropoxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, isohexyloxy, 3-methylpentyloxy group and the like are included.

  Therefore, specific examples of X include chlorine, methoxy group, ethoxy group, propoxy group, butoxy group and the like.

  As the hydrolyzable silane other than the hydrolyzable silane represented by the general formula (VII), a silsesquioxane compound is obtained by hydrolytic condensation together with the hydrolyzable silane represented by the general formula (VII). If it can manufacture, it will not specifically limit. Specific examples include alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane.

  Examples of the hydrolyzable silane represented by the general formula (VII) include hydrolyzable silanes represented by the following general formula (I-2).

[In General Formula (I-2), R ¹ , m, Y and X are the same as above. X may be the same or different. ].

  Specific examples of the hydrolyzable silane represented by the general formula (I-2) include a hydrolyzable silane represented by the following general formula (II-2) and the following general formula (III-2). The hydrolyzable silane represented by these is mentioned.

[In General Formula (II-2), R ² , R ³ , R ⁴ , R ⁵ and X are the same as above.
In General Formula (III-2), R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are the same as described above.
X may be the same or different. ].

  Examples of the hydrolyzable silane represented by the general formula (II-2) include a hydrolyzable silane represented by the following general formula (II-3) and a compound represented by the following general formula (II-4). Can be obtained by further reacting a compound represented by the following general formula (II-5) with the product.

[In General Formula (II-3), R ³ and X are the same as defined above.
In General Formula (II-4), R ² is the same as described above.
In general formula (II-5), R ⁴ and R ⁵ are the same as above. ].

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

  Specifically, the compound represented by the general formula (II-4) is acrylic acid and methacrylic acid.

  Specific examples of the compound represented by the general formula (II-5) include isocyanate methyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 3-isocyanatepropyl (meth) acrylate, and isocyanate octyl ( And (meth) acrylate. Moreover, the adduct of a hydroxyl group containing (meth) acrylate and a diisocyanate compound is mentioned, Specifically, the adduct of 2-hydroxyethyl (meth) acrylate and isophorone diisocyanate is mentioned, for example.

  Examples of the hydrolyzable silane represented by the general formula (III-2) include a hydrolyzable silane represented by the following general formula (III-3) and a compound represented by the following general formula (III-4). Can be obtained by further reacting the product with a compound represented by the following general formula (III-5).

[In General Formula (III-3), R ⁷ and X are the same as defined above.
In general formula (III-4), R ⁶ is the same as described above.
In General Formula (III-5), R ⁸ and R ⁹ are the same as described above. ].

  Specific examples of the hydrolyzable silane represented by the general formula (III-3) include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl). Examples thereof include ethyltriethoxysilane.

  Specifically, the compound represented by the general formula (III-4) is acrylic acid or methacrylic acid.

  Specific examples of the compound represented by the general formula (III-5) include the same compounds as those specifically shown in the description of the compound represented by the general formula (II-5). .

  Reaction of the hydrolyzable silane represented by the general formula (II-3) with the compound represented by the general formula (II-4), and the hydrolysis represented by the general formula (III-3) The reaction of the functional silane and the compound represented by the general formula (III-4) can be performed according to a conventional method in which a carboxyl group and an epoxy group are reacted.

  In the above reaction, the proportion of the hydrolyzable silane represented by the general formula (II-3) and the compound represented by the general formula (II-4) is usually 0.80 with respect to 1 mole of the former. About 1.20 mol, preferably about 0.90 to 1.10 mol.

  In the above reaction, the proportion of the hydrolyzable silane represented by the general formula (III-3) and the compound represented by the general formula (III-4) is usually 0.80 with respect to 1 mole of the former. About 1.20 mol, preferably about 0.90 to 1.10 mol.

  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.

  In the reaction, a catalyst may be appropriately used. 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, imidazoles, diaza Examples thereof include cyclic nitrogen-containing compounds such as bicycloundecene and phosphorus compounds such as triphenylphosphine and tributylphosphine. Although the usage-amount of a catalyst is not specifically limited, It is 0.01-5 mass% with respect to the reaction raw material.

  In the reaction, a solvent may be appropriately used. The solvent is not particularly limited. Specifically, for example, ketones 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. Esters; ethers such as tetrahydrofuran, dioxane, dimethoxyethane; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; toluene, xylene, etc. Aromatic hydrocarbons, aliphatic hydrocarbons and the like.

  A product obtained by reacting the hydrolyzable silane represented by the general formula (II-3) with the compound represented by the general formula (II-4) (hereinafter simply referred to as a product (II-3- 4) and the compound represented by the general formula (II-5), and the hydrolyzable silane represented by the general formula (III-3) and the general formula (III). -4) product obtained by reacting with the compound (hereinafter sometimes simply referred to as product (III-3-4)) and the compound represented by the general formula (III-5) The reaction with can be carried out according to a conventional method in which a hydroxyl group and an isocyanate group are reacted.

  The use ratio of the product (II-3-4) and the compound represented by the general formula (II-5) in the above reaction is usually about 0.90 to 1.10 mol of the latter with respect to 1 mol of the former. Preferably, it may be about 0.95 to 1.05 mol.

  The use ratio of the product (III-3-4) and the compound represented by the general formula (III-5) in the above reaction is usually about 0.90 to 1.10 mol of the latter with respect to 1 mol of the former. Preferably, it may be about 0.95 to 1.05 mol.

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

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

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

  Another specific example of the hydrolyzable silane represented by the general formula (I-2) is a hydrolyzable silane represented by the following general formula (IV-2).

[In General Formula (IV-2), R ¹⁰ , R ¹¹ , R ¹² and X are the same as above.
X may be the same or different. ].

  Examples of the hydrolyzable silane represented by the general formula (IV-2) include a hydrolyzable silane represented by the following general formula (IV-3) and a compound represented by the following general formula (IV-4). It can obtain by making it react.

^{R 12,} X in the general formula (IV-3) is the same as ^{R 12,} X in the general formula (IV-2). ^{R 10, R 11} in the general formula (IV-4) is the same as ^{R 10, R 11} in the general formula (IV-2).

  Specific examples of the hydrolyzable silane represented by the general formula (IV-3) include N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl). -3-aminopropyltriethoxysilane and the like.

  Specific examples of the compound represented by the general formula (IV-4) include the same compounds as those specifically shown in the description of the compound represented by the general formula (II-5). .

  The reaction between the hydrolyzable silane represented by the general formula (IV-3) and the compound represented by the general formula (IV-4) is usually performed by the hydrolysis represented by the general formula (IV-3). It is carried out using 2 mol or more of the compound represented by the general formula (IV-4) with respect to 1 mol of the decomposable silane.

  The reaction between the hydrolyzable silane represented by the general formula (IV-3) and the compound represented by the general formula (IV-4) may be performed according to a conventional method in which an amino group and an isocyanate group are reacted. it can.

  The reaction temperature is, for example, -78 ° C to 200 ° C, preferably -78 ° C to 100 ° C, more preferably -10 ° C to 40 ° C. Although this reaction can be carried out regardless of pressure, a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable. Since the reaction is very fast, the reaction usually ends as soon as the dropping is completed.

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

  Another specific example of the hydrolyzable silane represented by the general formula (I-2) is a hydrolyzable silane represented by the following general formula (V-2).

[N, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and X in the general formula (V-2) are the same as described above.
X may be the same or different. ].

  Examples of the hydrolyzable silane represented by the general formula (V-2) include a hydrolyzable silane represented by the following general formula (V-3) and a compound represented by the following general formula (V-4). Can be obtained by further reacting the product with a compound represented by the following general formula (V-5).

^{R 16} and X in the general formula (V-3) is the same as ^{R 16} and X in the general formula (V-2). N and ^{R 15} in the general formula (V-4) is the same as n and ^{R 15} in the general formula (V-2). ^{R 13} and ^{R 14} in the general formula (V-5) is the same as ^{R 13} and ^{R 14} in the general formula (V-2).

  Specific examples of the hydrolyzable silane represented by the general formula (V-3) include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane.

Specific examples of the compound represented by the general formula (V-4) include the same hydroxymonocarboxylic acid as the hydroxymonocarboxylic acid specifically shown in the description of R ^{15 in} the general formula (V-1). Carboxylic acid is mentioned.

  Specific examples of the compound represented by the general formula (V-5) include the same compounds as those specifically shown in the description of the compound represented by the general formula (II-5). .

  The reaction between the hydrolyzable silane represented by the general formula (V-3) and the compound represented by the general formula (V-4) may be performed according to a conventional method in which a carboxyl group and an epoxy group are reacted. it can. The reaction conditions such as the use ratio of the raw material compound, reaction temperature, catalyst, solvent, reaction time, etc. are the hydrolyzable silane represented by the general formula (II-3) and the general formula (II-4) described above. The same reaction conditions as the reaction conditions illustrated in the reaction with the represented compound can be mentioned.

  The product obtained by reacting the hydrolyzable silane represented by the general formula (V-3) with the compound represented by the general formula (V-4) and the general formula (V-5) The product 1 obtained by reacting the hydrolyzable silane represented by the general formula (V-3) and the compound represented by the general formula (V-4) is usually It is carried out using 2 mol or more of the compound represented by the general formula (V-5) with respect to mol.

  The product obtained by reacting the hydrolyzable silane represented by the general formula (V-3) with the compound represented by the general formula (V-4) and the general formula (V-5) The reaction with the compound can be carried out according to a conventional method in which a hydroxyl group and an isocyanate group are reacted. As reaction conditions such as reaction temperature, catalyst, solvent, and reaction time, the hydrolyzable silane represented by the general formula (II-3) and the compound represented by the general formula (II-4) described above are used. The same reaction conditions as the reaction conditions illustrated in the reaction of the product obtained by the reaction and the compound represented by the general formula (II-5) can be mentioned.

In order to obtain the silsesquioxane compound of the present invention using production method A, specifically,
Hydrolyzing and condensing in the presence of a catalyst using the hydrolyzable silane represented by the general formula (VII) as a starting material, or
The hydrolyzable silane represented by the general formula (VII) and the hydrolyzable silane other than the hydrolyzable silane represented by the general formula (VII) are used as a starting material for hydrolysis condensation in the presence of a catalyst. It can be mentioned.

  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 usage-amount of a catalyst becomes like this. Preferably it is 0.0001-1.0 mol with respect to 1 mol of hydrolysable silane, More preferably, it is the range of 0.0005-0.1 mol.

  Use water for hydrolysis and condensation. The quantity ratio of hydrolyzable silane and water is not particularly limited. The amount of water used is preferably 0.1 to 100 mol of water, more preferably 0.5 to 3 mol, per mol of hydrolyzable silane. If the amount of water is too small, the reaction slows down, and the yield of the desired silsesquioxane compound of the present invention may be lowered. If the amount of water is too large, the molecular weight increases and the desired structure is obtained. Product may be reduced. Moreover, when using a basic catalyst as aqueous solution, the water to be used may be substituted with the water, and water may be added separately.

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

  As the polar organic solvent, lower alcohols such as methanol, ethanol and 2-propanol, ketones such as acetone and methyl isobutyl ketone, and ethers such as tetrahydrofuran are used. Particularly, acetone and tetrahydrofuran have a low boiling point and the system is uniform. It is preferable because 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 hydrolysis condensation is 0 to 200 ° C, preferably 10 to 200 ° C, and more preferably 10 to 120 ° C. Although this reaction can be carried out regardless of pressure, a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable.

  In the hydrolysis-condensation reaction, the condensation reaction proceeds with hydrolysis, and most of the hydrolyzable group of the hydrolyzable silane [specifically, for example, X in the general formula (VII)], preferably 100% It is preferable from the viewpoint of liquid stability that it is hydrolyzed to a hydroxyl group (OH group), and further, most of the OH group, preferably 80% or more, more preferably 90% or more, particularly preferably 100%, is condensed.

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

  The silsesquioxane compound of this invention is manufactured by the above manufacturing method.

  Here, when 100% condensation does not occur in the hydrolysis condensation, the product obtained by the present production method includes a silsesquioxane compound having a structure in which all of the Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed. In addition, a silsesquioxane compound of the present invention obtained by the present production method, which may contain a ladder structure, an incomplete cage structure and / or a random condensate silsesquioxane compound in which a Si-OH group remains, may be included. The sun compound may contain a ladder structure, an incomplete cage structure and / or a random condensate. In the silsesquioxane compound of the present invention obtained by the present production method, the ratio of the silsesquioxane compound having a structure in which all Si—OH groups are hydrolyzed and condensed is preferably 80% by mass or more, more preferably. It is preferably 90% by mass or more from the viewpoint of liquid stability.

Manufacturing method B
Production method B includes a step of producing a silsesquioxane compound having a corresponding epoxy group or amino group using a hydrolyzable silane having an epoxy group or an amino group, and a silsesquioxane obtained by the step An organic group bonded directly to a silicon atom by reacting a compound having a (meth) acryloyloxy group with the silsesquioxane compound using an epoxy group or an amino group of the compound, and ( A production method for obtaining a silsesquioxane compound having an organic group having two or more (meth) acryloyloxy groups may be mentioned.

Manufacturing method B1
As one mode of manufacturing method B (manufacturing method B1), Step B1-1 for manufacturing a silsesquioxane compound having an epoxy group using hydrolyzable silane having an epoxy group, Step B1-1 The silsesquioxane having a secondary hydroxyl group and one (meth) acryloyl group by reacting the carboxyl group of the compound having a (meth) acryloyloxy group and a carboxyl group with the epoxy group of the silsesquioxane compound obtained by Step B1-2 for producing the compound, and the secondary hydroxyl group of the silsesquioxane compound obtained in Step B1-2 is reacted with the isocyanate group of the compound having a (meth) acryloyloxy group and an isocyanate group. A manufacturing method including the B1-3 process is mentioned.

Step B1-1 Specific examples of the hydrolyzable silane having an epoxy group used in Step B1-1 include the hydrolyzable silane represented by the following general formula (II-6) and the following general formula. A hydrolyzable silane represented by the formula (III-6) is mentioned.

^{R 3} in the general formula (II-6) is the same as ^{R 3} in the general formula (II-1).
X is chlorine or a C1-C6 alkoxy group, and X may be the same or different. Specific examples of X include chlorine, methoxy group, ethoxy group, propoxy group, butoxy group and the like.

^{R 7} in the general formula (III-6) is the same as ^{R 7} in the general formula (III-1). X is chlorine or a C1-C6 alkoxy group, and X may be the same or different. Specific examples of X include chlorine, methoxy group, ethoxy group, propoxy group, butoxy group and the like.

In order to obtain a silsesquioxane compound having an epoxy group in the step B1-1, specifically,
The hydrolyzable silane represented by the general formula (II-6) and / or the hydrolyzable silane represented by the general formula (III-6) is used as a starting material for hydrolysis condensation in the presence of a catalyst. Or
Hydrolyzable other than hydrolyzable silane represented by general formula (II-6) and / or hydrolyzable silane represented by general formula (III-6) and hydrolyzable silane having an epoxy group Examples include hydrolytic condensation using silane as a starting material in the presence of a catalyst.

  The hydrolyzable silane other than the hydrolyzable silane having an epoxy group is particularly limited as long as it can produce a silsesquioxane compound by hydrolytic condensation together with the hydrolyzable silane having the epoxy group. It is not a thing. Specific examples include alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane.

  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 usage-amount of a catalyst becomes like this. Preferably it is 0.0001-1.0 mol with respect to 1 mol of hydrolysable silane, More preferably, it is the range of 0.0005-0.1 mol.

  Use water for hydrolysis and condensation. The quantity ratio of hydrolyzable silane and water is not particularly limited. The amount of water used is preferably 0.1 to 100 moles of water, more preferably 1.5 to 3 moles per mole 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 be used or may not be used. It is preferable to use an organic solvent from the viewpoint of preventing gelation and adjusting the viscosity during production. As the organic solvent, polar organic solvents and nonpolar organic solvents can be used alone or as a mixture.

  As the polar organic solvent, lower alcohols such as methanol, ethanol and 2-propanol, ketones such as acetone and methyl isobutyl ketone, and ethers such as tetrahydrofuran are used. Particularly, acetone and tetrahydrofuran have a low boiling point and the system is uniform. It is preferable because 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 hydrolysis condensation is 0 to 200 ° C, preferably 10 to 200 ° C, and more preferably 10 to 120 ° C.

  In the hydrolysis-condensation reaction, the condensation reaction proceeds with hydrolysis, and the hydrolyzable group of the hydrolyzable silane [specifically, for example, X in the general formula (II-6) and the general formula (III- 6), most of X of X], 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 from the viewpoint of liquid stability.

Step B1-2 In Step B1-2, specifically, for example, an organic group bonded directly to the silicon atom obtained in Step B1-1 is represented by the following general formula (II-7). A compound represented by the following general formula (II-8) is reacted with a silsesquioxane compound having an organic group, and the organic group bonded directly to the silicon atom is represented by the following general formula (II-9). A silsesquioxane compound having an organic group is produced.

^{R 3} in the general formula (II-7) is the same as ^{R 3} in the general formula (II-1).
^{R 2} in the general formula (II-8) is the same as ^{R 2} in the general formula (II-1). ^{R 2} in the general formula (II-9) is the same as ^{R 2} in the general formula (II-8), ^{R 3} is the same as ^{R 3} in the general formula (II-7) is there.

  As another specific example, for example, a silsesquioxane compound having an organic group represented by the following general formula (III-7) as an organic group directly bonded to the silicon atom obtained in the step B1-1. A silsesquioxane compound having an organic group represented by the following general formula (III-9) as an organic group directly bonded to a silicon atom by reacting a compound represented by the following general formula (III-8) To manufacture.

[In General Formula (III-7), R ⁷ is the same as defined above.
In General Formula (III-8), R ⁶ is the same as described above.
In General Formula (III-9), R ⁶ and R ⁷ are the same as described above. ].

  A silsesquioxane compound having an organic group represented by the general formula (II-9) as an organic group directly bonded to the silicon atom, and the general formula (III) as an organic group directly bonded to the silicon atom. The reaction for producing the silsesquioxane compound having an organic group represented by -9) can be carried out according to a conventional method in which an epoxy group and a carboxyl group are reacted.

  The ratio of the silsesquioxane compound having an organic group represented by the general formula (II-7) and the compound represented by the general formula (II-8) in the above reaction is such that the silsesquioxane compound is used. The compound represented by the general formula (II-8) is usually about 0.80 to 1.20 mol, preferably 0.90 to 1 mol of the organic group represented by the general formula (II-7). What is necessary is just to be about 1.10 mol.

  The ratio of the silsesquioxane compound having an organic group represented by the general formula (III-7) and the compound represented by the general formula (III-8) in the above reaction is such that the silsesquioxane compound is used. The amount of the compound represented by the general formula (III-8) is usually about 0.80 to 1.20 mol, preferably 0.80 to 1 mol of the organic group represented by the general formula (III-7). What is necessary is just to be about 1.20 mol.

  These reactions are usually completed in about 10 to 24 hours. The reaction temperature is, for example, 0 to 200 ° C, preferably 20 to 200 ° C, more preferably 20 to 120 ° C.

  In the reaction, a catalyst may be appropriately used. 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, imidazoles, diaza Examples thereof include cyclic nitrogen-containing compounds such as bicycloundecene and phosphorus compounds such as triphenylphosphine and tributylphosphine. Although the usage-amount of a catalyst is not specifically limited, It is 0.01-5 mass% with respect to the reaction raw material.

  In the reaction, a solvent may be appropriately used. The solvent is not particularly limited. Specifically, for example, ketones 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. Esters; ethers such as tetrahydrofuran, dioxane, dimethoxyethane; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; toluene, xylene, etc. Aromatic hydrocarbons, aliphatic hydrocarbons and the like.

Step B1-3 Step In the step B1-3, specifically, for example, the organic group directly bonded to the silicon atom obtained by the step B1-2 is represented by the general formula (II-9). The isocyanate group of the compound represented by the following general formula (II-10) is reacted with the secondary hydroxyl group of the silsesquioxane compound having an organic group.

[In General Formula (II-10), R ⁴ and R ⁵ are the same as above. ].

  By carrying out this reaction, a silsesquioxane compound having an organic group represented by the general formula (II-1) as an organic group directly bonded to a silicon atom can be obtained.

  As another specific example, for example, a silsesquioxane compound having an organic group represented by the general formula (III-9) as an organic group directly bonded to a silicon atom obtained by the step B1-2 is used. The secondary hydroxyl group is reacted with an isocyanate group of a compound represented by the following general formula (III-10).

[R ⁸ and R ^{9 in} General Formula (III-10) are the same as above. ].

  By performing this reaction, a silsesquioxane compound having an organic group represented by the general formula (III-1) as an organic group directly bonded to a silicon atom can be obtained.

The said reaction can be performed in accordance with the conventional method with which a hydroxyl group and an isocyanate group are made to react.
As reaction temperature, it is 0-200 degreeC, Preferably it is 10-200 degreeC, More preferably, it is 10-120 degreeC. 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 (II-9) and the compound represented by the general formula (II-10) in the above reaction is such that the silsesquioxane compound is used. The compound represented by the general formula (II-10) is usually about 0.90 to 1.10 mol, preferably 0.95 to 1 mol of the organic group represented by the general formula (II-9). What is necessary is just to be about 1.05 mol.

  The ratio of the silsesquioxane compound having an organic group represented by the general formula (III-9) and the compound represented by the general formula (III-10) in the above reaction is such that the silsesquioxane compound is The compound represented by the general formula (III-10) is usually about 0.90 to 1.10 mol, preferably 0.95 to 1 mol of the organic group represented by the general formula (III-9). What is necessary is just to be about 1.05 mol.

  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 silsesquioxane compound of this invention is manufactured by the above manufacturing method.

  Here, in the case where 100% condensation is not performed in the hydrolysis and condensation in the step B1-1, the product obtained by the production method B1 has a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed. In addition to the silsesquioxane compound, a ladder structure in which a Si—OH group remains, an incomplete cage structure, and / or a random condensate silsesquioxane compound may be contained, but the production method B1 is used. The silsesquioxane compound of the present invention may contain a ladder structure, an incomplete cage structure and / or a random condensate.

Manufacturing method B2
As another embodiment of the production method B (production method B2), the step B2-1 for producing a silsesquioxane compound having two amino groups using a hydrolyzable silane having two amino groups, A production method comprising a step B2-2 in which the two amino groups of the silsesquioxane compound obtained in the step B2-1 are reacted with the isocyanate group of a compound having a (meth) acryloyloxy group and an isocyanate group. Is mentioned.

Step B2-1 Specific examples of the hydrolyzable silane having two amino groups used in Step B2-1 include hydrolyzable silanes represented by the following general formula (IV-5). It is done.

[In General Formula (IV-5), R ¹² and X are the same as defined above.
X may be the same or different. ].

In order to obtain a silsesquioxane compound having two amino groups in the step B2-1, specifically,
Hydrolyzing condensation in the presence of a catalyst using the hydrolyzable silane represented by the general formula (IV-5) as a starting material, or
Hydrolysis-condensation in the presence of a catalyst using a hydrolyzable silane represented by the general formula (IV-5) and a hydrolyzable silane other than a hydrolyzable silane having two amino groups as a starting material; Can be mentioned.

  The hydrolyzable silane other than the hydrolyzable silane having the two amino groups may be any one that can produce a silsesquioxane compound by hydrolytic condensation together with the hydrolyzable silane having the two amino groups. It is not particularly limited. Specific examples include alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane.

  Examples of reaction conditions such as a catalyst, a solvent, a reaction temperature, and a reaction time in the hydrolysis condensation include the same reaction conditions as the hydrolysis condensation reaction exemplified in the description of the step B1-1.

  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 X in the general formula (IV-5)], 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.

Step B2-2 In step B2-2, specifically, for example, an organic group directly bonded to a silicon atom obtained in step B2-1 is represented by the following general formula (IV-6). The isocyanate group of the compound represented by the following general formula (IV-7) is reacted with the amino group of the silsesquioxane compound having an organic group.

[In General Formula (IV-6), R ¹² is the same as defined above.
In General Formula (IV-7), R ¹⁰ and R ¹¹ are the same as described above. ].

  The reaction is usually performed using 2 mol or more of the compound represented by the general formula (IV-7) with respect to 1 mol of the organic group represented by the general formula (IV-6).

  By performing this reaction, a silsesquioxane compound having an organic group represented by the general formula (IV-1) as an organic group directly bonded to a silicon atom can be obtained.

  The said reaction can be performed in accordance with the conventional method with which an amino group and an isocyanate group are made to react. The reaction temperature is, for example, -78 ° C to 200 ° C, preferably -78 ° C to 100 ° C, more preferably -10 ° C to 40 ° C. Although this reaction can be carried out regardless of pressure, a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferable. Since the reaction is very fast, the reaction usually ends as soon as the dropping is completed.

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

  The silsesquioxane compound of this invention is manufactured by the above manufacturing method.

  Here, in the case where 100% condensation is not performed in the hydrolysis and condensation in the step B2-1, the product obtained by the production method B2 has a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed. In addition to the silsesquioxane compound, a ladder structure in which an Si—OH group remains, an incomplete cage structure, and / or a random condensate silsesquioxane compound may be contained, but the production method B2 may be used. The silsesquioxane compound of the present invention may contain a ladder structure, an incomplete cage structure and / or a random condensate. In the silsesquioxane compound of the present invention obtained by the present production method, the ratio of the silsesquioxane compound having a structure in which all Si—OH groups are hydrolyzed and condensed is preferably 80% by mass or more, more preferably. It is preferably 90% by mass or more from the viewpoint of liquid stability.

Manufacturing method B3
As another aspect of the production method B (production method B3), a step B3-1 for producing a silsesquioxane compound having an epoxy group using a hydrolyzable silane having an epoxy group, the step B3- Step B2-2 for producing a silsesquioxane compound having two or more hydroxyl groups by reacting the carboxyl group of hydroxymonocarboxylic acid with the epoxy group of the silsesquioxane compound obtained in one step, the B2 -2 The manufacturing method including the B3-3 process which makes this isocyanate group of the compound which has a (meth) acryloyloxy group and an isocyanate group react with the hydroxyl group of the silsesquioxane compound obtained by -2 process is mentioned.

Step B3-1 Specific examples of the hydrolyzable silane having an epoxy group used in Step B3-1 include hydrolyzable silanes represented by the following general formula (V-6).

[In General Formula (V-6), R ¹⁶ and X are the same as defined above.
X may be the same or different. ].

In order to obtain a silsesquioxane compound having an epoxy group in the step B3-1, specifically,
Hydrolyzing and condensing in the presence of a catalyst using the hydrolyzable silane represented by the general formula (V-6) as a starting material, or
Hydrolysis-condensation in the presence of a catalyst using a hydrolyzable silane represented by the general formula (V-6) and a hydrolyzable silane other than the hydrolyzable silane having an epoxy group as a starting material; Can be mentioned.

  The hydrolyzable silane other than the hydrolyzable silane having an epoxy group is particularly limited as long as it can produce a silsesquioxane compound by hydrolytic condensation together with the hydrolyzable silane having the epoxy group. It is not a thing. Specific examples include alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane.

  Examples of reaction conditions such as a catalyst, a solvent, a reaction temperature, and a reaction time in the hydrolysis condensation include the same reaction conditions as the hydrolysis condensation reaction exemplified in the description of the step B1-1.

  In the hydrolysis-condensation reaction, the condensation reaction proceeds with hydrolysis, and the hydrolyzable group of the hydrolyzable silane [specifically, for example, most of X in the general formula (V-6)], 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.

Step B3-2 In the step B3-2, specifically, for example, an organic group directly bonded to a silicon atom obtained by the step B3-1 is represented by the following general formula (V-7). A silsesquioxane compound having an organic group is reacted with a compound represented by the following general formula (V-8), and the organic group bonded directly to the silicon atom is represented by the following general formula (V-9). A silsesquioxane compound having an organic group is produced.

[In General Formula (V-7), R ¹⁶ is the same as defined above.
In general formula (V-8), n and R ¹⁵ are the same as above.
In the general formula (V-9), n, R ¹⁵ and R ¹⁶ are the same as described above. ].

  The reaction for producing a silsesquioxane compound having an organic group represented by the general formula (V-9) as an organic group directly bonded to the silicon atom is usually performed by reacting an epoxy group and a carboxyl group. Can be done according to law. As the reaction conditions such as the use ratio of the raw material compound, reaction temperature, catalyst, solvent, reaction time, etc., a silsesquioxane compound having an organic group represented by the general formula (II-7) in Step B1-2 The same reaction conditions as those exemplified for the reaction with the compound represented by formula (II-8) can be mentioned.

Step B3-3 In the step B3-3, specifically, for example, the organic group directly bonded to the silicon atom obtained by the step B3-2 is represented by the general formula (V-9). The isocyanate group of the compound represented by the following general formula (V-10) is reacted with the hydroxyl group of the silsesquioxane compound having an organic group.

[Formula (V-10) ^{R 13} and ^{R 14} in it is as defined above. ].

  The reaction is usually performed using 2 mol or more of the compound represented by the general formula (V-10) with respect to 1 mol of the organic group represented by the general formula (V-9).

  By performing this reaction, a silsesquioxane compound having an organic group represented by the general formula (V-1) as an organic group directly bonded to a silicon atom can be obtained.

  The said reaction can be performed in accordance with the conventional method with which a hydroxyl group and an isocyanate group are made to react. Examples of the reaction conditions such as reaction temperature, catalyst, reaction time, and the like include the same reaction conditions as those exemplified in Step B1-3.

  The silsesquioxane compound of this invention is manufactured by the above manufacturing method.

  Here, in the case where 100% condensation is not performed in the hydrolysis condensation in the step B3-1, the product obtained by the production method B3 has a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed. In addition to the silsesquioxane compound, a ladder structure in which a Si—OH group remains, an incomplete cage structure, and / or a random condensate silsesquioxane compound may be contained, but the production method B3 is used. The silsesquioxane compound of the present invention may contain a ladder structure, an incomplete cage structure and / or a random condensate. In the silsesquioxane compound of the present invention obtained by the present production method, the ratio of the silsesquioxane compound having a structure in which all Si—OH groups are hydrolyzed and condensed is preferably 80% by mass or more, more preferably. It is preferably 90% by mass or more from the viewpoint of liquid stability.

  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.

Active energy ray-curable composition The active energy ray-curable composition of the present invention contains the silsesquioxane compound of the present invention and a photopolymerization initiator.

  The use ratio of the silsesquioxane compound (nonvolatile content) of the present invention in the nonvolatile content of 100 parts by weight of the active energy ray-curable composition of the present invention is not particularly limited, but is preferably 5 to 99 parts by mass, more preferably 10 to 80 parts by mass.

The photopolymerization initiator is not particularly limited as long as it is an initiator that absorbs active energy rays and generates radicals.

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

  Examples of commercially available photopolymerization initiators include IRGACURE-184, 261, 500, 651, 907, CGI-1700 (trade name, manufactured by Ciba Specialty Chemicals), Darocur (Darocur). ) -1173, 1116, 2959, 1664, 4043 (trade name, manufactured by Merck Japan), KAYACURE-MBP, DETX-S, DMBI, EPA, OA (Nippon Kayaku ( Co., Ltd., trade name), VICURE-10, 55 (made by STAUFFER Co., LTD., Trade name), TRIGONAL P1 [AKZO Co., LTD.] Product name], SANDORAY 1000 (manufactured by SANDOZ Co., LTD., Product name), DEAP (manufactured by APJOHN Co., LTD., Product name), CANTACURE QUANTACURE) -PDO, the ITX, the EPD [Ward shake Kin Sopu, Inc. (WARD BLEKINSOP Co., LTD.), Trade name], and the like can be given.

  The photopolymerization initiator is preferably one or a mixture of two or more of thioxanthones, acetophenones and acylphosphine oxides from the viewpoint of photocurability, and among them, acetophenones and acylphosphine oxides. It is particularly preferred to be a mixture with.

  Although the usage-amount of a photoinitiator is not specifically limited, 0.5-10 mass parts is preferable with respect to 100 mass parts of total amounts of the silsesquioxane compound and polymerizable unsaturated compound of this invention. More preferably, it is the range of 1-5 mass parts. 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.

The polymerizable unsaturated compound or the active energy ray-curable composition of the present invention may contain a polymerizable unsaturated compound other than the silsesquioxane compound of the present invention. The polymerizable unsaturated compound is not particularly limited as long as it is a compound other than the silsesquioxane compound of the present invention and has at least one polymerizable unsaturated double bond in its chemical structure.

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

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

  Examples of the polyfunctional polymerizable unsaturated compound include an esterified product of a polyhydric alcohol and (meth) acrylic acid. Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, Dipentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, etc. Meth) acrylate compounds; glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, ε-caprolactone modified tris (acryloxyethyl) isocyanurate, etc. tri (meth) acrylate compound; pentaerythritol tetra (meth) acrylate etc. tetra (meth) acrylate compound; other dipentaerythritol penta (meth) acrylate And dipentaerythritol hexa (meth) acrylate. Furthermore, urethane (meth) acrylate resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin and the like can be mentioned. The urethane (meth) acrylate resin is prepared by, for example, using a polyisocyanate compound, a hydroxylalkyl (meth) acrylate, and a polyol compound as raw materials, and reacting them in an amount such that the hydroxyl group is equimolar or excessive with respect to the isocyanate group. Obtainable. These polymerizable unsaturated compounds can be used alone or in combination of two or more.

  The amount used in the case of containing the polymerizable unsaturated compound is not particularly limited, but from the viewpoint of the physical properties of the obtained coating film, the non-volatile content of the silsesquioxane compound of the present invention is 100 parts by mass. 0.1 to 1000 parts by mass is preferable, and 20 to 200 parts by mass is more preferable.

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

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

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

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

  The article to be coated is not particularly limited. Specific examples include metals, ceramics, glass, plastics, wood, and the like.

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

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

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

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

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

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

( ²⁹ Si-NMR, ¹ H-NMR analysis)
Apparatus: FT-NMR EX-400 manufactured by JEOL
Solvent: CDCl ₃
Internal standard: Tetramethylsilane (FT-IR analysis)
Apparatus: FT / IR-610 manufactured by JASCO Corporation

(SP value measurement method)
The SP value in this example is a solubility parameter, which can be measured by cloud point titration, which is a simple measurement method. W. SUH, J. et al. M.M. It is a value calculated according to the CORBETT equation (see description of Journalof Applied Polymer Science, 12, 2359, 1968).
Formula SP = (√Vml · δH + √Vmh · δD) / (√Vml + √Vmh)
In cloud point titration, when 0.5 g of sample was dissolved in 10 ml of acetone, n-hexane was added and the titration amount H (ml) at the cloud point was read, and similarly deionized water was added to the acetone solution. The titration amount D (ml) at the cloud point is read and applied to the following formula to calculate Vml, Vmh, δH, and δD. The molecular volume (mol / ml) of each solvent is acetone: 74.4, n-hexane: 130.3, deionized water: 18, and SP of each solvent is acetone: 9.75, n- Hexane: 7.24, deionized water: 23.43.
Vml = 74.4 × 130.3 / ((1−VH) × 130.3 + VH × 74.4)
Vmh = 74.4 × 18 / ((1−VD) × 18 + VD × 74.4)
VH = H / (10 + H)
VD = D / (10 + D)
δH = 9.75 × 10 / (10 + H) + 7.24 × H / (10 + H)
δD = 9.75 × 10 / (10 + D) + 23.43 × D / (10 + D)

Example 1
A separable flask equipped with a reflux condenser, thermometer, air inlet tube, and 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-isocyanatoethyl 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 (P1).

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

As a result of ²⁹ Si-NMR analysis of the product (P1), only a peak near −70 ppm derived from the T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si was confirmed. The T1 and T2 structures indicating the presence of were not confirmed.

Further, as a result of ¹ H-NMR analysis of the product (P1), 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.

  Moreover, as a result of performing FT-IR analysis about the product (P1), the peak of 1540cm <-1> vicinity which was attributed to the urethane bond which was not confirmed in the raw material Glycidyl POSS cage mixture was confirmed.

  Further, the NCO value of the product (P1) was 0 mg NCO / g.

  Moreover, the weight average molecular weight of the product (P1) was 5,000.

From the results of the ²⁹ Si-NMR, ¹ H-NMR, FT-IR, weight average molecular weight and the like for the product (P1), almost all of the organic groups in which the product (P1) was directly bonded to the silicon atom were found. Organic group represented by the following formula (II-11)

It was confirmed to be a silsesquioxane compound having a weight average molecular weight of 5,000. The resulting silsesquioxane compound had an SP value of 11.1.

(Example 2)
While adding 455 parts of 2-hydroxyethyl acrylate, 870 parts of isophorone diisocyanate, 1 part of methoquinone, and 883 parts of butyl acetate to a separable flask equipped with a reflux condenser, a thermometer, an air introduction tube, and a stirrer, blowing dry air The mixture was reacted at 60 ° C. for 24 hours to obtain a 60% nonvolatile solution of the product (P2). The NCO value of the product (P2) was 144 mg NCO / g.

  400 parts of Glycidyl POSS cage mixture and 600 parts of butyl acetate were charged into a separable flask equipped with a reflux condenser, a thermometer, an air introduction tube, and a stirrer, and dissolved while stirring at 60 ° C. 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, 1,350 parts of a 60% nonvolatile solution of the product (P2) and 246 parts of butyl acetate were blended and reacted at 80 ° C. for 12 hours to obtain a 50% nonvolatile solution of the product (P3).

As a result of ²⁹ Si-NMR analysis of the product (P3), only a peak around −70 ppm derived from the T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si was confirmed. The T1 and T2 structures indicating the presence of were not confirmed.

Further, as a result of ¹ H-NMR analysis of the product (P3), 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 2.05. Moreover, the peak attributed to an epoxy group was not confirmed. The epoxy equivalent was 10,000 g / eq or more.

  Moreover, as a result of performing FT-IR analysis about the product (P3), the peak of 1540cm <-1> vicinity attributed to the urethane bond which was not confirmed in Glycidyl POSS cage mixture which is a raw material was confirmed.

  Further, the NCO value of the product (P3) was 0 mg NCO / g.

  Moreover, the weight average molecular weight of the product (P3) was 7,000.

From the results of the ²⁹ Si-NMR, ¹ H-NMR, FT-IR, weight average molecular weight and the like for the product (P3), almost all of the organic groups in which the product (P3) was directly bonded to the silicon atom were found. Organic group represented by the following formula (II-12)

[In the formula (II-12), R ²⁰ represents an isophorone diisocyanate residue. It was confirmed that the compound was a silsesquioxane compound having a weight average molecular weight of 7,000. The resulting silsesquioxane compound had an SP value of 10.8.

(Example 3)
A separable flask equipped with a reflux condenser, thermometer, air inlet tube, and stirrer was charged with 400 parts of Epoxycyclohexyl POSS Cage Mixture (trade name, manufactured by Hybrid Plastics) and 600 parts of propylene glycol monomethyl ether acetate and stirred at 60 ° C. While dissolving. 195 parts of methacrylic acid, 1.5 parts of methoquinone, and 10 parts of tetrabutylammonium bromide were added thereto, and reacted at 100 ° C. for 48 hours while blowing dry air. Furthermore, 350 parts of 2-isocyanatoethyl methacrylate and 360 parts of propylene glycol monomethyl ether acetate were added and reacted at 80 ° C. for 12 hours to obtain a 50% non-volatile solution of the product (P4).

  Epoxycyclohexyl POSS Cage Mixture used as a raw material was 2- (3,4-epoxycyclohexyl) ethyl group-containing cage-type polysilsesquioxane, having a weight average molecular weight of 2,200 and an epoxy equivalent of 178 g / eq. .

As a result of ²⁹ Si-NMR analysis of the product (P4), only a peak near −70 ppm derived from the T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si was confirmed. The T1 and T2 structures indicating the presence of were not confirmed.

Further, as a result of ¹ H-NMR analysis of the product (P4), a peak of 0.6 ppm derived from a methylene group bonded to Si was confirmed. Moreover, the peak of 5.5 ppm and 6.1 ppm derived from the carbon-carbon unsaturated bond of a methacryloyloxy group was confirmed. The molar ratio of the carbon-carbon unsaturated bond of the methacryloyloxy group to the methylene group bonded to Si calculated from these peak intensity ratios was 2.01. Moreover, the peak attributed to an epoxy group was not confirmed. The epoxy equivalent was 10,000 g / eq or more.

  Moreover, as a result of conducting FT-IR analysis about the product (P4), the peak of 1540 cm <-1> vicinity which was attributed to the urethane bond which was not confirmed in Epoxycyclohexyl POSS Cage Mixture which is a raw material was confirmed.

  Further, the NCO value of the product (P4) was 0 mg NCO / g.

  The product (P4) had a weight average molecular weight of 6,000.

From the results of the ²⁹ Si-NMR, ¹ H-NMR, FT-IR, weight average molecular weight and the like for the product (P4), almost all of the organic groups in which the product (P4) was directly bonded to the silicon atom were found. Organic group represented by the following formula (III-11)

It was confirmed to be a silsesquioxane compound having a weight average molecular weight of 6,000. The resulting silsesquioxane compound had an SP value of 10.8.

Example 4
In a separable flask equipped with a reflux condenser, a thermometer, an air inlet tube, and a stirrer, 580 parts of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 2,320 parts of 2-propyl alcohol, tetrabutyl 2 parts of ammonium fluoride and 70 parts of deionized water were charged and reacted at 60 ° C. for 8 hours. After concentration to a non-volatile content of 60% by vacuum distillation, 300 parts of butyl acetate was added, and the vacuum distillation was continued to obtain a 60% non-volatile solution of the product (P5).

  A separable flask equipped with a reflux condenser, a thermometer, an air introduction tube, and a stirrer was mixed with 643 parts of butyl acetate and 552 parts of 2-isocyanatoethyl acrylate, and cooled to 10 ° C. while stirring in an ice bath. 500 parts of a non-volatile content 60% solution of the product (P5) was added dropwise thereto while maintaining the reaction temperature at 10 ° 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 (P6).

As a result of ²⁹ Si-NMR analysis of the product (P5), only a peak around −70 ppm derived from T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si was confirmed, and hydroxysilyl group The T1 and T2 structures indicating the presence of were not confirmed. The total amine value was 730 mg KOH / g.

  The weight average molecular weight of the product (P5) was 2,000.

As a result of ²⁹ Si-NMR analysis of the product (P6), only a peak near −70 ppm derived from the T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si was confirmed. The T1 and T2 structures indicating the presence of were not confirmed. 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 (P6), 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 methacryloyloxy group to the methylene group bonded to Si calculated from these peak intensity ratios was 2.01.

  The weight average molecular weight of the product (P6) was 5,600.

From the results of the ²⁹ Si-NMR, ¹ H-NMR, weight average molecular weight and the like for the product (P6), almost all of the organic groups in which the product (P6) was directly bonded to the silicon atom were represented by the following formula (IV Organic group represented by -8)

It was confirmed to be a silsesquioxane compound having a weight average molecular weight of 5,600. The resulting silsesquioxane compound had an SP value of 13.4.

(Example 5)
In a separable flask equipped with a reflux condenser, a thermometer, an air inlet tube, and a stirrer, 482 parts of butyl acetate and 1,910 parts of a 60% non-volatile solution of the product (P2) were blended and stirred in an ice bath. While cooling to 10 ° C. Here, 500 parts of a 60% nonvolatile solution of the product (P5) was added dropwise 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% nonvolatile solution of the product (P7).

As a result of ²⁹ Si-NMR analysis of the product (P7), only a peak near −70 ppm derived from T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si was confirmed, and hydroxysilyl group The T1 and T2 structures indicating the presence of were not confirmed. 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 (P7), 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 2.05.

  The weight average molecular weight of the product (P7) was 10,000.

From the results of the ²⁹ Si-NMR, ¹ H-NMR, weight average molecular weight and the like for the product (P7), almost all of the organic groups in which the product (P7) was directly bonded to the silicon atom were represented by the following formula (IV Organic group represented by -9)

[In formula (IV-9), R ²¹ represents an isophorone diisocyanate residue. And a silsesquioxane compound having a weight average molecular weight of 10,000. The resulting silsesquioxane compound had an SP value of 13.1.

(Example 6)
400 parts of Glycidyl POSS cage mixture and 600 parts of butyl acetate were charged into a separable flask equipped with a reflux condenser, a thermometer, an air introduction tube, and a stirrer, and dissolved while stirring at 60 ° C. Here, 355 parts of dimethylolpropionic acid and 10 parts of tetrabutylammonium bromide were charged and reacted at 100 ° C. for 24 hours. Further, 1,010 parts of 2-isocyanatoethyl acrylate, 1,200 parts of butyl acetate and 2 parts of methoquinone were blended and reacted at 80 ° C. for 12 hours while blowing dry air, and a 50% non-volatile solution of the product (P8) Got.

As a result of ²⁹ Si-NMR analysis of the product (P8), only a peak near −70 ppm derived from the T3 structure in which all three oxygen atoms bonded to Si were bonded to other Si was confirmed. The T1 and T2 structures indicating the presence of were not confirmed. The acid value was 0 mgKOH / g.

Further, as a result of ¹ H-NMR analysis of the product (P8), 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 3.00. Moreover, the peak attributed to an epoxy group was not confirmed. The epoxy equivalent was 10,000 g / eq or more.

  Moreover, as a result of performing FT-IR analysis about the product (P8), the peak of 1540cm <-1> vicinity attributed to the urethane bond which was not confirmed in Glycidyl POSS Cage Mixture which is a raw material was confirmed.

  Further, the NCO value of the product (P8) was 0 mg NCO / g.

  Moreover, the weight average molecular weight of the product (P8) was 8,000.

From the results of the ²⁹ Si-NMR, ¹ H-NMR, FT-IR, weight average molecular weight and the like for the product (P8), almost all of the organic groups in which the product (P8) was directly bonded to the silicon atom were found. Organic group represented by the following formula (V-11)

And a silsesquioxane compound having a weight average molecular weight of 8,000. The SP value of the obtained silsesquioxane compound was 11.0.

(Comparative Example 1)
A separable flask equipped with a reflux condenser, a thermometer, and a stirrer was charged with 300 parts of toluene, 30 parts of tetrabutylammonium hydroxide 40% methanol solution, and 12 parts of deionized water, and cooled to 2 ° C. with an ice bath. 110 parts of 3-acryloyloxypropyltrimethoxysilane diluted with 300 parts of tetrahydrofuran was added thereto and reacted at 20 ° C. for 24 hours. After removing the volatile components by distillation under reduced pressure, the product was dissolved in 100 parts of propylene glycol monomethyl ether acetate to obtain a 50% non-volatile solution of the product (P9).

As a result of ²⁹ Si-NMR analysis of the product (P9), 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.

Further, as a result of ¹ H-NMR analysis of the product (P9), 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 1.00.

  Moreover, the weight average molecular weight of the product (P9) was 1,500.

From the results of the ²⁹ Si-NMR, ¹ H-NMR, FT-IR, weight average molecular weight and the like for the product (P9), all the organic groups in which the product (P9) was directly bonded to the silicon atom were as follows: Organic group represented by formula (VIII)

It was confirmed to be a silsesquioxane compound having a weight average molecular weight of 1,500. The SP value of the obtained silsesquioxane compound was 9.5.

(Example 7)
A 50% non-volatile solution of the product (P1) obtained in Example 1 and the following polymerizable unsaturated compound (A1), the mass ratio of the product (P1) and polymerizable unsaturated compound (A1) is 1. 1 and mixed at 40 ° C. for 24 hours to obtain a mixed solution. By evaluating the compatibility of the mixed solution, the compatibility of the product (P1) obtained in Example 1 and the polymerizable unsaturated compound in a solution state was evaluated. The evaluation was carried out according to the following criteria by visually observing the compatible state. The evaluation results are shown in Table 1.

  Further, in the same manner as described above, the product (P1) and each of the following polymerizable unsaturated compounds (A2) to (A8) were mixed to obtain mixed solutions. And the compatibility of this mixed solution was evaluated on the same basis as the above. The evaluation results are shown in Table 1.

<Compatibility determination>
○: Uniform and transparent, good compatibility Δ: Slightly turbid, or fluctuating when shaken, poor compatibility ×: considerably turbid, or separation, aggregation, sediment, gel Any one or more of the above are observed, and the compatibility is poor <Polymerizable unsaturated compound>
A1: HDDA (trade name, manufactured by Daicel Cytec, 1,6-hexanediol diacrylate)
A2: Aronix M-140 (trade name, manufactured by Toa Gosei Co., Ltd., N-acryloyloxyethyl hexahydrophthalimide)
A3: Aronix M-325 [trade name, manufactured by Toa Gosei Co., Ltd., ε-caprolactone-modified tris (acryloxyethyl) isocyanurate]
A4: Trimethylolpropane diacrylate A5: Pentaerythritol diacrylate A6: Pentaerythritol triacrylate A7: Aronix M-403 (trade name, manufactured by Toa Gosei Co., Ltd., dipentaerythritol pentaacrylate and hexaacrylate)
A8: Aronix M-1200 (trade name, manufactured by Toagosei Co., Ltd., bifunctional urethane acrylate oligomer)

(Examples 8 to 12, Comparative Example 2)
In the same manner as in Example 7, for each product (P3, P4, P6, P7, P8, P9) obtained in Examples 2-6 and Comparative Example 1, the phase in a solution state with the polymerizable unsaturated compound The solubility was evaluated. The evaluation results are shown in Table 1.

(Example 13)
About the active energy ray curable composition containing the silsesquioxane compound of this invention, the compatibility at the time of mixing a polymerizable unsaturated compound was evaluated. The test method is shown below.

  100 parts of a 50% non-volatile solution of the product (P1) obtained in Example 1, 50 parts of a polymerizable unsaturated compound (A1), 1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator) 3.0 And 0.54 parts of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (photopolymerization initiator), diluted with ethyl acetate to a non-volatile content of 30%, stirred, and active energy ray curable A composition was prepared.

Next, the active energy ray-curable composition was applied to an intermediate coating plate (Note 1) with an applicator under a condition that the dry film thickness was 10 μm, dried at 80 ° C. for 10 minutes to remove the solvent, and then the high-pressure mercury lamp ( 80 W / cm), ultraviolet rays (peak top wavelength 365 nm) were irradiated at an irradiation amount of 20,000 J / m ² to cure the coating film. The appearance of the cured coating film was visually observed, and the compatibility state was evaluated according to the following criteria. The evaluation results are shown in Table 2.

Also, each polymerizable unsaturated compound (A2) to (A8) was prepared in the same manner as above except that the polymerizable unsaturated compound (A1) was changed to each of the polymerizable unsaturated compound (A2) to (A8). Each active energy ray-curable composition containing each of the above was prepared. Subsequently, the coating film hardened | cured on the same conditions as the above was created, this coating film was observed visually, and the compatible state was evaluated according to the following reference | standard.
The evaluation results are shown in Table 2.

  (Note 1) Intermediate coating plate: 0.8 × 150 × 70 mm cold-rolled steel plate chemical-treated with Palbond # 3020 (trade name, manufactured by Nihon Parkerizing Co., Ltd., zinc phosphate treatment agent), ELECRON GT-10 (trade name) Electrodeposition coating (made by Kansai Paint Co., Ltd., cationic electrodeposition coating) so as to have a film thickness of 20 μm was performed by baking at 170 ° C. for 30 minutes to form an electrodeposition coating film. After spray coating WP-300 (trade name, manufactured by Kansai Paint Co., Ltd., aqueous intermediate coating) on the electrodeposition coating film so that the cured film thickness is 25 μm, it is 140 ° C. × 30 minutes in an electric hot air dryer. Baking and drying were performed to prepare an intermediate coating plate.

<Compatibility determination>
○: Uniform and transparent, good compatibility △: Slightly turbid, poor compatibility ×: Slightly turbid, or any one or more of aggregates, bumps, and repelling , Poor compatibility

(Examples 14 to 18, Comparative Example 3)
The product (P1) with a non-volatile content of 50% was changed to each of the solutions of the products (P3, P4, P6, P7, P8, P9) obtained in Examples 2 to 6 and Comparative Example 1. Produced an active energy ray-curable composition in the same manner as in Example 13. Subsequently, the coating film which hardened this active energy ray curable composition on the conditions similar to Example 13 was created, and the compatibility at the time of mixing a polymerizable unsaturated compound was evaluated. The evaluation results are shown in Table 2.

(Examples 19 to 26)
In the same manner as in the method for producing the active energy ray curable composition and the method for producing the cured coating film in Example 13, an active energy ray curable composition having the composition shown in Table 3 was prepared, and an intermediate coating plate (Note 1) was prepared. ) A cured coating film having a dry film thickness of 10 μm was formed thereon to obtain a test plate. Each test plate obtained was evaluated for scratch resistance and weather resistance. The evaluation results are shown in Table 3.

<Abrasion resistance>
Commercially available steel wool (# 0000) was rubbed on each coating film, and the coating film was visually observed and evaluated according to the following criteria.
○: no scratches, cracks, peeling, or slight scratches, but no problem in practical use Δ: scratches are observed ×: cracks, peeling, significant scratches, etc. are observed

<Weather resistance>
About each obtained test board, after performing the test for 1000 hours using a sunshine weatherometer, the coating film was observed visually and evaluated according to the following reference | standard.
○: No abnormality, or slight swelling, discoloration, gloss change, peeling, etc. are observed, but there are no practical problems. Etc. are remarkably recognized

Claims (7)

  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 an organic group having two or more (meth) acryloyloxy groups. Silsesquioxane compound characterized by the above.   The silsesquioxy according to claim 1, wherein the organic group having two or more (meth) acryloyloxy groups is an organic group having two or more (meth) acryloyloxy groups and having a urethane bond and / or a urea bond. Sun compound. The silsesquide according to claim 2, wherein the organic group having two or more (meth) acryloyloxy groups and having a urethane bond and / or a urea bond is an organic group represented by the following general formula (I-1). Oxan compounds.

[In Formula (I-1), R ¹ represents a hydrogen atom or a methyl group, m represents an integer of 2 to 5, and Y represents a (m + 1) -valent organic group having a urethane bond and / or a urea bond. .
However, m H ₂ C═ (R ¹ ) COO— groups are each bonded to two or more different carbons constituting the organic group that is Y. The organic group represented by the general formula (I-1) is any one of organic groups represented by the following general formula (II-1) to general formula (V-1). Silsesquioxane compound.

{In Formula (II-1), R ² represents a hydrogen atom or a methyl group, R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ is a divalent hydrocarbon group having 1 to 10 carbon atoms or the following general formula (VI)

[In the formula (VI), R ¹⁷ represents a divalent hydrocarbon group having 2 to 4 carbon atoms, and R ¹⁸ represents a diisocyanate residue. ]
The bivalent group represented by these is shown.
In formula (III-1), R ⁶ represents a hydrogen atom or a methyl group,
R ⁷ represents a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ⁸ represents a hydrogen atom or a methyl group,
R ⁹ represents a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent group represented by the general formula (VI).
In formula (IV-1), each R ¹⁰ represents a hydrogen atom or a methyl group which may be the same or different,
R ¹¹ represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may be the same or different, or a divalent group represented by the general formula (VI),
R ¹² represents a divalent hydrocarbon group having 1 to 10 carbon atoms.
In formula (V-1), n represents an integer of 1 to 3,
R ¹³ represents a hydrogen atom or a methyl group, which may be the same or different,
R ¹⁴ represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may be the same or different, or a divalent group represented by the above general formula (VI),
R ¹⁵ represents an (n + 1) -valent hydrocarbon group having 1 to 10 carbon atoms,
R ¹⁶ represents a divalent hydrocarbon group having 1 to 10 carbon atoms.
However, when n is 2 or 3, the H ₂ C═C (R ¹³ ) COOR ¹⁴ NHCOO— group is bonded to two or more different carbons constituting the hydrocarbon group of R ^15. }   The silsesquioxane compound according to claim 1, which has a weight average molecular weight of 1,000 to 100,000.   An active energy ray-curable composition containing the silsesquioxane compound according to claim 1 and a photopolymerization initiator.   The active energy ray-curable composition according to claim 6, further comprising a polymerizable unsaturated compound other than the silsesquioxane compound.