WO2010067684A1 - Composé silsesquioxane ayant un groupe fonctionnel polymérisable - Google Patents

Composé silsesquioxane ayant un groupe fonctionnel polymérisable Download PDF

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WO2010067684A1
WO2010067684A1 PCT/JP2009/069138 JP2009069138W WO2010067684A1 WO 2010067684 A1 WO2010067684 A1 WO 2010067684A1 JP 2009069138 W JP2009069138 W JP 2009069138W WO 2010067684 A1 WO2010067684 A1 WO 2010067684A1
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group
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compound
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meth
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PCT/JP2009/069138
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Japanese (ja)
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彰典 永井
芳明 千野
政示 小畑
理 磯崎
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関西ペイント株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/148—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • 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.
  • 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. .
  • 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.
  • the compatibility with the polymerizable unsaturated compound having 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.
  • 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.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents an integer of 2 to 5
  • Y represents a (m + 1) -valent organic group having a urethane bond and / or a urea bond.
  • m H 2 C ⁇ (R 1 ) COO— groups are each bonded to two or more different carbons constituting the organic group which is Y].
  • 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)
  • R 17 represents a divalent hydrocarbon group having 2 to 4 carbon atoms
  • R 18 represents a diisocyanate residue.
  • the bivalent group represented by these is shown.
  • 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).
  • R 10 represents a hydrogen atom or a methyl group which may be the same or different
  • R 11 represents a divalent carbon atom having 1 to 10 carbon atoms which may be the same or different
  • R 2 represents a hydrogen group or a divalent group represented by the general formula (VI)
  • R 12 represents a divalent hydrocarbon group having 1 to 10 carbon atoms.
  • 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 may be the same or different.
  • 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.
  • 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. ⁇ .
  • silsesquioxane compound according to any one of items 1 to 4, having a weight average molecular weight of 1,000 to 100,000.
  • 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 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, simply referred to as “silsesquioxane compound of the present invention”) which is an organic group having two or more.
  • 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 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.
  • 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.
  • 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 90% by mass or more, and particularly preferably. Is preferably 100% by mass from the viewpoint of liquid stability.
  • 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.
  • 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).
  • R 1 represents a hydrogen atom or a methyl group
  • m represents an integer of 2 to 5
  • Y represents a (m + 1) -valent organic group having a urethane bond and / or a urea bond.
  • R 1 s may be the same or different.
  • organic group represented by the general formula (I-1) include organic groups represented by the following general formulas (II-1) to (V-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)
  • R 17 represents a divalent hydrocarbon group having 2 to 4 carbon atoms
  • R 18 represents a diisocyanate residue.
  • the bivalent group represented by these is shown.
  • 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).
  • R 10 represents a hydrogen atom or a methyl group which may be the same or different
  • R 11 represents a divalent carbon atom having 1 to 10 carbon atoms which may be the same or different
  • R 2 represents a hydrogen group or a divalent group represented by the general formula (VI)
  • R 12 represents a divalent hydrocarbon group having 1 to 10 carbon atoms.
  • 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 may be the same or different.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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,
  • aliphatic diisocyanate compounds particularly isophorone diisocyanate, are preferred from the viewpoint of excellent weather resistance.
  • the diisocyanate compound of molecular weight 300 or less is preferable from the point which is more excellent in abrasion resistance and active energy ray curability.
  • R 2 is preferable because it has excellent heat resistance, scratch resistance, compatibility with a highly polar polymerizable unsaturated compound and active energy ray curability.
  • 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 is preferable.
  • 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).
  • 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 include the same groups as the divalent hydrocarbon groups exemplified in the description of R 3 in the general formula (II-1). Among these, a divalent hydrocarbon group having 1 to 6 carbon atoms (more preferably 1 to 3 carbon atoms), particularly an ethylene group or a 1,3-propylene group, has excellent 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 these, a divalent hydrocarbon group having 1 to 6 carbon atoms (more preferably 1 to 3 carbon atoms), particularly an ethylene group or a 1,3-propylene group, has excellent 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.
  • 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 is preferable.
  • R 6 is a hydrogen atom
  • R 7 is an ethylene group or a 1,3-propylene group
  • R 8 is a hydrogen atom
  • R 9 is a divalent group represented by the general formula (VI).
  • 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 these, a divalent hydrocarbon group having 1 to 6 carbon atoms (more preferably 1 to 3 carbon atoms), particularly an ethylene group or a 1,3-propylene group, has excellent 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 include the same groups as the divalent hydrocarbon groups exemplified in the description of R 3 in the general formula (II-1). Among these, a divalent hydrocarbon group having 1 to 6 carbon atoms (more preferably 1 to 3 carbon atoms), particularly an ethylene group or a 1,3-propylene group, has excellent heat resistance, scratch resistance and polarity. It is preferable from the viewpoint of more excellent compatibility with a highly polymerizable unsaturated compound.
  • R 10 is preferable because it has excellent heat resistance, scratch resistance, compatibility with a highly polar polymerizable unsaturated compound, and active energy ray curability.
  • R 10 is a hydrogen atom
  • R 11 is a divalent group represented by the general formula (VI)
  • R 17 is an ethylene group
  • 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 these, a divalent hydrocarbon group having 1 to 6 carbon atoms (more preferably 1 to 3 carbon atoms), particularly an ethylene group or a 1,3-propylene group, has excellent 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.
  • divalent hydrocarbon group 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.
  • hydroxy monocarboxylic acid examples include hydroxypivalic acid, glycolic acid, lactic acid, 3-hydroxypropionic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyisobutyric acid, 2 -Hydroxy-2-methylpropionic acid, 3-hydroxyvaleric acid, 5-hydroxyvaleric acid, 2-hydroxycyclohexanecarboxylic acid, dimethylolpropionic acid, dimethylolbutanoic acid, o-hydroxybenzoic acid, m-hydroxybenzoic acid, Examples thereof include p-hydroxybenzoic acid. Of these, dimethylolpropionic acid and dimethylolbutanoic acid are preferred from the 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 include the same groups as the divalent hydrocarbon groups 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.
  • n is a compound having excellent heat resistance, scratch resistance, compatibility with a highly polar polymerizable unsaturated compound and active energy ray curability.
  • 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
  • R 18 is an isophorone diisocyanate residue.
  • Preferred is an organic group which is a divalent group, R 15 is a dimethylolpropionic acid residue, and R 16 is an ethylene group or a 1,3-propylene group.
  • 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 the weight average molecular weight is 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.
  • the weight average molecular weight is a weight average molecular weight measured by a light scattering method.
  • Zetasizer Nano Nano-ZS (Malvern Instruments Ltd.) was used for the measurement of the weight average molecular weight by the light scattering method.
  • the samples used for the measurement were 10 samples having different concentrations in which the silsesquioxane compound of the present invention was dissolved in propylene glycol monomethyl ether and the concentration was adjusted to 0.5 to 5.0% by mass.
  • the weight average molecular weight was determined by measuring the light scattering intensity of these 10 samples.
  • Production method of 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 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.
  • 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.
  • a method for producing the silsesquioxane compound of the present invention by hydrolytic condensation in the presence of a catalyst are used as a starting material.
  • R 19 in the general formula (VII) represents an organic group having two or more (meth) acryloyloxy groups.
  • X is chlorine or an alkoxy group having 1 to 6 carbon atoms, and X may be the same or different.
  • alkoxy group having 1 to 6 carbon atoms examples include linear or branched alkoxy groups having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms). 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.
  • X examples include chlorine, methoxy group, ethoxy group, propoxy group, butoxy group and the like.
  • 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.
  • hydrolyzable silane represented by the general formula (VII) examples include hydrolyzable silanes represented by the following general formula (I-2).
  • R 1 , m, Y and X are the same as defined above. X may be the same or different. ].
  • hydrolyzable silane represented by the general formula (I-2) examples include hydrolyzable silanes represented by the following general formula (II-2) and the following general formula (III-2).
  • the hydrolyzable silane represented by these is mentioned.
  • R 2 , R 3 , R 4 , R 5 and X are the same as defined above.
  • R 6 , R 7 , R 8 , R 9 and X are the same as defined above.
  • X may be the same or different. ].
  • hydrolyzable silane represented by the general formula (II-2) examples 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 the product with a compound represented by the following general formula (II-5).
  • hydrolyzable silane represented by the general formula (II-3) include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane.
  • the compounds represented by the general formula (II-4) are specifically 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, isocyanate octyl ( And (meth) acrylate.
  • an adduct of a hydroxyl group-containing (meth) acrylate and a diisocyanate compound can be mentioned.
  • an adduct of 2-hydroxyethyl (meth) acrylate and isophorone diisocyanate can be mentioned.
  • hydrolyzable silane represented by the general formula (III-2) examples 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 a compound represented by the following general formula (III-5) with the product.
  • hydrolyzable silane represented by the general formula (III-3) examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl). Examples thereof include ethyltriethoxysilane.
  • the compound represented by the general formula (III-4) is specifically acrylic acid or methacrylic acid.
  • 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.
  • 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 mol of the former.
  • 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.
  • a catalyst may be used as appropriate.
  • 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
  • the amount of the catalyst used is not particularly limited, but is 0.01 to 5% by mass with respect to the reaction raw material.
  • 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.
  • 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 such as tetrahydrofuran, dioxane and dimethoxyethane; 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; toluene, xylene and the like Aromatic hydrocarbons, aliphatic hydrocarbons and the like.
  • the reaction with can be carried out according to a conventional method in which a hydroxyl group and an isocyanate group are reacted.
  • the ratio of the product (II-3-4) and the compound represented by the general formula (II-5) used 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 ratio of the product (III-3-4) and the compound represented by the general formula (III-5) used 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.
  • This reaction can be carried out regardless of pressure, but a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferred.
  • the reaction is usually completed in about 2 to 10 hours.
  • a catalyst may be used as appropriate.
  • the catalyst include tertiary amines such as triethylamine and organometallic compounds such as dibutyltin dilaurate.
  • a solvent may be appropriately used.
  • 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.
  • hydrolyzable silane represented by the general formula (I-2) include hydrolyzable silanes represented by the following general formula (IV-2).
  • R 10 , R 11 , R 12 and X are the same as defined above. X may be the same or different. ].
  • hydrolyzable silane represented by the general formula (IV-2) examples 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).
  • hydrolyzable silane represented by the general formula (IV-3) include N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl). -3-aminopropyltriethoxysilane and the like.
  • 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 carried out by adding a hydrolyzate represented by the general formula (IV-3).
  • the reaction is performed 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) can 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.
  • This reaction can be carried out regardless of pressure, but a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferred. Since the reaction is very fast, the reaction usually ends as soon as the dropping is completed.
  • a solvent may be appropriately used.
  • 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.
  • hydrolyzable silane represented by the general formula (I-2) examples include hydrolyzable silanes represented by the following general formula (V-2).
  • 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 a compound represented by the following general formula (V-5) with the product.
  • 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).
  • 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, for example, 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.
  • the reaction between the hydrolyzable silane represented by the general formula (V-3) and the compound represented by the general formula (V-4) can 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 reaction with the compound is usually a product 1 obtained by reacting the hydrolyzable silane represented by the general formula (V-3) with the compound represented by the general formula (V-4).
  • the reaction is carried out using 2 mol or more of the compound represented by formula (V-5) with respect to mol.
  • a 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 product represented by 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.
  • Reaction conditions such as reaction temperature, catalyst, solvent, reaction time, etc. include the hydrolyzable silane represented by the general formula (II-3) and the compound represented by the general formula (II-4).
  • the same reaction conditions as the reaction conditions exemplified in the reaction of the product obtained by the reaction with the compound represented by the general formula (II-5) can be mentioned.
  • 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.
  • a basic catalyst is preferably used as the catalyst.
  • the basic catalyst include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethyl
  • ammonium hydroxide salts such as ammonium hydroxide and ammonium fluoride salts such as tetrabutylammonium fluoride.
  • the amount of the catalyst used is not particularly limited. However, if the amount is too large, there are problems such as high cost and difficulty in removal. On the other hand, if the amount is too small, the reaction becomes slow. Therefore, the amount of the catalyst used is preferably in the range of 0.0001 to 1.0 mol, more preferably 0.0005 to 0.1 mol, relative to 1 mol of hydrolyzable silane.
  • Water is used for hydrolysis condensation.
  • the quantity ratio of hydrolyzable silane and water is not particularly limited.
  • the amount of water used is preferably a ratio of 0.1 to 100 mol, more preferably 0.5 to 3 mol, of water relative to 1 mol of hydrolyzable silane. If the amount of water is too small, the reaction 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.
  • the water to be used may be substituted with the water, and water may be added separately.
  • an organic solvent may or may not be used. It is preferable to use an organic solvent from the viewpoint of preventing gelation and adjusting the viscosity during production.
  • organic solvent polar organic solvents and nonpolar organic solvents can be used alone or as a mixture.
  • 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.
  • 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.
  • mixing a polar organic solvent and a nonpolar organic solvent provides the above-described advantages, so that it is preferably used as a mixed solvent.
  • the reaction temperature during the hydrolysis condensation is 0 to 200 ° C., preferably 10 to 200 ° C., more preferably 10 to 120 ° C. This reaction can be carried out regardless of pressure, but a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferred.
  • the 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.
  • the catalyst is removed by washing with water from the viewpoint of efficiency.
  • the silsesquioxane compound of the present invention is produced by the above production method.
  • the product obtained by this production method includes a silsesquioxane compound having a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed.
  • a silsesquioxane compound of the present invention obtained by the present production method may include a ladder structure, an incomplete cage structure and / or a random condensate silsesquioxane compound in which a Si—OH group remains.
  • the sun compound may contain a ladder structure, an incomplete cage structure and / or a random condensate.
  • 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 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.
  • Step B1-1 One embodiment of the production method B (Production method B1) includes a step B1-1 for producing a silsesquioxane compound having an epoxy group using a hydrolyzable silane having an epoxy group, and the 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 a compound, the isocyanate group of a compound having a (meth) acryloyloxy group and an isocyanate group is reacted with the secondary hydroxyl group of the silsesquioxane compound obtained in Step B1-2
  • a production method including the step B1-3 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 And hydrolyzable silanes represented by the formula (III-6).
  • R 3 in the general formula (II-6) is the same as R 3 in the general formula (II-1).
  • X is chlorine or an alkoxy group having 1 to 6 carbon atoms, 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 an alkoxy group having 1 to 6 carbon atoms, 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.
  • 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.
  • 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.
  • a basic catalyst is preferably used as the catalyst.
  • the basic catalyst include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethyl
  • ammonium hydroxide salts such as ammonium hydroxide and ammonium fluoride salts such as tetrabutylammonium fluoride.
  • the amount of the catalyst used is not particularly limited. However, if the amount is too large, there are problems such as high cost and difficulty in removal. On the other hand, if the amount is too small, the reaction becomes slow. Therefore, the amount of the catalyst used is preferably in the range of 0.0001 to 1.0 mol, more preferably 0.0005 to 0.1 mol, relative to 1 mol of hydrolyzable silane.
  • Water is used for hydrolysis 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, more preferably 1.5 to 3 mol, of water per mol of hydrolyzable silane. If the amount of water is too small, the reaction may be slowed and the yield of the desired silsesquioxane 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.
  • the water to be used may be substituted with the water, and water may be added separately.
  • an organic solvent may or may not be used. It is preferable to use an organic solvent from the viewpoint of preventing gelation and adjusting the viscosity during production.
  • organic solvent polar organic solvents and nonpolar organic solvents can be used alone or as a mixture.
  • 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.
  • 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.
  • mixing a polar organic solvent and a nonpolar organic solvent provides the above-described advantages, so that it is preferably used as a mixed solvent.
  • the reaction temperature during the hydrolysis condensation is 0 to 200 ° C., preferably 10 to 200 ° C., more preferably 10 to 120 ° C.
  • the condensation reaction proceeds together 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 an organic group directly bonded to a silicon atom obtained in Step B1-1 is represented by the following general formula (II-7)
  • a silsesquioxane compound having an organic group is reacted with a compound represented by the following general formula (II-8), and the organic group directly bonded 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.
  • 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 is used.
  • R 7 is the same as defined above.
  • R 6 is the same as defined above.
  • R 7 is the same as defined above.
  • the reaction for producing the silsesquioxane compound having an organic group represented by ⁇ 9) can be performed according to a conventional method in which an epoxy group and a carboxyl group are reacted.
  • the use 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 amount of the compound represented by the general formula (II-8) is usually about 0.80 to 1.20 mol, preferably 0.90 to 1 mol per 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
  • the amount of the compound represented by the general formula (III-8) is usually about 0.80 to 1.20 moles, preferably 0.80 to 1 mole per 1 mole of the organic group represented by the general formula (III-7). What is necessary is just to be about 1.20 mol.
  • reaction temperature is, for example, 0 to 200 ° C, preferably 20 to 200 ° C, more preferably 20 to 120 ° C.
  • a catalyst may be used as appropriate.
  • 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
  • the amount of the catalyst used is not particularly limited, but is 0.01 to 5% by mass with respect to the reaction raw material.
  • 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.
  • 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 such as tetrahydrofuran, dioxane and dimethoxyethane; 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; toluene, xylene and the like Aromatic hydrocarbons, aliphatic hydrocarbons and the like.
  • Step B1-3 Step In the step B1-3, specifically, for example, an organic group directly bonded to a silicon atom obtained in 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.
  • 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).
  • 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.
  • the reaction temperature is, for example, 0 to 200 ° C., preferably 10 to 200 ° C., more preferably 10 to 120 ° C.
  • the reaction is usually completed in about 2 to 10 hours.
  • the ratio of the silsesquioxane compound having an organic group represented by the general formula (II-9) and the compound represented by the general formula (II-10) in the above reaction is such that the silsesquioxane compound is
  • the amount of the compound represented by the general formula (II-10) is usually about 0.90 to 1.10 mol, preferably 0.95 to 1 mol per 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 amount of the compound represented by the general formula (III-10) is usually about 0.90 to 1.10 mol, preferably 0.95 to 1 mol per 1 mol of the organic group represented by the general formula (III-9). What is necessary is just to be about 1.05 mol.
  • a catalyst may be used as appropriate.
  • the catalyst include tertiary amines such as triethylamine and organometallic compounds such as dibutyltin dilaurate.
  • the silsesquioxane compound of the present invention is produced by the above production method.
  • the product obtained by the production method B1 has a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed.
  • a ladder structure in which an Si—OH group remains, an incomplete cage structure, and / or a random condensate silsesquioxane compound may be included.
  • 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 wherein 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.
  • R 12 and X are the same as defined above. X may be the same or different. ].
  • 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.
  • reaction conditions such as a catalyst, a solvent, a reaction temperature, and a reaction time for the hydrolysis condensation include the same reaction conditions as the hydrolysis condensation reaction exemplified in the description of the step B1-1.
  • 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 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.
  • 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).
  • the reaction can be performed according to a conventional method in which an amino group and an isocyanate group are reacted.
  • the reaction temperature is, for example, ⁇ 78 ° C. to 200 ° C., preferably ⁇ 78 ° C. to 100 ° C., more preferably ⁇ 10 ° C. to 40 ° C.
  • This reaction can be carried out regardless of pressure, but a pressure range of 0.02 to 0.2 MPa, particularly 0.08 to 0.15 MPa is preferred. Since the reaction is very fast, the reaction usually ends as soon as the dropping is completed.
  • a solvent may be appropriately used.
  • 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 the present invention is produced by the above production method.
  • the product obtained by the production method B2 has a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed.
  • a ladder structure in which a Si—OH group remains, an incomplete cage structure, and / or a random condensate silsesquioxane compound may be included.
  • the silsesquioxane compound of the present invention may contain a ladder structure, an incomplete cage structure and / or a random condensate.
  • 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 embodiment 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 -The production method includes Step B3-3 in which the hydroxyl group of the silsesquioxane compound obtained in Step -2 is reacted with the isocyanate group of a compound having a (meth) acryloyloxy group and an isocyanate group.
  • 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).
  • R 16 and X are the same as defined above. X may be the same or different. ].
  • 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.
  • reaction conditions such as a catalyst, a solvent, a reaction temperature, and a reaction time for the hydrolysis condensation include the same reaction conditions as the hydrolysis condensation reaction exemplified in the description of the step B1-1.
  • 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 (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 directly bonded to the silicon atom is represented by the following general formula (V-9). A silsesquioxane compound having an organic group is produced.
  • R 16 is the same as defined above.
  • n and R 15 are the same as defined above.
  • n, R 15 and R 16 are the same as defined above.
  • the reaction for producing the silsesquioxane compound having the organic group represented by the general formula (V-9) as the 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.
  • the reaction conditions such as the use ratio of the raw material compound, the reaction temperature, the catalyst, the solvent, the reaction time and the like are the silsesquioxane compound having an organic group represented by the general formula (II-7) in the above-mentioned 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, an organic group directly bonded to a silicon atom obtained in 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.
  • 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).
  • the reaction can be performed according to a conventional method in which a hydroxyl group and an isocyanate group are reacted.
  • the reaction conditions such as reaction temperature, catalyst, reaction time and the like include the same reaction conditions as those exemplified in the aforementioned Step B1-3.
  • the silsesquioxane compound of the present invention is produced by the above production method.
  • the product obtained by the production method B3 has a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed.
  • 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 it is obtained by the production method B3.
  • the silsesquioxane compound of the present invention may contain a ladder structure, an incomplete cage structure and / or a random condensate.
  • 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.
  • 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 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 100 parts by weight of the nonvolatile content 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.
  • photopolymerization initiator examples include ⁇ -diketones such as benzyl and diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; thioxanthone, 2,4-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, ⁇ , ⁇ '-dimethoxy
  • 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, product name], SANDORAY 1000 (product name, SANDOZ Co., Ltd., product name), Deep (DEAP) (product name, APJOHN Co., Ltd., product name), Kang QUANTACURE-PDO, ITX, EPD (trade name, manufactured by WARD BLEKINSOP Co., Ltd.).
  • 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.
  • the amount of the photopolymerization initiator used is not particularly limited, but is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the total amount of the silsesquioxane compound and polymerizable unsaturated compound of the present invention. More preferably, it is in the range of 1 to 5 parts by mass. The lower limit of this range is significant in terms of improving active energy ray curability, and the upper limit is significant in terms of cost and deep curability.
  • 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 monofunctional polymerizable unsaturated compounds and polyfunctional polymerizable unsaturated compounds.
  • 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.
  • 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, ⁇ -methylstyrene, vinyltoluene, ⁇ -chlorostyrene; N, N-dimethylaminoethyl (meth)
  • polyfunctional polymerizable unsaturated compound examples include esterified products of polyhydric alcohol and (meth) acrylic acid.
  • esterified products of polyhydric alcohol and (meth) acrylic acid Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, Dipentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaeryth
  • 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, ⁇ -caprolactone modified tris (acryloxyethyl) isocyanurate, etc. tri (meth) acrylate compound; pentaerythritol tetra (meth) acrylate etc.
  • 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.
  • the content is preferably 0.1 to 1000 parts by mass, and more preferably 20 to 200 parts by mass.
  • the active energy ray-curable composition of the present invention may contain various additives as necessary, and may be diluted with a solvent if desired.
  • 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.
  • the content is preferably 20 to 100% by mass, and more preferably 25 to 70% by mass. These ranges are significant in terms of smoothness of the coating film and shortening of the drying time.
  • the method for applying the active energy ray-curable composition of the present invention to the surface of an object to be coated is not particularly limited.
  • 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.
  • drying can be performed as necessary.
  • the drying is not particularly limited as long as the solvent that is added can be removed.
  • the drying can be performed at a drying temperature of 20 to 100 ° C. for a drying time of 3 to 20 minutes.
  • the film thickness of the coating is appropriately set according to the purpose.
  • the film thickness is preferably 1 to 100 ⁇ m, more preferably 1 to 20 ⁇ m.
  • the film thickness is at least the lower limit of these ranges, the coating film is excellent in smoothness and appearance.
  • 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.
  • the active energy ray irradiation source includes ultra-high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, sunlight and the like.
  • the irradiation dose is, for example, preferably in the range of 5 to 20,000 J / m 2 , more preferably 100 to 10,000 J / m 2 .
  • the active energy ray irradiation may be performed in an air atmosphere or an inert gas atmosphere.
  • the inert gas include nitrogen and carbon dioxide. Active energy ray irradiation in an inert gas atmosphere is preferable from the viewpoint of curability.
  • the coating film may be heated as necessary.
  • the heating may improve the hardness and adhesion of the coating film.
  • the heating can usually be performed at an atmospheric temperature of 150 to 250 ° C. for 1 to 30 minutes.
  • Part and % indicate “part by mass” and “% by mass” unless otherwise specified.
  • 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.
  • 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.
  • Formula SP ( ⁇ Vml ⁇ ⁇ H + ⁇ Vmh ⁇ ⁇ D) / ( ⁇ Vml + ⁇ Vmh)
  • 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.
  • 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, ⁇ H, and ⁇ D.
  • the molecular volume (mol / ml) of each solvent is acetone: 74.4, n-hexane: 130.3, deionized water: 18, and the 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)
  • 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% non-volatile solution of the product (P1).
  • Glycidyl POSS cage mixture trade name, manufactured by Hybrid Plastics
  • Glycidyl POSS cage mixture used as a raw material was 3-glycidoxypropyl group-containing cage-type polysilsesquioxane, having a weight average molecular weight of 1,800 and an epoxy equivalent of 168 g / eq.
  • the NCO value of the product (P1) was 0 mg NCO / g.
  • the weight average molecular weight of the product (P1) was 5,000.
  • 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, while 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.
  • the NCO value of the product (P3) was 0 mg NCO / g.
  • the weight average molecular weight of the product (P3) was 7,000.
  • 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.
  • Epoxycyclohexyl POSS Cage Mixture trade name, manufactured by Hybrid Plastics
  • Epoxycyclohexyl POSS Cage Mixture used as a raw material is a 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. .
  • the NCO value of the product (P4) was 0 mg NCO / g.
  • the weight average molecular weight of the product (P4) was 6,000.
  • 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, thermometer, air inlet tube, and 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).
  • the weight average molecular weight of the product (P5) was 2,000.
  • the weight average molecular weight of the product (P6) was 5,600.
  • 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).
  • the weight average molecular weight of the product (P7) was 10,000.
  • R 21 represents an isophorone diisocyanate residue.
  • 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.
  • 355 parts of dimethylolpropionic acid and 10 parts of tetrabutylammonium bromide were charged and reacted at 100 ° C. for 24 hours.
  • 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 to obtain a 50% non-volatile solution of the product (P8) Got.
  • the NCO value of the product (P8) was 0 mg NCO / g.
  • the weight average molecular weight of the product (P8) was 8,000.
  • silsesquioxane compound having a weight average molecular weight of 8,000.
  • the SP value of the obtained silsesquioxane compound was 11.0.
  • the weight average molecular weight of the product (P9) was 1,500.
  • 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.
  • 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.
  • ⁇ Compatibility determination> ⁇ : Uniform and transparent, good compatibility ⁇ : 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>
  • A2 Aronix M-140 (trade name, manufactured by Toa Gosei Co., Ltd., N-acryloyloxyethyl hexahydrophthalimide)
  • A3 Aronix M-325 [trade name, manufactured by Toagosei Co., Ltd., ⁇ -caprolactone-modified tris (acryloxyethyl) isocyanurate]
  • Example 8 to 12 Comparative Example 2
  • each product (P3, P4, P6, P7, P8, P9) obtained in Examples 2 to 6 and Comparative Example 1 was 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.
  • 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 ⁇ m, 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.
  • 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
  • Example 14 to 18, Comparative Example 3 The solution of the product (P1) with a nonvolatile 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.
  • Example 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 ⁇ m 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 ⁇ : scratches are observed ⁇ : cracks, peeling, significant scratches, etc. are observed
  • ⁇ Weather resistance> Each test plate obtained was tested for 1000 hours using a sunshine weatherometer, and then the coating film was visually observed and evaluated according to the following criteria. ⁇ : No abnormality, or slight swelling, discoloration, gloss change, peeling, etc. are observed, but there is no problem in practical use. ⁇ : Blurring, discoloration, gloss change, peeling, etc. are recognized. ⁇ : Blurring, discoloration, gloss change, peeling Etc. are remarkably recognized

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Abstract

L'invention porte sur : un composé silsesquioxane qui permet la production d'un film de revêtement ayant d'excellentes résistance à la chaleur, résistance à la rayure et résistance aux intempéries ; et un composé silsesquioxane qui a une excellente compatibilité avec des composés insaturés polymérisables classiques ainsi qu'avec des composés insaturés polymérisables ayant une polarité élevée. De façon spécifique, l'invention porte sur un composé silsesquioxane caractérisé en ce qu'il a des groupes organiques chacun directement lié à un atome de silicium dans le composé silsesquioxane, au moins l'un des groupes organiques étant un groupe organique ayant deux ou plus de deux groupes (méth)acryloyloxy. Dans le composé silsesquioxane, le groupe organique ayant deux ou plus de deux groupes (méth)acryloyloxy peut être un groupe organique ayant deux ou plus de groupes (méth)acryloyloxy et une liaison uréthane et/ou une liaison urée.
PCT/JP2009/069138 2008-12-10 2009-11-10 Composé silsesquioxane ayant un groupe fonctionnel polymérisable WO2010067684A1 (fr)

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JP2010248424A (ja) * 2009-04-17 2010-11-04 Kansai Paint Co Ltd 重合性官能基を有するシルセスキオキサン化合物
JP2010270230A (ja) * 2009-05-22 2010-12-02 Kansai Paint Co Ltd 重合性官能基及び紫外線吸収性基を有するシルセスキオキサン化合物
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JP2013035274A (ja) * 2011-07-13 2013-02-21 Kansai Paint Co Ltd 積層体及び積層体の製造方法
JP2015021044A (ja) * 2013-07-18 2015-02-02 新中村化学工業株式会社 耐熱性および寸法精度に優れる硬化物を形成する光硬化性樹脂組成物
JPWO2016047415A1 (ja) * 2014-09-26 2017-04-27 Dic株式会社 水性ウレタン樹脂組成物、コーティング剤及び物品
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CN115572567B (zh) * 2022-10-27 2023-10-20 南宝树脂（佛山）有限公司 一种耐水洗的环保水性鞋垫贴合胶

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