WO2016170850A1 - Epoxy group-containing cyclic organosiloxane - Google Patents

Epoxy group-containing cyclic organosiloxane Download PDF

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WO2016170850A1
WO2016170850A1 PCT/JP2016/056363 JP2016056363W WO2016170850A1 WO 2016170850 A1 WO2016170850 A1 WO 2016170850A1 JP 2016056363 W JP2016056363 W JP 2016056363W WO 2016170850 A1 WO2016170850 A1 WO 2016170850A1
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group
epoxy
substituent
integer
carbon atoms
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Japanese (ja)
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哲郎 山田
裕司 吉川
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信越化学工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule

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  • the present invention relates to a cyclic organosiloxane containing one or more hydrolyzable silyl groups and two or more epoxy groups in one molecule having a cyclic siloxane as a main skeleton.
  • a silane coupling agent having an epoxy group and a hydrolyzable silyl group includes an adhesion improver (Patent Document 1: Japanese Patent Laid-Open No. 06-287456) and a silica surface treatment (Patent Document 2: Japanese Patent Laid-Open No. 08-146435).
  • an adhesion improver Patent Document 1: Japanese Patent Laid-Open No. 06-287456
  • a silica surface treatment Patent Document 2: Japanese Patent Laid-Open No. 08-146435.
  • paints, coating agents, electronic parts, etc. In this case, one hydrolyzable silyl group and one epoxy group per molecule. It is only a silane coupling agent having one by one, and a binder effect cannot be expected.
  • an organooligosiloxane obtained by partially hydrolytic condensation of a silane coupling agent (hereinafter referred to as a siloxane oligomer) is a material having a plurality of organic groups and hydrolyzable silyl groups in the structure.
  • a hydrolyzable organic group such as an epoxy group
  • the epoxy group also reacts simultaneously with the hydrolytic condensation of the silyl group portion, so the same technology cannot be applied, and stability over time was required.
  • Patent Document 3 Patent No. 2816082
  • Patent Document 4 Patent No. 3067312).
  • the siloxane compounds synthesized by these methods have a problem that the molecular weight distribution is wide and compatibility with other compounds deteriorates due to the influence of polymer components.
  • the present invention has been made in view of the above circumstances, and provides a cyclic organosiloxane having one or more hydrolyzable silyl groups and two or more epoxy groups in one molecule having a cyclic siloxane as a main skeleton. Objective.
  • the crosslink density of the resin can be dramatically increased by using a trifunctional or higher functional epoxy group-containing compound, the mechanical strength of the obtained resin molded product is expected to be improved.
  • a compound having, for example, a hydrolyzable silyl group as another organic group functions as a binder in the resin and is expected to be effective as a silane coupling agent. .
  • the present invention provides the following epoxy group-containing cyclic organosiloxane.
  • An epoxy group-containing cyclic organosiloxane represented by the following general formula (1).
  • R 1 is each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms
  • R 2 is each independently having 1 to 14 carbon atoms which may have a hydrogen atom or a substituent
  • the substituent is a halogen atom, vinyl group, epoxy group, thiirane group, (meth) acryl group, mercapto group, iso (thio) cyanate group, hydrolyzable silyl group, succinic anhydride group, perfluoroalkyl group, those selected from polyether groups and perfluoropolyether group
  • R 2 is one or more of the inner hydrolyzable silyl group and a substituted group, R 2 to the epoxy group with a substituent 2 or more, and n is an integer of 3
  • R 1 is as defined above, R 3 is each independently a substituent containing an epoxy group, R 4 is each independently an alkyl group having 1 to 4 carbon atoms, and R 5 is each independently a halogen atom. , An alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms, which may have an oxygen atom between them, and each R 6 may independently have a hydrogen atom or a substituent.
  • the substituent is a halogen atom, vinyl group, thiirane group, (meth) acryl group, mercapto group, iso (thio) cyanate group, succinic anhydride group, perfluoroalkyl group, polyether Group and a perfluoropolyether group, k is an integer of 2 to 8, m is an integer of 2 to 14, and x is an integer of 1 to 3.
  • p ⁇ 2, q ⁇ 1, r ⁇ 0 and p + q + r are integers of 3 to 6.
  • the cyclic organosiloxane of the present invention has two or more epoxy groups in one molecule
  • the compound contains an organic group (for example, amine, hydroxyl group, acid anhydride group) having reactivity with the functional group,
  • an organic group for example, amine, hydroxyl group, acid anhydride group
  • it since it does not contain a high molecular weight substance, it has excellent compatibility with other organic resins, and functions as a binder. Since it contains a decomposable silyl group, it is an unprecedented material that can be expected to be effective as a silane coupling agent.
  • Example 1 is a 1 H-NMR spectrum of 1,3,5-tris (2- (3,4-epoxycyclohexyl) ethyl) -7-trimethoxysilyloctyltetramethylcyclotetrasiloxane obtained in Example 1.
  • 4 is an IR spectrum of 1,3,5-tris (2- (3,4-epoxycyclohexyl) ethyl) -7-trimethoxysilyloctyltetramethylcyclotetrasiloxane obtained in Example 1.
  • FIG. 2 is a 1 H-NMR spectrum of 1,3,5-tris (3-glycidoxypropyl) -7-trimethoxysilyloctyltetramethylcyclotetrasiloxane obtained in Example 2.
  • FIG. 3 is an IR spectrum of 1,3,5-tris (3-glycidoxypropyl) -7-trimethoxysilyloctyltetramethylcyclotetrasiloxane obtained in Example 2.
  • FIG. 2 is a 1 H-NMR spectrum of 1,3,5-tris (3-glycidoxypropyl) -7-trimethoxysilylethyltetramethylcyclotetrasiloxane obtained in Example 3.
  • 3 is an IR spectrum of 1,3,5-tris (3-glycidoxypropyl) -7-trimethoxysilylethyltetramethylcyclotetrasiloxane obtained in Example 3.
  • FIG. 3 is an IR spectrum of 1,3,5-tris (3-glycid
  • the cyclic organosiloxane of the present invention has only to have a cyclic siloxane structure as a main skeleton and one molecule containing one or more hydrolyzable silyl groups and two or more epoxy groups, and more preferably an epoxy. It contains 3 or more groups.
  • the detailed structure of the organosiloxane is a cyclic siloxane represented by the following general formula (1), and may have the organic functional groups listed below in addition to the hydrolyzable silyl group and the epoxy group.
  • R 1 is each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms
  • R 2 is each independently having 1 to 14 carbon atoms which may have a hydrogen atom or a substituent
  • the substituent is a halogen atom, vinyl group, epoxy group, thiirane group, (meth) acryl group, mercapto group, iso (thio) cyanate group, hydrolyzable silyl group, succinic anhydride group, perfluoroalkyl group, those selected from polyether groups and perfluoropolyether group
  • R 2 is one or more of the inner hydrolyzable silyl group and a substituted group, R 2 to the epoxy group with a substituent 2 or more
  • n is an integer of 3 to 6. Arrangement of each repeating unit is arbitrary.
  • R 1 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, typically a methyl group.
  • Ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, decyl group, etc. are mentioned as alkyl groups, phenyl group, naphthyl group, etc. Are mentioned as an aryl group.
  • R 2 is a hydrogen atom or an optionally substituted alkyl group having 1 to 14 carbon atoms, particularly 1 to 8 carbon atoms, and the alkyl group of the main structure is the same as the alkyl group for R 1 described above.
  • substituents halogen atoms such as chlorine and fluorine atoms, vinyl groups, epoxy groups, thiirane groups, (meth) acryl groups, mercapto groups, iso (thio) cyanate groups, hydrolyzable silyl groups, succinic anhydride Group, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, tridecafluorohexyl group, heptadecafluorooctyl group and other perfluoroalkyl groups, poly (ethylene oxide) group, poly (propylene oxide) ) Groups such as polyether groups and poly (hexafluoroethylene oxide) groups
  • the organosiloxane of the present invention must contain a hydrolyzable silyl group in addition to the epoxy group.
  • a hydrolyzable silyl group By containing a hydrolyzable silyl group, the organosiloxane functions as a silane coupling agent.
  • the hydrolyzable silyl group is composed of a monovalent hydrolyzable atom directly bonded to a silicon atom (an atom that generates a silanol group by reacting with water) and a monovalent hydrolyzable group directly bonded to a silicon atom (reacted with water).
  • the group is not particularly limited as long as it is a silyl group having at least one of groups capable of producing a silanol group.
  • One or two or more hydrolyzable silyl groups may be present in the organosiloxane, and when two or more hydrolyzable silyl groups are present, they may be the same or different.
  • the specific structure of the organosiloxane having a hydrolyzable silyl group and an epoxy group can be represented by the following general formula (2).
  • R 1 is as defined above, R 3 is each independently a substituent containing an epoxy group, R 4 is each independently an alkyl group having 1 to 4 carbon atoms, and R 5 is each independently a halogen atom.
  • R 4 is each independently an alkyl group having 1 to 4 carbon atoms, and R 5 is each independently a halogen atom.
  • p ⁇ 2, q ⁇ 1, r ⁇ 0, p + Q + r is an integer of 3 to 6.
  • the arrangement of each repeating unit is arbitrary.)
  • Examples of the substituent containing the epoxy group of R 3 include substituents represented by the following general formulas (A) to (C).
  • R 4 may be linear or branched, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.
  • a methyl group is preferred because of the ease of production of the raw material.
  • R 5 is a group that generates silanol by reacting with water, specifically, a halogen atom such as a chlorine atom or a bromine atom, or an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, or a butoxy group.
  • alkoxy groups in which some carbon atoms are substituted with oxygen atoms such as aryloxy groups such as phenoxy groups, ethylene glycol monoalkyl ether groups (for example, ethylene glycol monobutyl ether groups), and the like. Not limited to things. Among these, a methoxy group and an ethoxy group are preferable from the standpoint of ease of raw material production and hydrolyzability.
  • halogen atom, perfluoroalkyl group, polyether group, and perfluoropolyether group of the substituent of R 6 include the same as those described for R 2 in the general formula (1).
  • organosiloxane represented by the general formula (2) include, for example, those represented by the following general formula (3) or (4).
  • organosiloxane of the present invention for example, a compound represented by the following general formula (5), (6) or (7), that is, 1,3,5-tris (2- (3,4-) Epoxycyclohexyl) ethyl) -7-trimethoxysilyloctyltetramethylcyclotetrasiloxane, 1,3-bis (2- (3,4-epoxycyclohexyl) ethyl) -5,7-bis (trimethoxysilyloctyl) tetramethyl Cyclotetrasiloxane, 1,5-bis (2- (3,4-epoxycyclohexyl) ethyl) -3,7-bis (trimethoxysilyloctyl) tetramethylcyclotetrasiloxane, 1,3-bis (2- (3 , 4-Epoxycyclohexyl) ethyl) -5,7-bis (trimethoxysilylethy
  • the organosiloxane of the present invention comprises a cyclic organohydrogensiloxane having at least two Si—H groups and at least one hydrolyzable silyl group in one molecule, and an epoxy group-containing compound having a carbon-carbon unsaturated bond Are hydrosilylated in the presence of platinum and / or platinum complexes.
  • an epoxy group-containing compound having a carbon-carbon unsaturated bond are hydrosilylated in the presence of platinum and / or platinum complexes.
  • the desired compound can be obtained by hydrosilylating the Si—H group remaining in the cyclic organohydrogensiloxane with an epoxy group-containing compound having a carbon-carbon unsaturated bond.
  • the order of hydrosilylation is not particularly limited, but it is preferable that the epoxy group-containing compound containing a carbon-carbon unsaturated bond is hydrosilylated later from the viewpoint of reaction efficiency.
  • Si—H groups contained in a cyclic organohydrogensiloxane having at least two Si—H groups and at least one hydrolyzable silyl group in one molecule and if necessary, as substituents At least one selected from a halogen atom, vinyl group, thiirane group, (meth) acryl group, mercapto group, iso (thio) cyanate group, succinic anhydride group, perfluoroalkyl group, polyether group and perfluoropolyether group
  • the hydrosilylation reaction of a substituted or unsubstituted unsaturated hydrocarbon compound with a seed in the presence of platinum and / or a platinum complex the remaining Si—H group in the resulting cyclic organohydrogensiloxane and carbon-carbon It is preferable to carry out a hydrosilylation reaction with an epoxy group-containing compound having an unsaturated bond.
  • the reaction temperature is room temperature (25 ° C.) to 150 ° C., preferably 40 to 130 ° C., more preferably 70 to 120 ° C. If the temperature is lower than room temperature, the reaction does not proceed, or the reaction rate is extremely low, so that productivity may be lacking. On the other hand, when it exceeds 150 ° C., there is a possibility that thermal decomposition or unintended side reaction may occur.
  • the reaction time is 10 minutes to 24 hours.
  • the time may be a time at which the raw material is sufficiently consumed by the progress of the reaction, but it is preferably 1 to 10 hours, more preferably 2 to 7 hours. If it is less than 10 minutes, the consumption of the raw material may be insufficient, and if it exceeds 24 hours, the raw material has already been completely consumed, which may be an unnecessary process and may reduce the production efficiency.
  • a reaction solvent may be appropriately used in the method for producing an organosiloxane of the present invention.
  • an aliphatic hydrocarbon solvent such as hexane or heptane, or an aromatic such as toluene or xylene.
  • hydrocarbon solvents include hydrocarbon solvents, alcohol solvents such as methanol, ethanol, propanol and isopropanol, and ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone.
  • the organohydrogensiloxane in the present invention is not particularly limited as long as it has a cyclic siloxane as a main skeleton and contains at least two Si—H groups and at least one hydrolyzable silyl group in one molecule.
  • the structure may have a linear structure or a branched structure.
  • an unnecessary increase in crosslink density can be avoided if the molecular weight distribution is narrow to some extent, so that it is essential to be a cyclic siloxane in order to achieve a low molecular weight.
  • cyclic organohydrogensiloxane examples include 1,3,5-trimethyl-1-trimethoxysilyloctylcyclotrisiloxane, 1,3,5-trimethyl-1-trimethoxysilylhexylcyclotrisiloxane, , 3,5-trimethyl-1-trimethoxysilylethylcyclotrisiloxane, 1,3,5-trimethyl-1-triethoxysilyloctylcyclotrisiloxane, 1,3,5-trimethyl-1-triethoxysilylhexylcyclo Trisiloxane, 1,3,5-trimethyl-1-triethoxysilylethylcyclotrisiloxane, 1,3,5,7-tetramethyl-1-trimethoxysilyloctylcyclotetrasiloxane, 1,3,5,7- Tetramethyl-1-trimethoxysilyloctyl-3-pro Rucyclotetrasiloxane, 1,3,5,7-tetramethyl
  • 1,3,5,7-tetramethyl-1-trimethoxysilyloctylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1-trimethoxy are explained above and the raw materials are easily available.
  • Most preferred is silylethylcyclotetrasiloxane.
  • the unsaturated hydrocarbon compound added if necessary is represented by the following formula CH 2 ⁇ CH—R 6a.
  • R 6a is a hydrogen atom or an alkyl group having 1 to 14, particularly 1 to 8 carbon atoms which may have a substituent, and the substituent is a halogen atom, a vinyl group, a thiirane group, (meta )
  • An epoxy group-containing compound having a carbon-carbon unsaturated bond is represented by the following formula:
  • R 3 is a substituent containing an epoxy group, and k1 is an integer of 0 to 6)
  • R 1 is as defined above, R 3 is each independently a substituent containing an epoxy group, R 4 is each independently an alkyl group having 1 to 4 carbon atoms, and R 5 is each independently a halogen atom.
  • R 4 is each independently an alkyl group having 1 to 4 carbon atoms, and R 5 is each independently a halogen atom.
  • p ⁇ 2, q ⁇ 1, r ⁇ 0, p + Q + r is an integer of 3 to 6.
  • the arrangement of each repeating unit is arbitrary.)
  • the epoxy group-containing compound having a carbon-carbon unsaturated bond in the present invention is not particularly limited as long as it is an olefin-containing epoxy group-containing compound having hydrosilylation reactivity, and specifically, 1,2-epoxy-4- Examples include, but are not limited to, vinylcyclohexane, allyl glycidyl ether, 1,2-epoxy-5-hexene, and 1,2-epoxy-7-octene.
  • an olefin compound having the substituent (described above, CH 2 ⁇ CH—R 6a ) may be used.
  • the ratio of the reaction raw materials used in the present invention is preferably 0.7 to 1.5 moles, more preferably a total of compounds having a carbon-carbon unsaturated bond per mole of Si—H groups in the organohydrogensiloxane. 0.9 to 1.1 mol.
  • the hydrosilylation reaction catalyst in the present invention is a complex compound having platinum (Pt) and / or platinum (Pt) as a central metal, which is known as a known technique.
  • a complex compound having platinum (Pt) and / or platinum (Pt) as a central metal which is known as a known technique.
  • an alcohol solution of chloroplatinic acid, a 1,3-divinyltetramethyldisiloxane complex of chloroplatinic acid, a compound obtained by neutralizing the complex, and the oxidation number of the central metal is Pt (II) or Pt ( 0) 1,3-divinyltetramethyldisiloxane complex.
  • the oxidation number of the central metal is a complex other than Pt (IV) from the viewpoint of addition site selectivity, and Pt (0) and Pt (II) are particularly preferable.
  • the amount of the hydrosilylation reaction catalyst used in the present invention is not particularly limited as long as the catalytic effect of the hydrosilylation reaction is manifested, but is preferably 0.000001 to 0.000001 to in terms of platinum metal with respect to 1 mol of the total amount of olefin compounds. 1 mol, more preferably 0.000003 to 0.01 mol.
  • the amount is less than 0.000001 mol, there is a possibility that a sufficient catalytic effect may not be exhibited.
  • the amount is more than 1 mol, the effect is saturated, and the production cost may be increased, which may be uneconomical.
  • a viscosity shows the value in 25 degreeC measured with the Ostwald viscometer.
  • the title siloxane was obtained as a colorless transparent liquid having a viscosity of 74 mm 2 / s and a refractive index of 1.4559 (25 ° C.) by removing toluene and excess allyl glycidyl ether by distillation under reduced pressure (80 ° C., 2 mmHg).
  • the obtained title siloxane was subjected to 1 H-NMR and IR measurement. The results are shown in FIGS. 3 and 4, respectively.
  • the title siloxane was obtained as a colorless transparent liquid having a viscosity of 64 mm 2 / s and a refractive index of 1.4552 (25 ° C.) by removing toluene and excess allyl glycidyl ether by distillation under reduced pressure (80 ° C., 2 mmHg).
  • the obtained title siloxane was subjected to 1 H-NMR and IR measurement. The results are shown in FIGS. 5 and 6, respectively.

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Abstract

This epoxy group-containing cyclic organosiloxane represented by formula (1) includes at least two epoxy groups in a single molecule, and thus has excellent compatibility with other organic resins when prepared into a composition with a compound including an organic group that is reactive with said functional groups, and also exhibits a function as a binder. The epoxy group-containing cyclic organosiloxane also includes a hydrolyzable silyl group, and can thus also be expected to be effective as a silane coupling agent. (R1 is an alkyl group or an aryl group; R2 is a hydrogen atom or an alkyl group that may have a substituent selected from a halogen atom, a vinyl group, an epoxy group, a thiirane group, a (meth)acrylic group, a mercapto group, an iso(thio)cyanate group, a hydrolyzable silyl group, a succinic anhydride group, a perfluoroalkyl group, a polyether group, and a perfluoropolyether group, wherein there is at least one R2 including a hydrolyzable silyl group as a substituent and at least two R2s including an epoxy group as a substituent; and n is an integer of from 3 to 6.)

Description

エポキシ基含有環状オルガノシロキサンEpoxy group-containing cyclic organosiloxane
　本発明は、環状シロキサンを主骨格とした１分子中に１個以上の加水分解性シリル基と２個以上のエポキシ基を含有する環状オルガノシロキサンに関する。 The present invention relates to a cyclic organosiloxane containing one or more hydrolyzable silyl groups and two or more epoxy groups in one molecule having a cyclic siloxane as a main skeleton.
　エポキシ基と加水分解性シリル基とを有するシランカップリング剤は、密着性向上剤（特許文献１：特開平０６－２８７４５６号公報）、シリカ表面の処理（特許文献２：特開平０８－１４６４３５号公報）等の特性を付与することが可能であり、塗料、コーティング剤、電子部品等様々な分野で使用されているが、この場合は加水分解性シリル基とエポキシ基とを１分子中に１個ずつ有するシランカップリング剤のみであり、バインダー効果は期待できない。 A silane coupling agent having an epoxy group and a hydrolyzable silyl group includes an adhesion improver (Patent Document 1: Japanese Patent Laid-Open No. 06-287456) and a silica surface treatment (Patent Document 2: Japanese Patent Laid-Open No. 08-146435). Such as paints, coating agents, electronic parts, etc. In this case, one hydrolyzable silyl group and one epoxy group per molecule. It is only a silane coupling agent having one by one, and a binder effect cannot be expected.
　一般に、シランカップリング剤を部分加水分解縮合して得られるオルガノオリゴシロキサン（以下、シロキサンオリゴマーと呼称する。）は、構造中に有機基と加水分解性シリル基を複数持った材料であるが、エポキシ基のような加水分解性のある有機基である場合には、シリル基部分の加水分解縮合と同時にエポキシ基も反応してしまうため同技術が応用できず、経時安定性が求められていた。
　また、直鎖構造のハイドロジェンポリシロキサンにアリルグリシジルエーテルとビニルアルコキシシランなどを共付加させることが提案されている（特許文献３：特許第２８１６０８２号公報、特許文献４：特許第３０６３７１２号公報）。しかし、これらの方法で合成されたシロキサン化合物は、分子量分布が広く、高分子成分の影響により他の化合物との相溶性が悪化するなどの問題があった。 In general, an organooligosiloxane obtained by partially hydrolytic condensation of a silane coupling agent (hereinafter referred to as a siloxane oligomer) is a material having a plurality of organic groups and hydrolyzable silyl groups in the structure. In the case of a hydrolyzable organic group such as an epoxy group, the epoxy group also reacts simultaneously with the hydrolytic condensation of the silyl group portion, so the same technology cannot be applied, and stability over time was required. .
Further, it has been proposed to co-add allyl glycidyl ether and vinyl alkoxysilane to a linear structure hydrogenpolysiloxane (Patent Document 3: Patent No. 2816082, Patent Document 4: Patent No. 3067312). . However, the siloxane compounds synthesized by these methods have a problem that the molecular weight distribution is wide and compatibility with other compounds deteriorates due to the influence of polymer components.
特開平０６－２８７４５６号公報Japanese Patent Laid-Open No. 06-287456 特開平０８－１４６４３５号公報Japanese Patent Laid-Open No. 08-146435 特許第２８１６０８２号公報Japanese Patent No. 2816082 特許第３０６３７１２号公報Japanese Patent No. 3067312
　本発明は、上記事情に鑑みなされたものであり、環状シロキサンを主骨格とした１分子中に加水分解性シリル基を１個以上及びエポキシ基を２個以上有する環状オルガノシロキサンを提供することを目的とする。 The present invention has been made in view of the above circumstances, and provides a cyclic organosiloxane having one or more hydrolyzable silyl groups and two or more epoxy groups in one molecule having a cyclic siloxane as a main skeleton. Objective.
　３官能以上のエポキシ基含有化合物を使用することで樹脂の架橋密度を飛躍的に増大できることから、得られる樹脂成形品の機械的強度の向上が期待される。また、２官能エポキシ基含有化合物である場合にも、その他の有機基として例えば加水分解性シリル基を有する化合物は、樹脂中のバインダーとして機能する他、シランカップリング剤としての効果が期待される。 Since the crosslink density of the resin can be dramatically increased by using a trifunctional or higher functional epoxy group-containing compound, the mechanical strength of the obtained resin molded product is expected to be improved. Even in the case of a bifunctional epoxy group-containing compound, a compound having, for example, a hydrolyzable silyl group as another organic group functions as a binder in the resin and is expected to be effective as a silane coupling agent. .
　本発明者らは、かかる点から、上記目的を達成するため鋭意検討を重ねた結果、１分子中に複数のヒドロシリル基及び１つ以上の加水分解性シリル基を有する環状オルガノハイドロジェンシロキサンと、炭素－炭素不飽和結合を有するエポキシ基含有化合物とを白金及び／又は白金錯体存在下においてヒドロシリル化させることで得られる、一般式（１）で示される化合物が、上記課題の解決に有用であることを見出し、本発明をなすに至った。 From these points, the present inventors have conducted extensive studies to achieve the above object, and as a result, a cyclic organohydrogensiloxane having a plurality of hydrosilyl groups and one or more hydrolyzable silyl groups in one molecule; A compound represented by the general formula (1) obtained by hydrosilylating an epoxy group-containing compound having a carbon-carbon unsaturated bond in the presence of platinum and / or a platinum complex is useful for solving the above problems. As a result, the inventors have made the present invention.
　従って、本発明は、下記に示すエポキシ基含有環状オルガノシロキサンを提供する。
〔１〕　下記一般式（１）で示されるエポキシ基含有環状オルガノシロキサン。
Figure JPOXMLDOC01-appb-C000005
 （式中、Ｒ1は各々独立に炭素数１～１０のアルキル基又は炭素数６～１０のアリール基、Ｒ2は各々独立に水素原子又は置換基を有してもよい炭素数１～１４のアルキル基であって、該置換基はハロゲン原子、ビニル基、エポキシ基、チイラン基、（メタ）アクリル基、メルカプト基、イソ（チオ）シアネート基、加水分解性シリル基、無水コハク酸基、パーフルオロアルキル基、ポリエーテル基及びパーフルオロポリエーテル基から選ばれるものであり、その内加水分解性シリル基を置換基とするＲ2が１個以上、エポキシ基を置換基とするＲ2が２個以上である。ｎは３～６の整数である。）
〔２〕　下記一般式（２）で示される〔１〕記載のエポキシ基含有環状オルガノシロキサン。
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ1は上記と同様であり、Ｒ3は各々独立にエポキシ基を含有する置換基、Ｒ4は各々独立に炭素数１～４のアルキル基、Ｒ5は各々独立にハロゲン原子、酸素原子を間に挟んでもよい炭素数１～２０のアルコキシ基、又は炭素数６～１０のアリーロキシ基であり、Ｒ6は各々独立に水素原子又は置換基を有してもよい炭素数１～１４のアルキル基であって、該置換基はハロゲン原子、ビニル基、チイラン基、（メタ）アクリル基、メルカプト基、イソ（チオ）シアネート基、無水コハク酸基、パーフルオロアルキル基、ポリエーテル基及びパーフルオロポリエーテル基から選ばれるものであり、ｋは２～８の整数、ｍは２～１４の整数、ｘは１～３の整数である。ｐ≧２、ｑ≧１、ｒ≧０、ｐ＋ｑ＋ｒは３～６の整数である。）
〔３〕　下記一般式（３）又は（４）で示される〔２〕記載のエポキシ基含有環状オルガノシロキサン。
Figure JPOXMLDOC01-appb-C000007
（式中、各々独立にｐ’≧２、ｑ’≧１、ｐ’＋ｑ’は４～５の整数、ｎ’は２～８の整数である。）
〔４〕　下記一般式（５）、（６）又は（７）で示される〔３〕記載のエポキシ基含有環状オルガノシロキサン。
Figure JPOXMLDOC01-appb-C000008

（式中、各々独立にｐ”≧２、ｑ”≧１、ｐ”＋ｑ”は４～５の整数である。）
〔５〕　環状シロキサンがシクロテトラシロキサンである〔１〕～〔４〕のいずれかに記載のエポキシ基含有環状オルガノシロキサン。
を提供する。 Accordingly, the present invention provides the following epoxy group-containing cyclic organosiloxane.
[1] An epoxy group-containing cyclic organosiloxane represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000005
 (Wherein R 1 is each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 2 is each independently having 1 to 14 carbon atoms which may have a hydrogen atom or a substituent) Wherein the substituent is a halogen atom, vinyl group, epoxy group, thiirane group, (meth) acryl group, mercapto group, iso (thio) cyanate group, hydrolyzable silyl group, succinic anhydride group, perfluoroalkyl group, those selected from polyether groups and perfluoropolyether group, R 2 is one or more of the inner hydrolyzable silyl group and a substituted group, R 2 to the epoxy group with a substituent 2 or more, and n is an integer of 3 to 6.)
[2] The epoxy group-containing cyclic organosiloxane according to [1] represented by the following general formula (2).
Figure JPOXMLDOC01-appb-C000006
 Wherein R 1 is as defined above, R 3 is each independently a substituent containing an epoxy group, R 4 is each independently an alkyl group having 1 to 4 carbon atoms, and R 5 is each independently a halogen atom. , An alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms, which may have an oxygen atom between them, and each R 6 may independently have a hydrogen atom or a substituent. Wherein the substituent is a halogen atom, vinyl group, thiirane group, (meth) acryl group, mercapto group, iso (thio) cyanate group, succinic anhydride group, perfluoroalkyl group, polyether Group and a perfluoropolyether group, k is an integer of 2 to 8, m is an integer of 2 to 14, and x is an integer of 1 to 3. p ≧ 2, q ≧ 1, r ≧ 0 and p + q + r are integers of 3 to 6.)
[3] The epoxy group-containing cyclic organosiloxane according to [2] represented by the following general formula (3) or (4).
Figure JPOXMLDOC01-appb-C000007
(In the formula, p ′ ≧ 2, q ′ ≧ 1, p ′ + q ′ is an integer of 4 to 5 and n ′ is an integer of 2 to 8).
[4] The epoxy group-containing cyclic organosiloxane according to [3] represented by the following general formula (5), (6) or (7).
Figure JPOXMLDOC01-appb-C000008

(In the formula, p ″ ≧ 2, q ″ ≧ 1, and p ″ + q ″ are each independently an integer of 4 to 5.)
[5] The epoxy group-containing cyclic organosiloxane according to any one of [1] to [4], wherein the cyclic siloxane is cyclotetrasiloxane.
I will provide a.
　本発明の環状オルガノシロキサンは、１分子中にエポキシ基を２個以上有しているため該官能基と反応性を有する有機基（例えば、アミン、水酸基、酸無水物基）を含有した化合物との組成物を調製した際に、それら化合物との反応性に優れる上に、高分子量体を含まないことから他の有機樹脂との相溶性も優れ、バインダーとしての機能を発現する他、更に加水分解性シリル基も含むためシランカップリング剤としての効果も期待できるこれまでに実例のない材料である。 Since the cyclic organosiloxane of the present invention has two or more epoxy groups in one molecule, the compound contains an organic group (for example, amine, hydroxyl group, acid anhydride group) having reactivity with the functional group, In addition to being excellent in reactivity with these compounds, since it does not contain a high molecular weight substance, it has excellent compatibility with other organic resins, and functions as a binder. Since it contains a decomposable silyl group, it is an unprecedented material that can be expected to be effective as a silane coupling agent.
実施例１で得られた１，３，５－トリス（２－（３，４－エポキシシクロヘキシル）エチル）－７－トリメトキシシリルオクチルテトラメチルシクロテトラシロキサンの1Ｈ－ＮＭＲスペクトルである。1 is a 1 H-NMR spectrum of 1,3,5-tris (2- (3,4-epoxycyclohexyl) ethyl) -7-trimethoxysilyloctyltetramethylcyclotetrasiloxane obtained in Example 1. 実施例１で得られた１，３，５－トリス（２－（３，４－エポキシシクロヘキシル）エチル）－７－トリメトキシシリルオクチルテトラメチルシクロテトラシロキサンのＩＲスペクトルである。4 is an IR spectrum of 1,3,5-tris (2- (3,4-epoxycyclohexyl) ethyl) -7-trimethoxysilyloctyltetramethylcyclotetrasiloxane obtained in Example 1. FIG. 実施例２で得られた１，３，５－トリス（３－グリシドキシプロピル）－７－トリメトキシシリルオクチルテトラメチルシクロテトラシロキサンの1Ｈ－ＮＭＲスペクトルである。2 is a 1 H-NMR spectrum of 1,3,5-tris (3-glycidoxypropyl) -7-trimethoxysilyloctyltetramethylcyclotetrasiloxane obtained in Example 2. FIG. 実施例２で得られた１，３，５－トリス（３－グリシドキシプロピル）－７－トリメトキシシリルオクチルテトラメチルシクロテトラシロキサンのＩＲスペクトルである。3 is an IR spectrum of 1,3,5-tris (3-glycidoxypropyl) -7-trimethoxysilyloctyltetramethylcyclotetrasiloxane obtained in Example 2. FIG. 実施例３で得られた１，３，５－トリス（３－グリシドキシプロピル）－７－トリメトキシシリルエチルテトラメチルシクロテトラシロキサンの1Ｈ－ＮＭＲスペクトルである。2 is a 1 H-NMR spectrum of 1,3,5-tris (3-glycidoxypropyl) -7-trimethoxysilylethyltetramethylcyclotetrasiloxane obtained in Example 3. 実施例３で得られた１，３，５－トリス（３－グリシドキシプロピル）－７－トリメトキシシリルエチルテトラメチルシクロテトラシロキサンのＩＲスペクトルである。3 is an IR spectrum of 1,3,5-tris (3-glycidoxypropyl) -7-trimethoxysilylethyltetramethylcyclotetrasiloxane obtained in Example 3. FIG.
　以下、本発明について具体的に説明する。
［環状オルガノシロキサン］
　本発明の環状オルガノシロキサンは、環状シロキサン構造を主骨格とし、１分子中に加水分解性シリル基を１個以上、及びエポキシ基を２個以上含んでなるものであればよく、より好ましくはエポキシ基を３個以上含むものである。該オルガノシロキサンの詳細な構造は下記一般式（１）に示す環状シロキサンであり、加水分解性シリル基及びエポキシ基以外にも下記に列挙した有機官能基を有してもよい。 Hereinafter, the present invention will be specifically described.
[Cyclic organosiloxane]
The cyclic organosiloxane of the present invention has only to have a cyclic siloxane structure as a main skeleton and one molecule containing one or more hydrolyzable silyl groups and two or more epoxy groups, and more preferably an epoxy. It contains 3 or more groups. The detailed structure of the organosiloxane is a cyclic siloxane represented by the following general formula (1), and may have the organic functional groups listed below in addition to the hydrolyzable silyl group and the epoxy group.
Figure JPOXMLDOC01-appb-C000009
 （式中、Ｒ1は各々独立に炭素数１～１０のアルキル基又は炭素数６～１０のアリール基、Ｒ2は各々独立に水素原子又は置換基を有してもよい炭素数１～１４のアルキル基であって、該置換基はハロゲン原子、ビニル基、エポキシ基、チイラン基、（メタ）アクリル基、メルカプト基、イソ（チオ）シアネート基、加水分解性シリル基、無水コハク酸基、パーフルオロアルキル基、ポリエーテル基及びパーフルオロポリエーテル基から選ばれるものであり、その内加水分解性シリル基を置換基とするＲ2が１個以上、エポキシ基を置換基とするＲ2が２個以上である。ｎは３～６の整数である。各繰り返し単位の配列は任意である。）
Figure JPOXMLDOC01-appb-C000009
 (Wherein R 1 is each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 2 is each independently having 1 to 14 carbon atoms which may have a hydrogen atom or a substituent) Wherein the substituent is a halogen atom, vinyl group, epoxy group, thiirane group, (meth) acryl group, mercapto group, iso (thio) cyanate group, hydrolyzable silyl group, succinic anhydride group, perfluoroalkyl group, those selected from polyether groups and perfluoropolyether group, R 2 is one or more of the inner hydrolyzable silyl group and a substituted group, R 2 to the epoxy group with a substituent 2 or more, n is an integer of 3 to 6. Arrangement of each repeating unit is arbitrary.)
　上記オルガノシロキサンの一般式（１）において、ｎはシロキサンのユニット数を示し、ｎは３～６の範囲であれば分布を持つものであっても問題ないが、より好ましくは熱力学的に安定であり、原料シロキサンの製造が容易なｎ＝４（シロキサン４量体；シクロテトラシロキサン）が好ましい。シロキサン構造が環状であることから、他の有機化合物との相溶性が優れ、硬化した際の収縮も抑えられる。 In the above general formula (1) of organosiloxane, n represents the number of siloxane units, and if n is in the range of 3 to 6, there is no problem even if it has a distribution, but more preferably thermodynamically stable N = 4 (siloxane tetramer; cyclotetrasiloxane), which is easy to produce a raw material siloxane, is preferable. Since the siloxane structure is cyclic, the compatibility with other organic compounds is excellent, and shrinkage when cured is also suppressed.
　上記オルガノシロキサンの一般式（１）において、Ｒ1は炭素数１～１０の直鎖状、分岐状又は環状のアルキル基、又は炭素数６～１０のアリール基であり、代表的にはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、イソペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、オクチル基、デシル基等がアルキル基として挙げられ、フェニル基、ナフチル基等がアリール基として挙げられる。また、Ｒ2は水素原子、置換基を有してもよい炭素数１～１４、特に１～８のアルキル基であって、主構造のアルキル基は先述したＲ1についてのアルキル基と同様であり、置換基としては塩素原子、フッ素原子等のハロゲン原子、ビニル基、エポキシ基、チイラン基、（メタ）アクリル基、メルカプト基、イソ（チオ）シアネート基、加水分解性シリル基、無水コハク酸基、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、ノナフルオロブチル基、トリデカフルオロヘキシル基、ヘプタデカフルオロオクチル基等のパーフルオロアルキル基、ポリ（エチレンオキシド）基、ポリ（プロピレンオキシド）基等のポリエーテル基、ポリ（ヘキサフルオロエチレンオキシド）基等のパーフルオロポリエーテル基が挙げられる。 In the general formula (1) of the organosiloxane, R 1 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, typically a methyl group. , Ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, decyl group, etc. are mentioned as alkyl groups, phenyl group, naphthyl group, etc. Are mentioned as an aryl group. R 2 is a hydrogen atom or an optionally substituted alkyl group having 1 to 14 carbon atoms, particularly 1 to 8 carbon atoms, and the alkyl group of the main structure is the same as the alkyl group for R 1 described above. Yes, as substituents, halogen atoms such as chlorine and fluorine atoms, vinyl groups, epoxy groups, thiirane groups, (meth) acryl groups, mercapto groups, iso (thio) cyanate groups, hydrolyzable silyl groups, succinic anhydride Group, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, tridecafluorohexyl group, heptadecafluorooctyl group and other perfluoroalkyl groups, poly (ethylene oxide) group, poly (propylene oxide) ) Groups such as polyether groups and poly (hexafluoroethylene oxide) groups. It is done.
　本発明のオルガノシロキサンは、エポキシ基以外に加水分解性シリル基を含むことが必須である。加水分解性シリル基を含有することにより該オルガノシロキサンはシランカップリング剤としての機能を有する。加水分解性シリル基は、ケイ素原子に直結した１価の加水分解性原子（水と反応することでシラノール基を生成する原子）及びケイ素原子に直結した１価の加水分解性基（水と反応することでシラノール基を生成する基）の少なくとも一方を有するシリル基である限り特に限定されない。加水分解性シリル基は、前記オルガノシロキサン中に１個のみ存在しても２個以上存在してもよく、２個以上存在する場合は同種であっても異種であってもよい。加水分解性シリル基及びエポキシ基を有するオルガノシロキサンの具体的な構造としては、下記一般式（２）で表すことができる。 The organosiloxane of the present invention must contain a hydrolyzable silyl group in addition to the epoxy group. By containing a hydrolyzable silyl group, the organosiloxane functions as a silane coupling agent. The hydrolyzable silyl group is composed of a monovalent hydrolyzable atom directly bonded to a silicon atom (an atom that generates a silanol group by reacting with water) and a monovalent hydrolyzable group directly bonded to a silicon atom (reacted with water). The group is not particularly limited as long as it is a silyl group having at least one of groups capable of producing a silanol group. One or two or more hydrolyzable silyl groups may be present in the organosiloxane, and when two or more hydrolyzable silyl groups are present, they may be the same or different. The specific structure of the organosiloxane having a hydrolyzable silyl group and an epoxy group can be represented by the following general formula (2).
Figure JPOXMLDOC01-appb-C000010
 （式中、Ｒ1は上記と同様であり、Ｒ3は各々独立にエポキシ基を含有する置換基、Ｒ4は各々独立に炭素数１～４のアルキル基、Ｒ5は各々独立にハロゲン原子、酸素原子を間に挟んでもよい炭素数１～２０、特に１～６のアルコキシ基、又は炭素数６～１０のアリーロキシ基であり、Ｒ6は各々独立に水素原子又は置換基を有してもよい炭素数１～１４、特に１～８のアルキル基であって、該置換基はハロゲン原子、ビニル基、チイラン基、（メタ）アクリル基、メルカプト基、イソ（チオ）シアネート基、無水コハク酸基、パーフルオロアルキル基、ポリエーテル基、及びパーフルオロポリエーテル基から選ばれるものであり、ｋは２～８の整数、ｍは２～１４、特に２～８の整数、ｘは１～３の整数である。ｐ≧２、ｑ≧１、ｒ≧０、ｐ＋ｑ＋ｒは３～６の整数である。各繰り返し単位の配列は任意である。）
Figure JPOXMLDOC01-appb-C000010
 Wherein R 1 is as defined above, R 3 is each independently a substituent containing an epoxy group, R 4 is each independently an alkyl group having 1 to 4 carbon atoms, and R 5 is each independently a halogen atom. , An alkoxy group having 1 to 20 carbon atoms, particularly 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms, in which an oxygen atom may be interposed, and each R 6 independently has a hydrogen atom or a substituent. An alkyl group having 1 to 14 carbon atoms, particularly 1 to 8 carbon atoms, and the substituent is a halogen atom, vinyl group, thiirane group, (meth) acryl group, mercapto group, iso (thio) cyanate group, anhydrous succinate Selected from an acid group, a perfluoroalkyl group, a polyether group, and a perfluoropolyether group, k is an integer of 2 to 8, m is an integer of 2 to 14, particularly 2 to 8, and x is 1 to It is an integer of 3. p ≧ 2, q ≧ 1, r ≧ 0, p + Q + r is an integer of 3 to 6. The arrangement of each repeating unit is arbitrary.)
　Ｒ3のエポキシ基を含有する置換基としては、下記一般式（Ａ）～（Ｃ）に示す置換基等が挙げられる。 Examples of the substituent containing the epoxy group of R 3 include substituents represented by the following general formulas (A) to (C).
Figure JPOXMLDOC01-appb-C000011
 （但し、波線が付されている手が結合手を示す。）
Figure JPOXMLDOC01-appb-C000011
 (However, a hand with a wavy line indicates a bond.)
　加水分解性シリル基の構造の詳細として、Ｒ4は直鎖状又は分岐状であってよく、具体的にはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基等が挙げられ、原料の製造容易さからメチル基が好ましい。Ｒ5は水と反応することでシラノールを生成する基であり、具体的には塩素原子、臭素原子等のハロゲン原子、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基等のアルコキシ基、フェノキシ基等のアリーロキシ基、エチレングリコールモノアルキルエーテル基（例えば、エチレングリコールモノブチルエーテル基）等の炭素原子の一部が酸素原子で置換されたアルコキシ基などが挙げられるが、ここに例示されたものに限らない。それらの中でも原料製造の容易さ、加水分解性のバランスからメトキシ基、エトキシ基が好ましい。また、Ｒ6の置換基のハロゲン原子、パーフルオロアルキル基、ポリエーテル基、パーフルオロポリエーテル基としては、上記一般式（１）のＲ2について説明したものと同じものを挙げることができる。 As details of the structure of the hydrolyzable silyl group, R 4 may be linear or branched, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. A methyl group is preferred because of the ease of production of the raw material. R 5 is a group that generates silanol by reacting with water, specifically, a halogen atom such as a chlorine atom or a bromine atom, or an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, or a butoxy group. And alkoxy groups in which some carbon atoms are substituted with oxygen atoms, such as aryloxy groups such as phenoxy groups, ethylene glycol monoalkyl ether groups (for example, ethylene glycol monobutyl ether groups), and the like. Not limited to things. Among these, a methoxy group and an ethoxy group are preferable from the standpoint of ease of raw material production and hydrolyzability. Examples of the halogen atom, perfluoroalkyl group, polyether group, and perfluoropolyether group of the substituent of R 6 include the same as those described for R 2 in the general formula (1).
　上記一般式（２）で示されるオルガノシロキサンの具体例としては、例えば下記一般式（３）又は（４）で示されるものが挙げられる。 Specific examples of the organosiloxane represented by the general formula (2) include, for example, those represented by the following general formula (3) or (4).
Figure JPOXMLDOC01-appb-C000012
 （式中、各々独立にｐ’≧２、ｑ’≧１、ｐ’＋ｑ’は４～５の整数、ｎ’は２～８の整数である。各繰り返し単位の配列は任意である。）
Figure JPOXMLDOC01-appb-C000012
 (In the formula, p ′ ≧ 2, q ′ ≧ 1, p ′ + q ′ is an integer of 4 to 5 and n ′ is an integer of 2 to 8. The arrangement of each repeating unit is arbitrary.)
　本発明のオルガノシロキサンとして、より具体的には、例えば下記一般式（５）、（６）又は（７）で示される化合物、即ち、１，３，５－トリス（２－（３，４－エポキシシクロヘキシル）エチル）－７－トリメトキシシリルオクチルテトラメチルシクロテトラシロキサン、１，３－ビス（２－（３，４－エポキシシクロヘキシル）エチル）－５，７－ビス（トリメトキシシリルオクチル）テトラメチルシクロテトラシロキサン、１，５－ビス（２－（３，４－エポキシシクロヘキシル）エチル）－３，７－ビス（トリメトキシシリルオクチル）テトラメチルシクロテトラシロキサン、１，３－ビス（２－（３，４－エポキシシクロヘキシル）エチル）－５，７－ビス（トリメトキシシリルエチル）テトラメチルシクロテトラシロキサン、１，５－ビス（２－（３，４－エポキシシクロヘキシル）エチル）－３，７－ビス（トリメトキシシリルエチル）テトラメチルシクロテトラシロキサン、１，３，５－トリス（３－グリシドキシプロピル）－７－トリメトキシシリルオクチルテトラメチルシクロテトラシロキサン、１，３－ビス（３－グリシドキシプロピル）－５，７－ビス（トリメトキシシリルオクチル）テトラメチルシクロテトラシロキサン、１，５－ビス（３－グリシドキシプロピル）－３，７－ビス（トリメトキシシリルオクチル）テトラメチルシクロテトラシロキサン、１，３，５－トリス（３－グリシドキシプロピル）－７－トリメトキシシリルエチルテトラメチルシクロテトラシロキサン、１，５－ビス（３－グリシドキシプロピル）－３，７－ビス（トリメトキシシリルエチル）テトラメチルシクロテトラシロキサン、１，３－ビス（２－（３，４－エポキシシクロヘキシル）エチル）－５－（トリメトキシシリルオクチル）－７－プロピルテトラメチルシクロテトラシロキサン、１，５－ビス（２－（３，４－エポキシシクロヘキシル）エチル）－３－（トリメトキシシリルオクチル）－７－プロピルテトラメチルシクロテトラシロキサン、１，３－ビス（２－（３，４－エポキシシクロヘキシル）エチル）－５－（トリメトキシシリルエチル）－７－プロピルテトラメチルシクロテトラシロキサン、１，５－ビス（２－（３，４－エポキシシクロヘキシル）エチル）－３－（トリメトキシシリルエチル）－７－プロピルテトラメチルシクロテトラシロキサン、１，３－ビス（３－グリシドキシプロピル）－５－（トリメトキシシリルオクチル）－７－プロピルテトラメチルシクロテトラシロキサン、１，５－ビス（３－グリシドキシプロピル）－３－（トリメトキシシリルオクチル）－７－プロピルテトラメチルシクロテトラシロキサン、１，３－ビス（３－グリシドキシプロピル）－５－（トリメトキシシリルエチル）－７－プロピルテトラメチルシクロテトラシロキサン、１，５－ビス（３－グリシドキシプロピル）－３－（トリメトキシシリルエチル）－７－プロピルテトラメチルシクロテトラシロキサン等が挙げられる。 More specifically, as the organosiloxane of the present invention, for example, a compound represented by the following general formula (5), (6) or (7), that is, 1,3,5-tris (2- (3,4-) Epoxycyclohexyl) ethyl) -7-trimethoxysilyloctyltetramethylcyclotetrasiloxane, 1,3-bis (2- (3,4-epoxycyclohexyl) ethyl) -5,7-bis (trimethoxysilyloctyl) tetramethyl Cyclotetrasiloxane, 1,5-bis (2- (3,4-epoxycyclohexyl) ethyl) -3,7-bis (trimethoxysilyloctyl) tetramethylcyclotetrasiloxane, 1,3-bis (2- (3 , 4-Epoxycyclohexyl) ethyl) -5,7-bis (trimethoxysilylethyl) tetramethylcyclotetrasiloxane 1,5-bis (2- (3,4-epoxycyclohexyl) ethyl) -3,7-bis (trimethoxysilylethyl) tetramethylcyclotetrasiloxane, 1,3,5-tris (3-glycidoxypropyl ) -7-trimethoxysilyloctyltetramethylcyclotetrasiloxane, 1,3-bis (3-glycidoxypropyl) -5,7-bis (trimethoxysilyloctyl) tetramethylcyclotetrasiloxane, 1,5-bis (3-Glycidoxypropyl) -3,7-bis (trimethoxysilyloctyl) tetramethylcyclotetrasiloxane, 1,3,5-tris (3-glycidoxypropyl) -7-trimethoxysilylethyltetramethyl Cyclotetrasiloxane, 1,5-bis (3-glycidoxypropyl) -3,7-bis (tri Toxisilylethyl) tetramethylcyclotetrasiloxane, 1,3-bis (2- (3,4-epoxycyclohexyl) ethyl) -5- (trimethoxysilyloctyl) -7-propyltetramethylcyclotetrasiloxane, 1,5 -Bis (2- (3,4-epoxycyclohexyl) ethyl) -3- (trimethoxysilyloctyl) -7-propyltetramethylcyclotetrasiloxane, 1,3-bis (2- (3,4-epoxycyclohexyl) Ethyl) -5- (trimethoxysilylethyl) -7-propyltetramethylcyclotetrasiloxane, 1,5-bis (2- (3,4-epoxycyclohexyl) ethyl) -3- (trimethoxysilylethyl) -7 -Propyltetramethylcyclotetrasiloxane, 1,3-bis (3-glycidoxy Propyl) -5- (trimethoxysilyloctyl) -7-propyltetramethylcyclotetrasiloxane, 1,5-bis (3-glycidoxypropyl) -3- (trimethoxysilyloctyl) -7-propyltetramethylcyclo Tetrasiloxane, 1,3-bis (3-glycidoxypropyl) -5- (trimethoxysilylethyl) -7-propyltetramethylcyclotetrasiloxane, 1,5-bis (3-glycidoxypropyl) -3 -(Trimethoxysilylethyl) -7-propyltetramethylcyclotetrasiloxane and the like.
Figure JPOXMLDOC01-appb-C000013
 （式中、各々独立にｐ”≧２、ｑ”≧１、ｐ”＋ｑ”は４～５の整数である。）
Figure JPOXMLDOC01-appb-C000013
 (In the formula, p ″ ≧ 2, q ″ ≧ 1, and p ″ + q ″ are each independently an integer of 4 to 5.)
　本発明のオルガノシロキサンは、１分子中に少なくとも２個のＳｉ－Ｈ基及び少なくとも１個の加水分解性シリル基を有する環状オルガノハイドロジェンシロキサンと、炭素－炭素不飽和結合を有するエポキシ基含有化合物とを白金及び／又は白金錯体存在下においてヒドロシリル化させることにより製造される。必要により他の有機官能基を導入する場合には、対応する有機官能基を含有する不飽和化合物を上記オルガノハイドロジェンシロキサン中の一部のＳｉ－Ｈ基に対してヒドロシリル化した後に、得られた環状オルガノハイドロジェンシロキサン中に残るＳｉ－Ｈ基を炭素－炭素不飽和結合を有するエポキシ基含有化合物でヒドロシリル化させることで所望の化合物を得ることができる。この際、ヒドロシリル化させる順序としては特に限定されないが、反応効率の観点から炭素－炭素不飽和結合を含有するエポキシ基含有化合物を後でヒドロシリル化させることが好ましい。 The organosiloxane of the present invention comprises a cyclic organohydrogensiloxane having at least two Si—H groups and at least one hydrolyzable silyl group in one molecule, and an epoxy group-containing compound having a carbon-carbon unsaturated bond Are hydrosilylated in the presence of platinum and / or platinum complexes. When other organic functional groups are introduced as required, it is obtained after hydrosilylation of the unsaturated compound containing the corresponding organic functional group with respect to some Si—H groups in the organohydrogensiloxane. The desired compound can be obtained by hydrosilylating the Si—H group remaining in the cyclic organohydrogensiloxane with an epoxy group-containing compound having a carbon-carbon unsaturated bond. In this case, the order of hydrosilylation is not particularly limited, but it is preferable that the epoxy group-containing compound containing a carbon-carbon unsaturated bond is hydrosilylated later from the viewpoint of reaction efficiency.
　即ち、１分子中に少なくとも２個のＳｉ－Ｈ基及び少なくとも１個の加水分解性シリル基を有する環状オルガノハイドロジェンシロキサン中に含まれる一部のＳｉ－Ｈ基と、必要により、置換基としてハロゲン原子、ビニル基、チイラン基、（メタ）アクリル基、メルカプト基、イソ（チオ）シアネート基、無水コハク酸基、パーフルオロアルキル基、ポリエーテル基及びパーフルオロポリエーテル基から選択される少なくとも１種による置換又は非置換の不飽和炭化水素化合物とを白金及び／又は白金錯体存在下においてヒドロシリル化反応させた後、得られた環状オルガノハイドロジェンシロキサン中に残るＳｉ－Ｈ基と、炭素－炭素不飽和結合を有するエポキシ基含有化合物とをヒドロシリル化反応させることが好ましい。 That is, some Si—H groups contained in a cyclic organohydrogensiloxane having at least two Si—H groups and at least one hydrolyzable silyl group in one molecule, and if necessary, as substituents At least one selected from a halogen atom, vinyl group, thiirane group, (meth) acryl group, mercapto group, iso (thio) cyanate group, succinic anhydride group, perfluoroalkyl group, polyether group and perfluoropolyether group After the hydrosilylation reaction of a substituted or unsubstituted unsaturated hydrocarbon compound with a seed in the presence of platinum and / or a platinum complex, the remaining Si—H group in the resulting cyclic organohydrogensiloxane and carbon-carbon It is preferable to carry out a hydrosilylation reaction with an epoxy group-containing compound having an unsaturated bond.
　本発明のオルガノシロキサンの製造方法において、反応温度は室温（２５℃）～１５０℃であり、好ましくは４０～１３０℃、より好ましくは７０～１２０℃である。室温未満であると反応が進行しない、又は著しく反応速度が低いため生産性に欠ける場合がある。一方、１５０℃を超える場合には熱分解、又は意図しない副反応が生じるおそれがある。 In the method for producing organosiloxane of the present invention, the reaction temperature is room temperature (25 ° C.) to 150 ° C., preferably 40 to 130 ° C., more preferably 70 to 120 ° C. If the temperature is lower than room temperature, the reaction does not proceed, or the reaction rate is extremely low, so that productivity may be lacking. On the other hand, when it exceeds 150 ° C., there is a possibility that thermal decomposition or unintended side reaction may occur.
　本発明のオルガノシロキサンの製造方法において、反応時間は１０分～２４時間である。反応の進行により原料が十分に消費されるような時間であればよいが、好ましくは１～１０時間、より好ましくは２～７時間である。１０分未満であると原料消費が不十分となるおそれがあり、２４時間を超えると既に原料が完全に消費されていて、不要な工程となり生産効率が低下してしまう場合がある。 In the method for producing organosiloxane of the present invention, the reaction time is 10 minutes to 24 hours. The time may be a time at which the raw material is sufficiently consumed by the progress of the reaction, but it is preferably 1 to 10 hours, more preferably 2 to 7 hours. If it is less than 10 minutes, the consumption of the raw material may be insufficient, and if it exceeds 24 hours, the raw material has already been completely consumed, which may be an unnecessary process and may reduce the production efficiency.
　本発明のオルガノシロキサンの製造方法において適宜反応溶媒を使用してもよい。原料と非反応性で、反応に使用する白金錯体の触媒毒にならないようなものであれば特に限定されないが、代表的にはヘキサン、ヘプタンといった脂肪族炭化水素系溶媒、トルエン、キシレンといった芳香族炭化水素系溶媒、メタノール、エタノール、プロパノール、イソプロパノールといったアルコール系溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトンといったケトン系溶媒が挙げられる。 A reaction solvent may be appropriately used in the method for producing an organosiloxane of the present invention. Although it is not particularly limited as long as it is non-reactive with the raw material and does not become a catalyst poison of the platinum complex used in the reaction, typically, an aliphatic hydrocarbon solvent such as hexane or heptane, or an aromatic such as toluene or xylene. Examples thereof include hydrocarbon solvents, alcohol solvents such as methanol, ethanol, propanol and isopropanol, and ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone.
　本発明におけるオルガノハイドロジェンシロキサンは、環状シロキサンを主骨格とし、１分子中にＳｉ－Ｈ基を２個以上及び加水分解性シリル基を１個以上含むものであれば特に限定されず、その他の構造として直鎖状、分岐状といった構造を有してもよい。但し、バインダー成分として用いた際に、ある程度分子量分布が狭い方が不必要な架橋密度の増大を避けることができるため、低分子量とするためにも環状シロキサンであることは必須である。 The organohydrogensiloxane in the present invention is not particularly limited as long as it has a cyclic siloxane as a main skeleton and contains at least two Si—H groups and at least one hydrolyzable silyl group in one molecule. The structure may have a linear structure or a branched structure. However, when it is used as a binder component, an unnecessary increase in crosslink density can be avoided if the molecular weight distribution is narrow to some extent, so that it is essential to be a cyclic siloxane in order to achieve a low molecular weight.
　環状オルガノハイドロジェンシロキサンの具体的な例としては、１，３，５－トリメチル－１－トリメトキシシリルオクチルシクロトリシロキサン、１，３，５－トリメチル－１－トリメトキシシリルヘキシルシクロトリシロキサン、１，３，５－トリメチル－１－トリメトキシシリルエチルシクロトリシロキサン、１，３，５－トリメチル－１－トリエトキシシリルオクチルシクロトリシロキサン、１，３，５－トリメチル－１－トリエトキシシリルヘキシルシクロトリシロキサン、１，３，５－トリメチル－１－トリエトキシシリルエチルシクロトリシロキサン、１，３，５，７－テトラメチル－１－トリメトキシシリルオクチルシクロテトラシロキサン、１，３，５，７－テトラメチル－１－トリメトキシシリルオクチル－３－プロピルシクロテトラシロキサン、１，３，５，７－テトラメチル－１－トリメトキシシリルオクチル－５－プロピルシクロテトラシロキサン、１，３，５，７－テトラメチル－１－トリメトキシシリルヘキシルシクロテトラシロキサン、１，３，５，７－テトラメチル－１－トリメトキシシリルエチルシクロテトラシロキサン、１，３，５，７－テトラメチル－１－トリメトキシシリルエチル－３－プロピルシクロテトラシロキサン、１，３，５，７－テトラメチル－１－トリメトキシシリルエチル－５－プロピルシクロテトラシロキサン、１，３，５，７－テトラメチル－１－トリエトキシシリルオクチルシクロテトラシロキサン、１，３，５，７－テトラメチル－１－トリエトキシシリルオクチル－３－プロピルシクロテトラシロキサン、１，３，５，７－テトラメチル－１－トリエトキシシリルオクチル－５－プロピルシクロテトラシロキサン、１，３，５，７－テトラメチル－１－トリエトキシシリルヘキシルシクロテトラシロキサン、１，３，５，７－テトラメチル－１－トリエトキシシリルエチルシクロテトラシロキサン、１，３，５，７－テトラメチル－１－トリエトキシシリルエチル－３－プロピルシクロテトラシロキサン、１，３，５，７－テトラメチル－１－トリエトキシシリルエチル－５－プロピルシクロテトラシロキサン、１，３，５，７－テトラメチル－１，３－ビス（トリメトキシシリルオクチル）シクロテトラシロキサン、１，３，５，７－テトラメチル－１，３－ビス（トリメトキシシリルヘキシル）シクロテトラシロキサン、１，３，５，７－テトラメチル－１，３－ビス（トリメトキシシリルエチル）シクロテトラシロキサン、１，３，５，７－テトラメチル－１，３－ビス（トリエトキシシリルオクチル）シクロテトラシロキサン、１，３，５，７－テトラメチル－１，３－ビス（トリエトキシシリルヘキシル）シクロテトラシロキサン、１，３，５，７－テトラメチル－１，３－ビス（トリエトキシシリルエチル）シクロテトラシロキサン、１，３，５，７－テトラメチル－１，５－ビス（トリメトキシシリルオクチル）シクロテトラシロキサン、１，３，５，７－テトラメチル－１，５－ビス（トリメトキシシリルヘキシル）シクロテトラシロキサン、１，３，５，７－テトラメチル－１，５－ビス（トリメトキシシリルエチル）シクロテトラシロキサン、１，３，５，７－テトラメチル－１，５－ビス（トリエトキシシリルオクチル）シクロテトラシロキサン、１，３，５，７－テトラメチル－１，５－ビス（トリエトキシシリルヘキシル）シクロテトラシロキサン、１，３，５，７－テトラメチル－１，５－ビス（トリエトキシシリルエチル）シクロテトラシロキサン、１，３，５，７，９－ペンタメチル－１－トリメトキシシリルオクチルシクロペンタシロキサン、１，３，５，７，９－ペンタメチル－１－トリメトキシシリルヘキシルシクロペンタシロキサン、１，３，５，７，９－ペンタメチル－１－トリメトキシシリルエチルシクロペンタシロキサン、１，３，５，７，９－ペンタメチル－１－トリエトキシシリルオクチルシクロペンタシロキサン、１，３，５，７，９－ペンタメチル－１－トリエトキシシリルヘキシルシクロペンタシロキサン、１，３，５，７，９－ペンタメチル－１－トリエトキシシリルエチルシクロペンタシロキサン等が挙げられるが、ここに例示されたものに限らない。これらの中でも上述した理由と原料の入手の容易さから１，３，５，７－テトラメチル－１－トリメトキシシリルオクチルシクロテトラシロキサン、１，３，５，７－テトラメチル－１－トリメトキシシリルエチルシクロテトラシロキサンが最も好ましい。 Specific examples of the cyclic organohydrogensiloxane include 1,3,5-trimethyl-1-trimethoxysilyloctylcyclotrisiloxane, 1,3,5-trimethyl-1-trimethoxysilylhexylcyclotrisiloxane, , 3,5-trimethyl-1-trimethoxysilylethylcyclotrisiloxane, 1,3,5-trimethyl-1-triethoxysilyloctylcyclotrisiloxane, 1,3,5-trimethyl-1-triethoxysilylhexylcyclo Trisiloxane, 1,3,5-trimethyl-1-triethoxysilylethylcyclotrisiloxane, 1,3,5,7-tetramethyl-1-trimethoxysilyloctylcyclotetrasiloxane, 1,3,5,7- Tetramethyl-1-trimethoxysilyloctyl-3-pro Rucyclotetrasiloxane, 1,3,5,7-tetramethyl-1-trimethoxysilyloctyl-5-propylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1-trimethoxysilylhexylcyclotetrasiloxane 1,3,5,7-tetramethyl-1-trimethoxysilylethylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1-trimethoxysilylethyl-3-propylcyclotetrasiloxane, 1,3 , 5,7-tetramethyl-1-trimethoxysilylethyl-5-propylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1-triethoxysilyloctylcyclotetrasiloxane, 1,3,5,7 -Tetramethyl-1-triethoxysilyloctyl-3-propylcyclotetrasiloxane, , 3,5,7-tetramethyl-1-triethoxysilyloctyl-5-propylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1-triethoxysilylhexylcyclotetrasiloxane, 1,3,5 , 7-tetramethyl-1-triethoxysilylethylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1-triethoxysilylethyl-3-propylcyclotetrasiloxane, 1,3,5,7-tetra Methyl-1-triethoxysilylethyl-5-propylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3-bis (trimethoxysilyloctyl) cyclotetrasiloxane, 1,3,5,7- Tetramethyl-1,3-bis (trimethoxysilylhexyl) cyclotetrasiloxane, 1,3,5,7-teto Lamethyl-1,3-bis (trimethoxysilylethyl) cyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3-bis (triethoxysilyloctyl) cyclotetrasiloxane, 1,3,5,7 -Tetramethyl-1,3-bis (triethoxysilylhexyl) cyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3-bis (triethoxysilylethyl) cyclotetrasiloxane, 1,3,5 , 7-tetramethyl-1,5-bis (trimethoxysilyloctyl) cyclotetrasiloxane, 1,3,5,7-tetramethyl-1,5-bis (trimethoxysilylhexyl) cyclotetrasiloxane, 1,3 , 5,7-Tetramethyl-1,5-bis (trimethoxysilylethyl) cyclotetrasiloxane, 1,3,5,7-teto Methyl-1,5-bis (triethoxysilyloctyl) cyclotetrasiloxane, 1,3,5,7-tetramethyl-1,5-bis (triethoxysilylhexyl) cyclotetrasiloxane, 1,3,5,7 -Tetramethyl-1,5-bis (triethoxysilylethyl) cyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1-trimethoxysilyloctylcyclopentasiloxane, 1,3,5,7,9 -Pentamethyl-1-trimethoxysilylhexylcyclopentasiloxane, 1,3,5,7,9-pentamethyl-1-trimethoxysilylethylcyclopentasiloxane, 1,3,5,7,9-pentamethyl-1-tri Ethoxysilyloctylcyclopentasiloxane, 1,3,5,7,9-pentamethyl-1-triethoxy Li hexyl cyclopentasiloxane, 1,3,5,7,9-pentamethyl-1-but-triethoxysilylethyl cyclopentasiloxane and the like, not limited to those exemplified here. Among these, 1,3,5,7-tetramethyl-1-trimethoxysilyloctylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1-trimethoxy are explained above and the raw materials are easily available. Most preferred is silylethylcyclotetrasiloxane.
　ここで、本発明においては、必要により加えられる不飽和炭化水素化合物が、下記式
ＣＨ2＝ＣＨ－Ｒ6a
（式中、Ｒ6aは水素原子又は置換基を有してもよい炭素数１～１４、特に１～８のアルキル基であって、該置換基はハロゲン原子、ビニル基、チイラン基、（メタ）アクリル基、メルカプト基、イソ（チオ）シアネート基、無水コハク酸基、パーフルオロアルキル基、ポリエーテル基及びパーフルオロポリエーテル基から選ばれるものである。）
で示されるものであり、炭素－炭素不飽和結合を有するエポキシ基含有化合物が、下記式 Here, in the present invention, the unsaturated hydrocarbon compound added if necessary is represented by the following formula CH 2 ═CH—R 6a.
(In the formula, R 6a is a hydrogen atom or an alkyl group having 1 to 14, particularly 1 to 8 carbon atoms which may have a substituent, and the substituent is a halogen atom, a vinyl group, a thiirane group, (meta ) An acrylic group, a mercapto group, an iso (thio) cyanate group, a succinic anhydride group, a perfluoroalkyl group, a polyether group, and a perfluoropolyether group.
An epoxy group-containing compound having a carbon-carbon unsaturated bond is represented by the following formula:
Figure JPOXMLDOC01-appb-C000014
 （式中、Ｒ3はエポキシ基を含有する置換基、ｋ１は０～６の整数である。）
Figure JPOXMLDOC01-appb-C000014
 (Wherein R 3 is a substituent containing an epoxy group, and k1 is an integer of 0 to 6)
で示されるものであり、下記一般式（２）で示されるエポキシ基含有環状オルガノシロキサンを得ることが好ましい。 It is preferable to obtain an epoxy group-containing cyclic organosiloxane represented by the following general formula (2).
Figure JPOXMLDOC01-appb-C000015
 （式中、Ｒ1は上記と同様であり、Ｒ3は各々独立にエポキシ基を含有する置換基、Ｒ4は各々独立に炭素数１～４のアルキル基、Ｒ5は各々独立にハロゲン原子、酸素原子を間に挟んでもよい炭素数１～２０、特に１～６のアルコキシ基、又は炭素数６～１０のアリーロキシ基であり、Ｒ6は各々独立に水素原子又は置換基を有してもよい炭素数１～１４、特に１～８のアルキル基であって、該置換基はハロゲン原子、ビニル基、チイラン基、（メタ）アクリル基、メルカプト基、イソ（チオ）シアネート基、無水コハク酸基、パーフルオロアルキル基、ポリエーテル基、及びパーフルオロポリエーテル基から選ばれるものであり、ｋは２～８の整数、ｍは２～１４、特に２～８の整数、ｘは１～３の整数である。ｐ≧２、ｑ≧１、ｒ≧０、ｐ＋ｑ＋ｒは３～６の整数である。各繰り返し単位の配列は任意である。）
Figure JPOXMLDOC01-appb-C000015
 Wherein R 1 is as defined above, R 3 is each independently a substituent containing an epoxy group, R 4 is each independently an alkyl group having 1 to 4 carbon atoms, and R 5 is each independently a halogen atom. , An alkoxy group having 1 to 20 carbon atoms, particularly 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms, in which an oxygen atom may be interposed, and each R 6 independently has a hydrogen atom or a substituent. An alkyl group having 1 to 14 carbon atoms, particularly 1 to 8 carbon atoms, and the substituent is a halogen atom, vinyl group, thiirane group, (meth) acryl group, mercapto group, iso (thio) cyanate group, anhydrous succinate Selected from an acid group, a perfluoroalkyl group, a polyether group, and a perfluoropolyether group, k is an integer of 2 to 8, m is an integer of 2 to 14, particularly 2 to 8, and x is 1 to It is an integer of 3. p ≧ 2, q ≧ 1, r ≧ 0, p + Q + r is an integer of 3 to 6. The arrangement of each repeating unit is arbitrary.)
　本発明における炭素－炭素不飽和結合を有するエポキシ基含有化合物は、ヒドロシリル化反応性を有するオレフィン含有のエポキシ基含有化合物であれば特に限定されないが、具体的には１，２－エポキシ－４－ビニルシクロヘキサン、アリルグリシジルエーテル、１，２－エポキシ－５－ヘキセン、１，２－エポキシ－７－オクテンが挙げられるが、ここに例示されたものに限らない。 The epoxy group-containing compound having a carbon-carbon unsaturated bond in the present invention is not particularly limited as long as it is an olefin-containing epoxy group-containing compound having hydrosilylation reactivity, and specifically, 1,2-epoxy-4- Examples include, but are not limited to, vinylcyclohexane, allyl glycidyl ether, 1,2-epoxy-5-hexene, and 1,2-epoxy-7-octene.
　エポキシ基以外の上述した置換基Ｒ6を導入する場合は、その置換基を有するオレフィン化合物（上述した、ＣＨ2＝ＣＨ－Ｒ6a）を用いればよい。 When the above-mentioned substituent R 6 other than an epoxy group is introduced, an olefin compound having the substituent (described above, CH 2 ═CH—R 6a ) may be used.
　本発明における反応原料の使用比率はオルガノハイドロジェンシロキサン中のＳｉ－Ｈ基１モルに対して炭素－炭素不飽和結合を有する化合物を合計で０．７～１．５モルが好ましく、より好ましくは０．９～１．１モルである。 The ratio of the reaction raw materials used in the present invention is preferably 0.7 to 1.5 moles, more preferably a total of compounds having a carbon-carbon unsaturated bond per mole of Si—H groups in the organohydrogensiloxane. 0.9 to 1.1 mol.
　なお、上記環状シロキサンのＳｉ－Ｈ基数に対し、上記炭素－炭素不飽和結合を有するエポキシ基含有化合物、更に必要により添加されるオレフィン化合物の合計炭素－炭素不飽和結合基の数が少ない場合、Ｒ6が水素原子であるものが得られる。 When the number of the total carbon-carbon unsaturated bond groups of the epoxy group-containing compound having the carbon-carbon unsaturated bond and the olefin compound added as necessary is small with respect to the number of Si-H groups of the cyclic siloxane, A compound in which R 6 is a hydrogen atom is obtained.
　本発明におけるヒドロシリル化反応触媒は、公知の技術として知られている白金（Ｐｔ）及び／又は白金（Ｐｔ）を中心金属とする錯体化合物である。具体的には、塩化白金酸のアルコール溶液、塩化白金酸の１，３－ジビニルテトラメチルジシロキサン錯体並びに該錯体を中和処理した化合物や、中心金属の酸化数がＰｔ（ＩＩ）やＰｔ（０）の１，３－ジビニルテトラメチルジシロキサン錯体が挙げられる。好ましくは中心金属の酸化数がＰｔ（ＩＶ）以外の錯体であることが付加位置選択性の点から望ましく、特にＰｔ（０）、Ｐｔ（ＩＩ）であることが好ましい。 The hydrosilylation reaction catalyst in the present invention is a complex compound having platinum (Pt) and / or platinum (Pt) as a central metal, which is known as a known technique. Specifically, an alcohol solution of chloroplatinic acid, a 1,3-divinyltetramethyldisiloxane complex of chloroplatinic acid, a compound obtained by neutralizing the complex, and the oxidation number of the central metal is Pt (II) or Pt ( 0) 1,3-divinyltetramethyldisiloxane complex. Preferably, the oxidation number of the central metal is a complex other than Pt (IV) from the viewpoint of addition site selectivity, and Pt (0) and Pt (II) are particularly preferable.
　本発明におけるヒドロシリル化反応触媒の使用量は、ヒドロシリル化反応の触媒効果が発現する量であれば特に限定されないが、好ましくはオレフィン化合物の合計量１モルに対して白金金属換算で０．０００００１～１モルであり、より好ましくは０．０００００３～０．０１モルである。０．０００００１モル未満である場合には十分な触媒効果が発現しないおそれがあり、１モルより多い場合には効果が飽和するため生産コストが高くなり不経済になってしまうおそれがある。 The amount of the hydrosilylation reaction catalyst used in the present invention is not particularly limited as long as the catalytic effect of the hydrosilylation reaction is manifested, but is preferably 0.000001 to 0.000001 to in terms of platinum metal with respect to 1 mol of the total amount of olefin compounds. 1 mol, more preferably 0.000003 to 0.01 mol. When the amount is less than 0.000001 mol, there is a possibility that a sufficient catalytic effect may not be exhibited. When the amount is more than 1 mol, the effect is saturated, and the production cost may be increased, which may be uneconomical.
　以下、実施例を挙げて、本発明をより詳しく説明するが、本発明はこれらの実施例に限定されるものではない。なお、粘度はオストワルド粘度計により測定した２５℃における値を示す。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In addition, a viscosity shows the value in 25 degreeC measured with the Ostwald viscometer.
［実施例１］１，３，５－トリス（２－（３，４－エポキシシクロヘキシル）エチル）－７－トリメトキシシリルオクチルテトラメチルシクロテトラシロキサンの合成
　撹拌機、還流冷却器、滴下ロート及び温度計を備えた５００ｍｌセパラブルフラスコに、１，３，５，７－テトラメチル－１－トリメトキシシリルオクチルシクロテトラシロキサン１００．０質量部（０．２１モル）、トルエン１００．０質量部、イソプロパノール３０．０質量部、アセトニトリル０．０９質量部、白金錯体（Ｐｔ（０）の１，３－ジビニルテトラメチルジシロキサン錯体）のトルエン溶液を、Ｓｉ－Ｈ基１モルに対して白金錯体が０．０００００３モル（白金換算）に相当する量を納め撹拌混合した。その後、加熱して内温８５℃となったところで１，２－エポキシ－４－ビニルシクロヘキサン８６．５質量部（０．７０モル）を１時間かけて滴下した。滴下と同時に反応が起こり、発熱が生じ、反応液温度が８５℃から徐々に上昇したため、加熱を停止し、反応液温度が９０℃を超えないように調整しながら滴下を継続した。滴下終了後、内温８０℃となるように加熱をしながら反応液を１時間熟成した後に、反応液のＩＲ並びに水素ガス発生量測定を行いＳｉ－Ｈ基の残存が無いことを確認した。その後、トリフェニルホスフィンの２５質量％トルエン溶液０．０１質量部を添加し、減圧留去（８０℃、２ｍｍＨｇ）によりトルエン、イソプロパノール、アセトニトリル、過剰の１，２－エポキシ－４－ビニルシクロヘキサンを除去することで表題シロキサンを粘度２６２ｍｍ2／ｓ、屈折率１．４７３８（２５℃）の無色透明液体として得た。得られた表題シロキサンについて1Ｈ－ＮＭＲ並びにＩＲ測定を行った。結果をそれぞれ図１及び２に示す。 [Example 1] Synthesis of 1,3,5-tris (2- (3,4-epoxycyclohexyl) ethyl) -7-trimethoxysilyloctyltetramethylcyclotetrasiloxane Stirrer, reflux condenser, dropping funnel and temperature In a 500 ml separable flask equipped with a meter, 100.0 parts by mass (0.21 mol) of 1,3,5,7-tetramethyl-1-trimethoxysilyloctylcyclotetrasiloxane, 100.0 parts by mass of toluene, isopropanol 30.0 parts by mass, 0.09 parts by mass of acetonitrile, a toluene solution of a platinum complex (1,3-divinyltetramethyldisiloxane complex of Pt (0)) An amount corresponding to 0.000003 mol (in terms of platinum) was placed and mixed with stirring. Thereafter, when the internal temperature reached 85 ° C. by heating, 86.5 parts by mass (0.70 mol) of 1,2-epoxy-4-vinylcyclohexane was added dropwise over 1 hour. At the same time as the dropping, a reaction occurred, an exotherm was generated, and the temperature of the reaction solution gradually increased from 85 ° C. Therefore, the heating was stopped, and the dropping was continued while adjusting the reaction solution temperature to not exceed 90 ° C. After completion of the dropping, the reaction solution was aged for 1 hour while being heated to an internal temperature of 80 ° C., and then IR and hydrogen gas generation amount of the reaction solution were measured to confirm that no Si—H group remained. Then, 0.01 parts by mass of a 25% by weight toluene solution of triphenylphosphine was added, and toluene, isopropanol, acetonitrile, and excess 1,2-epoxy-4-vinylcyclohexane were removed by distillation under reduced pressure (80 ° C., 2 mmHg). As a result, the title siloxane was obtained as a colorless transparent liquid having a viscosity of 262 mm 2 / s and a refractive index of 1.4738 (25 ° C.). The obtained title siloxane was subjected to 1 H-NMR and IR measurement. The results are shown in FIGS. 1 and 2, respectively.
［実施例２］１，３，５－トリス（３－グリシドキシプロピル）－７－トリメトキシシリルオクチルテトラメチルシクロテトラシロキサンの合成
　撹拌機、還流冷却器、滴下ロート及び温度計を備えた５００ｍｌセパラブルフラスコに、１，３，５，７－テトラメチル－１－トリメトキシシリルオクチルシクロテトラシロキサン１００．０質量部（０．２１モル）、トルエン１００．０質量部、白金錯体（Ｐｔ（０）の１，３－ジビニルテトラメチルジシロキサン錯体）のトルエン溶液を、Ｓｉ－Ｈ基１モルに対して白金錯体が０．０００００３モル（白金換算）に相当する量を納め撹拌混合した。その後、加熱して内温８５℃となったところでアリルグリシジルエーテル７９．７質量部（０．７０モル）を１時間かけて滴下した。滴下と同時に反応が起こり、発熱が生じ、反応液温度が８５℃から徐々に上昇したため、加熱を停止し、反応液温度が９０℃を超えないように調整しながら滴下を継続した。滴下終了後、内温８０℃となるように加熱をしながら反応液を１時間熟成した後に、反応液のＩＲ並びに水素ガス発生量測定を行いＳｉ－Ｈ基の残存が無いことを確認した。その後、減圧留去（８０℃、２ｍｍＨｇ）によりトルエン、過剰のアリルグリシジルエーテルを除去することで表題シロキサンを粘度７４ｍｍ2／ｓ、屈折率１．４５５９（２５℃）の無色透明液体として得た。得られた表題シロキサンについて1Ｈ－ＮＭＲ並びにＩＲ測定を行った。結果をそれぞれ図３及び４に示す。 Example 2 Synthesis of 1,3,5-tris (3-glycidoxypropyl) -7-trimethoxysilyloctyltetramethylcyclotetrasiloxane 500 ml equipped with stirrer, reflux condenser, dropping funnel and thermometer In a separable flask, 100.0 parts by mass (0.21 mol) of 1,3,5,7-tetramethyl-1-trimethoxysilyloctylcyclotetrasiloxane, 100.0 parts by mass of toluene, platinum complex (Pt (0 1) of 1,3-divinyltetramethyldisiloxane complex) was stirred and mixed in an amount corresponding to 0.000003 mol of platinum complex (in terms of platinum) with respect to 1 mol of Si—H group. Thereafter, when the internal temperature reached 85 ° C. by heating, 79.7 parts by mass (0.70 mol) of allyl glycidyl ether was added dropwise over 1 hour. At the same time as the dropping, a reaction occurred, an exotherm was generated, and the temperature of the reaction solution gradually increased from 85 ° C. Therefore, the heating was stopped, and the dropping was continued while adjusting the reaction solution temperature to not exceed 90 ° C. After completion of the dropping, the reaction solution was aged for 1 hour while being heated to an internal temperature of 80 ° C., and then IR and hydrogen gas generation amount of the reaction solution were measured to confirm that no Si—H group remained. Thereafter, the title siloxane was obtained as a colorless transparent liquid having a viscosity of 74 mm 2 / s and a refractive index of 1.4559 (25 ° C.) by removing toluene and excess allyl glycidyl ether by distillation under reduced pressure (80 ° C., 2 mmHg). The obtained title siloxane was subjected to 1 H-NMR and IR measurement. The results are shown in FIGS. 3 and 4, respectively.
［実施例３］１，３，５－トリス（３－グリシドキシプロピル）－７－トリメトキシシリルエチルテトラメチルシクロテトラシロキサンの合成
　撹拌機、還流冷却器、滴下ロート及び温度計を備えた５００ｍｌセパラブルフラスコに、１，３，５，７－テトラメチル－１－トリメトキシシリルエチルシクロテトラシロキサン１００．０質量部（０．２６モル）、トルエン１００．０質量部、白金錯体（Ｐｔ（０）の１，３－ジビニルテトラメチルジシロキサン錯体）のトルエン溶液を、Ｓｉ－Ｈ基１モルに対して白金錯体が０．０００００３モル（白金換算）に相当する量を納め撹拌混合した。その後、加熱して内温８５℃となったところでアリルグリシジルエーテル１１７．４質量部（１．０３モル）を１時間かけて滴下した。滴下と同時に反応が起こり、発熱が生じ、反応液温度が８５℃から徐々に上昇したため、加熱を停止し、反応液温度が９０℃を超えないように調整しながら滴下を継続した。滴下終了後、内温８０℃となるように加熱をしながら反応液を１時間熟成した後に、反応液のＩＲ並びに水素ガス発生量測定を行いＳｉ－Ｈ基の残存が無いことを確認した。その後、減圧留去（８０℃、２ｍｍＨｇ）によりトルエン、過剰のアリルグリシジルエーテルを除去することで表題シロキサンを粘度６４ｍｍ2／ｓ、屈折率１．４５５２（２５℃）の無色透明液体として得た。得られた表題シロキサンについて1Ｈ－ＮＭＲ並びにＩＲ測定を行った。結果をそれぞれ図５及び６に示す。 [Example 3] Synthesis of 1,3,5-tris (3-glycidoxypropyl) -7-trimethoxysilylethyltetramethylcyclotetrasiloxane 500 ml equipped with stirrer, reflux condenser, dropping funnel and thermometer In a separable flask, 100.0 parts by mass (0.26 mol) of 1,3,5,7-tetramethyl-1-trimethoxysilylethylcyclotetrasiloxane, 100.0 parts by mass of toluene, platinum complex (Pt (0 1) of 1,3-divinyltetramethyldisiloxane complex) was stirred and mixed in an amount corresponding to 0.000003 mol of platinum complex (in terms of platinum) with respect to 1 mol of Si—H group. Thereafter, when the internal temperature reached 85 ° C. by heating, 117.4 parts by mass (1.03 mol) of allyl glycidyl ether was added dropwise over 1 hour. At the same time as the dropping, a reaction occurred, an exotherm was generated, and the temperature of the reaction solution gradually increased from 85 ° C. Therefore, the heating was stopped, and the dropping was continued while adjusting the reaction solution temperature to not exceed 90 ° C. After completion of the dropping, the reaction solution was aged for 1 hour while being heated to an internal temperature of 80 ° C., and then IR and hydrogen gas generation amount of the reaction solution were measured to confirm that no Si—H group remained. Thereafter, the title siloxane was obtained as a colorless transparent liquid having a viscosity of 64 mm 2 / s and a refractive index of 1.4552 (25 ° C.) by removing toluene and excess allyl glycidyl ether by distillation under reduced pressure (80 ° C., 2 mmHg). The obtained title siloxane was subjected to 1 H-NMR and IR measurement. The results are shown in FIGS. 5 and 6, respectively.

Claims (5)

  1. 　下記一般式（１）で示されるエポキシ基含有環状オルガノシロキサン。
    Figure JPOXMLDOC01-appb-C000001
    （式中、Ｒ1は各々独立に炭素数１～１０のアルキル基又は炭素数６～１０のアリール基、Ｒ2は各々独立に水素原子又は置換基を有してもよい炭素数１～１４のアルキル基であって、該置換基はハロゲン原子、ビニル基、エポキシ基、チイラン基、（メタ）アクリル基、メルカプト基、イソ（チオ）シアネート基、加水分解性シリル基、無水コハク酸基、パーフルオロアルキル基、ポリエーテル基及びパーフルオロポリエーテル基から選ばれるものであり、その内加水分解性シリル基を置換基とするＲ2が１個以上、エポキシ基を置換基とするＲ2が２個以上である。ｎは３～６の整数である。）     An epoxy group-containing cyclic organosiloxane represented by the following general formula (1).
    Figure JPOXMLDOC01-appb-C000001
    (Wherein R 1 is each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 2 is each independently having 1 to 14 carbon atoms which may have a hydrogen atom or a substituent) Wherein the substituent is a halogen atom, vinyl group, epoxy group, thiirane group, (meth) acryl group, mercapto group, iso (thio) cyanate group, hydrolyzable silyl group, succinic anhydride group, perfluoroalkyl group, those selected from polyether groups and perfluoropolyether group, R 2 is one or more of the inner hydrolyzable silyl group and a substituted group, R 2 to the epoxy group with a substituent 2 or more, and n is an integer of 3 to 6.)
  2. 　下記一般式（２）で示される請求項１記載のエポキシ基含有環状オルガノシロキサン。
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ1は上記と同様であり、Ｒ3は各々独立にエポキシ基を含有する置換基、Ｒ4は各々独立に炭素数１～４のアルキル基、Ｒ5は各々独立にハロゲン原子、酸素原子を間に挟んでもよい炭素数１～２０のアルコキシ基、又は炭素数６～１０のアリーロキシ基であり、Ｒ6は各々独立に水素原子又は置換基を有してもよい炭素数１～１４のアルキル基であって、該置換基はハロゲン原子、ビニル基、チイラン基、（メタ）アクリル基、メルカプト基、イソ（チオ）シアネート基、無水コハク酸基、パーフルオロアルキル基、ポリエーテル基及びパーフルオロポリエーテル基から選ばれるものであり、ｋは２～８の整数、ｍは２～１４の整数、ｘは１～３の整数である。ｐ≧２、ｑ≧１、ｒ≧０、ｐ＋ｑ＋ｒは３～６の整数である。）     The epoxy group-containing cyclic organosiloxane according to claim 1, which is represented by the following general formula (2).
    Figure JPOXMLDOC01-appb-C000002
     Wherein R 1 is as defined above, R 3 is each independently a substituent containing an epoxy group, R 4 is each independently an alkyl group having 1 to 4 carbon atoms, and R 5 is each independently a halogen atom. , An alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms, which may have an oxygen atom between them, and each R 6 may independently have a hydrogen atom or a substituent. Wherein the substituent is a halogen atom, vinyl group, thiirane group, (meth) acryl group, mercapto group, iso (thio) cyanate group, succinic anhydride group, perfluoroalkyl group, polyether Group and a perfluoropolyether group, k is an integer of 2 to 8, m is an integer of 2 to 14, and x is an integer of 1 to 3. p ≧ 2, q ≧ 1, r ≧ 0 and p + q + r are integers of 3 to 6.)
  3. 　下記一般式（３）又は（４）で示される請求項２記載のエポキシ基含有環状オルガノシロキサン。
    Figure JPOXMLDOC01-appb-C000003
     （式中、各々独立にｐ’≧２、ｑ’≧１、ｐ’＋ｑ’は４～５の整数、ｎ’は２～８の整数である。）     The epoxy group-containing cyclic organosiloxane according to claim 2, represented by the following general formula (3) or (4).
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, p ′ ≧ 2, q ′ ≧ 1, p ′ + q ′ is an integer of 4 to 5 and n ′ is an integer of 2 to 8).
  4. 　下記一般式（５）、（６）又は（７）で示される請求項３記載のエポキシ基含有環状オルガノシロキサン。
    Figure JPOXMLDOC01-appb-C000004
     （式中、各々独立にｐ”≧２、ｑ”≧１、ｐ”＋ｑ”は４～５の整数である。）     The epoxy group-containing cyclic organosiloxane according to claim 3, which is represented by the following general formula (5), (6) or (7).
    Figure JPOXMLDOC01-appb-C000004
     (In the formula, p ″ ≧ 2, q ″ ≧ 1, and p ″ + q ″ are each independently an integer of 4 to 5.)
  5. 　環状シロキサンがシクロテトラシロキサンである請求項１～４のいずれか１項に記載のエポキシ基含有環状オルガノシロキサン。 The epoxy group-containing cyclic organosiloxane according to any one of claims 1 to 4, wherein the cyclic siloxane is cyclotetrasiloxane.
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