TWI595026B - Polyether-modified alkoxysiloxane containing organofunctional groups and its production method - Google Patents

Description

Polyether modified alkoxy oxirane containing organofunctional group and preparation method thereof

The present invention relates to a resin curing agent, a resin modifier, a paint modifier, an adhesive modifier, a surface treatment agent for fibers, an inorganic material (an inorganic pigment for a coating, an inorganic filler for a plastic, and a cosmetic). An organofunctional group-containing polyether-modified alkoxy oxirane such as a surface treatment agent for inorganic powder, glass, concrete, or the like, and a method for producing the same. Further, the present invention relates to a resin composition containing the alkoxy siloxane.

A polyoxyxene oligomer type coupling agent containing an organic functional group such as an epoxy group, a fluorenyl group, a (meth) acryloxy group, an alkenyl group, a haloalkyl group or an amine group and an alkoxyalkyl group in one molecule It is a useful material for coatings, coating agents, and resin modification.

For example, when an organic resin reactive with an organic functional group of a coupling agent is reacted with a coupling agent, an alkoxyalkyl group is introduced into the organic resin. In this way, the organic resin is modified, and the adhesion to the inorganic substrate or the adhesion is greatly improved (Patent Documents 1 to 3: JP-A-H09-040908, JP-A-09-040911, and JP-A JP-A, Japan) 09- Bulletin No. 111188).

Further, in recent years, an organic functional group such as an epoxy group, a carboxyl group, a hydroxyl group or an amine group has been reported in a side chain of a polyoxygenated oil, and a polyether group and an alkoxyalkylene group have been co-modified. A polyoxyxene oligomer type coupling agent which is used for applications such as an adhesive, a primer, or an adhesive. By introducing a polyether group into the molecule of the coupling agent, the compatibility between the coupling agent and the organic resin can be improved, and the adhesion between the organic resin and the inorganic substrate can be improved. This material is subjected to addition reaction of a polyether group by reacting a polyether compound containing a reactive double bond with an organooxane having a Si-H group under a platinum catalyst (Patent Documents 4 and 5). Japanese Laid-Open Patent Publication No. Hei 05-043696, and Japanese Laid-Open Patent Publication No. Hei 07-331206.

However, in the case where a plurality of polyether groups are introduced into a molecule of a siloxane, there is a problem that the reactivity is lowered as the amount of introduction increases, and the reaction is not completed, leaving unreacted polyether. Further, since a platinum catalyst is used, there is a problem that the color of the catalyst is caused by the use of the catalyst. Further, in the presence of an organofunctional group such as a thiol group, the reactivity of the polyether compound containing a reactive double bond under a platinum catalyst with the Si-H group is lowered, making it difficult to introduce a polyether group. That is, in this method, depending on the selected organic functional group, there is a problem that it cannot be modified with the polyether.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 09-040908

[Patent Document 2] Japanese Patent Publication No. 09-040911

[Patent Document 3] Japanese Patent Publication No. 09-111188

[Patent Document 4] Japanese Patent Publication No. 05-043696

[Patent Document 5] Japanese Patent Laid-Open Publication No. Hei 07-331206

The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel organofunctional group-containing polyether modified alkoxy siloxane having a reduced residual of an unreacted polyether or a coloring of a platinum catalyst and A manufacturing method and a resin composition containing the alkoxysilane.

In order to achieve the above object, the inventors of the present invention have found that the organic group-containing alkoxysilane and the polyether group-containing alkoxysilane are partially co-hydrolyzed and polycondensed to contain organic substances. The functional group-based polyether-modified alkoxy siloxane has solved the above problems, and completed the present invention.

That is, the present invention provides an organic decane which is represented by the following average composition formula (1) and which contains an organic functional group, a polyether group and an alkoxy group in one molecule.

[Chemical Formula 1] Y _a Z _b R ¹ _c Si(OR ² ) _d (OH) _e O _(4-abcde)/2 (1) (wherein Y represents a group containing a fluorenyl group, an epoxy group, or a (meth) group At least one organic group selected from the group consisting of a propylene decyloxy group, an alkenyl group and an amine group. Z represents an organic group containing a polyether group. R ¹ represents a substituted or unsubstituted carbon atom number 1 having no aliphatic unsaturated bond. ~8 one-valent hydrocarbon group. R ² represents an alkyl group having 1 to 4 carbon atoms. a, b, c, d, and e represent 0.01≦a<1, 0.01≦b<1, 0≦c<1, 0.1≦ d≦2, 0≦e≦1, and satisfy the number of 0.1≦d+e≦2 and 1<a+b+c+d+e≦3).

Further, Y in the above average composition formula (1) is preferably an organic group containing a mercapto group.

Further, Z in the above average composition formula (1) is preferably an organic group containing a polyether group represented by the following formula (2).

(wherein R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms; R ⁴ represents a divalent hydrocarbon group having 2 to 10 carbon atoms; R ⁵ represents a hydrogen atom, a hydrocarbon atom having 1 to 6 carbon atoms, or An organic group represented by the following formula (3): R ⁶ represents a hydrogen atom or a hydroxyl group, and f and g represent an integer of 0 or 1. h and i represent an integer of 0 or more. However, at least one of h and i is 1 or more. The integer).

(wherein R ⁷ represents a one-valent hydrocarbon group having 1 to 4 carbon atoms).

Further, among the organic groups having a polyether group represented by the above formula (2), g = 1 is preferable.

The present invention further provides a resin composition characterized by containing the aforementioned organic decane.

The resin composition of the present invention is preferably contained in an amount of 0.001 to 5 parts by mass based on 100 parts by mass of the acrylic polymer.

Furthermore, the organic oxoxane of the present invention is a method for producing the above-described organic siloxane, which is characterized by comprising at least one alkoxy decane having an organofunctional group represented by the following general formula (4). And at least one of the alkoxy decane having a polyether group represented by the following general formula (5) and at least one of the alkoxy decane represented by the following general formula (6), which is partially co-hydrolyzed , polycondensation.

[Chemical 4] YR ¹ _p Si(OR ² ) _3-p (4) ZR ¹ _q Si(OR ² ) _3-q (5) R ¹ _r Si(OR ² ) _4-r (6) (wherein Y, Z, R ¹ and R ² respectively represent the same contents as described above. p and q represent integers of 0 to 2. r represents an integer of 0 to 3).

Further, the alkoxydecane having an organofunctional group represented by the above formula (4) is preferably an alkoxydecane having a mercapto group represented by the following formula (7).

(R ² O) _3-p R ¹ _p Si-R ⁸ -SH (7) (wherein R ¹ , R ² , and p respectively represent the same contents as described above. R ⁸ represents a carbon number of 1 ~10 divalent hydrocarbon groups).

Further, the polyether group-containing alkoxydecane represented by the above formula (5) is preferably a compound having a structure represented by the following formula (8).

(wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , f, g, h, i, q represent the same as described above).

Further, the partial alkoxy decane represented by the above general formulas (4) to (6) is co-hydrolyzed or polycondensed, and is preferably carried out in a ketone solvent, more preferably in diacetone alcohol.

Further, the organic siloxane of the present invention is preferably used as a surface modifier for a resin modifier, a paint modifier, an inter-material modifier, a surface treatment for fibers, and an inorganic material.

Further, the resin composition containing the organic siloxane is preferably used as a pressure-sensitive adhesive composition for a liquid crystal element.

The organic siloxane of the present invention is one in which an organic functional group, a polyether group, and an alkoxy group are contained in the molecule, and each functional group can be freely adjusted. number. Thereby, the compatibility of the organic decane with the organic resin can be improved, and the affinity with the surface of the inorganic substrate can be controlled.

When the organic decane is used in a resin curing agent, a resin modifier, a paint modifier, or an adhesion improver between an organic-inorganic material, the adhesion between the organic material and the inorganic material can be freely adjusted or Follow-up.

Further, according to the production method of the present invention, the polyether group can be efficiently introduced into the molecule without an addition reaction using a platinum catalyst. Thereby, the residue of the unreacted polyether is suppressed, and the original characteristics of the product are sufficiently exhibited. Moreover, the coloring caused by the platinum catalyst is also suppressed. Further, even in the presence of an organic functional group such as a thiol group which is toxic, the introduction of the polyether group into the molecule can be efficiently carried out.

The invention is described in detail below.

The organopolyoxane of the present invention is a polyether-modified alkoxy oxirane having an organofunctional group represented by the following average composition formula (1), which is capable of freely adjusting an organic functional group contained in one molecule The number of bases, polyether groups, and alkoxy groups.

[7] Y _a Z _b R ¹ _c Si(OR ² ) _d (OH) _e O _(4-abcde)/2 (1) (wherein Y represents a group consisting of a fluorenyl group, an epoxy group, and a (meth) group At least one organic group selected from the group consisting of a propylene decyloxy group, an alkenyl group and an amine group. Z represents an organic group containing a polyether group. R ¹ represents a substituted or unsubstituted carbon atom number 1 having no aliphatic unsaturated bond. ~8 one-valent hydrocarbon group. R ² represents an alkyl group having 1 to 4 carbon atoms. a, b, c, d, and e represent 0.01≦a<1, 0.01≦b<1, 0≦c<1, 0.1≦ d≦2, 0≦e≦1, and satisfy the number of 0.1≦d+e≦2 and 1<a+b+c+d+e≦3).

Here, Y has at least one organic group selected from the group consisting of a mercapto group, an epoxy group, a (meth)acryloxy group, an alkenyl group, and an amine group. These functional groups are usually bonded to a ruthenium atom through a linking group. Examples of the linking group include an ether bond (-O-), a thioether bond (-S-), and an imido group (-NH). -) a linear, branched or cyclic carbon group having 1 to 12 carbon atoms, a heterocyclic ring having a carbon number of 6 to 12, and a bond such as a hetero atom or a phenyl group. Examples of the group and the like include an alkylene group such as a methylene group, an ethylidene group, a trimethylene group, a hexamethylene group, and a decamethylene group; and a divalent group having an aromatic ring therebetween; Hydrocarbyl group and the like. The alkenyl group may be bonded to the ruthenium atom through the linking group or may be directly bonded to the ruthenium atom.

As the organic group having a mercapto group, a mercaptomethyl group, a 3-mercaptopropyl group, a 6-fluorenylhexyl group, a 10-mercaptopurinyl group, a (4-fluorenylmethyl)phenylethyl group, or the like can be exemplified as an organic group having an epoxy group. The base may, for example, be a glycidoxymethyl group, a 3-glycidoxypropyl group, a 5,6-epoxyhexyl group, a 9,10-epoxyfluorenyl group or a 2-(3,4-epoxy group). Ethylcyclohexyl)ethyl, 2-(3,4-epoxy-4-methylcyclohexyl)propyl, etc., and, as an organic group having a (meth)acryloxycarbonyl group, propylene oxide can be exemplified. Methyl, 3-propenyloxypropyl, 6-propenyloxyhexyl, 10-propenyloxycarbonyl, methacryloxymethyl, 3-methylpropenyloxypropyl, 6-Methyl propylene methoxy hexyl group, 10-methyl propylene fluorenyl fluorenyl group, etc., as an organic group having an alkenyl group, for example a vinyl group, an allyl group, a 5-hexenyl group, a 9-nonenyl group, a 3-vinyloxypropyl group, a p-styryl group, a cyclohexenylethyl group or the like, as an organic group having an amine group, Aminomethyl, 3-aminopropyl, 6-aminopropyl, N-methyl-3-aminopropyl, N,N-dimethyl-3-aminopropyl, N- Phenyl-3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl, N-(6-aminohexyl)-3-aminopropyl, N-(vinyl Benzyl)-2-aminoethyl-3-aminopropyl and the like.

In the organopolysiloxane of the present invention, when the organic functional group has an organic group having a mercapto group, an epoxy group or a (meth)acryloxy group, it is suitable for various uses because of its high reactivity. More preferably, those having a mercapto group or an epoxy group are more valuable and more preferable.

Further, Z in the above average composition formula (1) is an organic group containing a polyether group. The polyether group has an effect of improving the compatibility of the organic decane with an organic resin, or an effect of controlling affinity with the surface of the inorganic substrate. The polyether group is usually bonded to a ruthenium atom through a linking group, and examples of the linking group include an ether bond (-O-), a thioether bond (-S-), an imine group (-NH-), and the like. Examples of the linear or branched or cyclic alkyl group having 1 to 12 carbon atoms in the aromatic ring such as a hetero atom or a phenyl group, and examples thereof include a methylene group, an ethyl group, a trimethylene group, and a sixth group. An alkylene group such as a methylene group or a decamethylene group; a divalent hydrocarbon group having an aromatic ring in the middle of a methylphenylethyl group or the like.

The monovalent hydrocarbon group having a polyether group is preferably a structure of the following formula (2).

(wherein R ³ represents a divalent hydrocarbon group such as a C 1 to 10, preferably 3 to 8 alkyl group; and R ⁴ represents an alkylene group having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, etc. a divalent hydrocarbon group: R ⁵ represents a monovalent hydrocarbon group such as a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or an organic group represented by the following formula (3): R ⁶ represents a hydrogen atom or a hydroxyl group, and f and g represent 0 or An integer of 1. h, i represents an integer of 0 or more. However, at least one of h and i is an integer of 1 or more.

(wherein R ⁷ represents a monovalent hydrocarbon group such as an alkyl group having 1 to 4 carbon atoms).

The polyether group portion may be an ethylene oxide type (hereinafter referred to as EO type), a propylene oxide type (hereinafter referred to as PO type), or an ethylene oxide-propylene oxide type (hereinafter referred to as EO-PO type). Any of them, in the case of the EO-PO type, may be any of random, block, and interaction.

In this case, h is preferably 0 to 50, more preferably 1 to 25, still more preferably 5 to 15, i is preferably 0 to 50, more preferably 0 to 25, and still more preferably 0 to 10, h. +i is preferably from 1 to 50, more preferably from 1 to 25, still more preferably from 5 to 15.

In the above formula (2), when g=0, the structure represented by the following formula (9) is adopted.

(R ³ , R ⁵ , R ⁶ , h, i represent the same contents as described above).

As such a configuration, for example, 3-[poly(ethylene glycol)methyl ether]propyl, 3-[poly(propylene glycol)monomethyl ether]propyl, 3-[poly(ethylene glycol-propylene glycol) single can be cited. Methyl ether] propyl, 3-[poly(ethylene glycol-propylene glycol) monoethyl decyl ether] propyl or the like, and specific examples thereof include an organic group represented by the following formula.

In the above formula (2), when g=1 and f=0, the structure represented by the following formula (10) is obtained.

(R ³ , R ⁴ , R ⁵ , R ⁶ , h, i represent the same contents as described above).

Specific examples of the compound having such a structure include an organic group represented by the following formula.

Further, in the above formula (2), when g=1 and f=1, the structure represented by the following formula (11) is obtained.

(R ³ , R ⁴ , R ⁵ , R ⁶ , h, i represent the same as described above. However, R ⁴ here means a divalent hydrocarbon group having 2 to 3 carbon atoms).

Specific examples of the compound having such a structure include an organic group represented by the following formula.

R ¹ in the above average composition formula (1) has an effect of controlling compatibility with a resin composition. Specifically, it means a substituted or unsubstituted one-valent hydrocarbon group having 1 to 8 carbon atoms which does not have an aliphatic unsaturated bond. Methyl, ethyl, propyl, isopropyl, 1-methylpropyl, butyl, isobutyl, t-butyl, hexyl, octyl, phenyl, tolyl, benzyl, phenyl Examples of the alkyl group, the aryl group, the aralkyl group and the like of the ethyl group include a chloromethyl group, a 3-chloropropyl group, a 6-chlorohexyl group, a 10-chloroindenyl group, a bromomethyl group, a 3-bromopropyl group and the like. Haloalkyl. It is particularly preferably a methyl group from the influence of the steric hindrance on the reactivity of the above organofunctional group or the cost.

Further, the organic siloxane of the present invention contains an alkoxy group in the molecule. When an inorganic substrate such as glass is surface-treated with the organic siloxane, the alkoxy group reacts with an -OH group present on the surface of the inorganic substrate to form a chemical bond between the organic siloxane and the inorganic substrate. . Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and the like, and at least one selected from the group consisting of these may be used.

Further, in the above average composition formula (1), a, b, c, d, e, is 0.01≦a<1, 0.01≦b<1, 0≦c<2, 0.1≦d<2, 0≦e≦1, and indicates that 0.1≦d+e≦2 and 1<a+ are satisfied. b+c+d+e≦3 number.

Here, the coefficient a is a numerical value indicating the degree of substitution of an organic functional group with a ruthenium atom, and when it is too small, when the organic polysiloxane is used, the reactivity due to the reactivity of an organic functional group which is originally possessed cannot be exhibited. On the other hand, when the degree of substitution of the organic functional group is more than 1, it is difficult in terms of synthesis or cost, and therefore it must be in the range of 0.01 ≦ a < 1, preferably 0.1 ≦ a < 1, preferably better. It is a range of 0.1≦a≦0.8.

Further, the coefficient b is a value indicating a degree of substitution of a monovalent hydrocarbon group of a polyether group with a ruthenium atom. When the amount is too small, compatibility with an organic resin may be insufficient or uncontrollable when the organic polysiloxane is used. Affinity or reactivity of the inorganic substrate. On the other hand, when the degree of substitution is 1 or more, there is a possibility that the reactivity of the organic functional group and the resin is lowered, or the reactivity of the alkoxy group and the inorganic substrate is lowered, and therefore it is necessary to be 0.01 ≦b<1. The range is preferably in the range of 0.1 ≦ b < 1, more preferably 0.1 ≦ b ≦ 0.8.

Further, the coefficient c is a numerical value indicating the degree of substitution of the one-valent hydrocarbon group having 1 to 8 carbon atoms with respect to the ruthenium atom, and is appropriately introduced as needed in order to control the compatibility with the organic resin. When the degree of substitution is 1 or more, there is a possibility that the compatibility with the resin is lost or the reaction between the organic functional group and the organic resin is hindered. Therefore, it is necessary to have a range of 0 ≦ c < 1, preferably 0.1 ≦ c < 1, and more preferably 0.1 ≦ c ≦ 0.8.

Further, the coefficient d indicates the degree of substitution of the alkoxy group with the ruthenium atom. Although the degree of substitution can be arbitrarily set according to the purpose of use, it must be in the range of 0.1 ≦ d < 2. It is preferably in the range of 0.1 ≦d ≦ 1.8, 0.2 ≦ d ≦ 1.5.

Further, the coefficient e is a value indicating the degree of substitution of a hydroxyl group with a halogen atom, that is, a content of a sterol group, and the sterol group may be responsible for a decylation reaction or a condensation reaction, and imparts hydrophilicity to an organic polyoxane. The effect is preferably as small as possible from the viewpoint of ensuring the preservation stability of the organic polyoxyalkylene mixed composition. Therefore, it must be in the range of 0≦e≦1, preferably in the range of 0≦e≦0.5, more preferably in the range of 0≦e≦0.2.

Further, the total of the above coefficients (a+b+c+d+e) is determined by [4-(a+b+) indicating the degree of condensation of the organopolyoxane represented by the above average composition formula (1). The value of c+d+e)]/2 must be in the range of 1<a+b+c+d+e≦3. Further, the degree of polymerization of the organopolysiloxane may be in the range of a polymer having two dimers of a ruthenium atom to several hundreds of ruthenium atoms, and when the average degree of polymerization is 2, the produced organic oxime is produced. The content of the monomer in the oxane is increased, which may damage the original purpose of the polyoxyalkylene alkoxy oligomer, and when the average degree of polymerization is too large, it becomes a high-viscosity product or a paste or a solid, which makes the operation complicated. Therefore, the average degree of polymerization is preferably in the range of 3 to 100, more preferably in the range of 3 to 50. From this point of view, with respect to the above (a+b+c+d+e), it is also preferably 1.5≦a+b+c+d+e≦2.67, and more preferably 2.0≦a+b+c+ The range of d+e≦2.67.

The above average composition formula (1) is expressed in one molecule The organic polyoxyalkylene having a functional group, a polyether group or an alkoxy group may be a linear, branched, or cyclical group, or a combination thereof, as long as a to e are respectively in the above range. The construction of these.

Further, the organic siloxane of the present invention has a polystyrene-equivalent weight average molecular weight of gel permeation chromatography (GPC), preferably 400 to 35,000, more preferably 400 to 10,000, still more preferably 450 to 5,000.

Next, the above average composition formula (1) of the present invention is represented by an organopolysiloxane having an organic functional group, a polyether group and an alkoxy group in one molecule, and for example, at least one of the following may be used. The alkoxy decane having an organofunctional group represented by the formula (4) and the alkoxy decane having a polyether group represented by the following general formula (5), and the general formula (6) The alkoxydecane represented by the method is partially co-hydrolyzed and polycondensed.

YR ¹ _p Si(OR ² ) _3-p (4) ZR ¹ _q Si(OR ² ) _3-q (5) R ¹ _r Si(OR ² ) _4-r (6) (wherein Y, Z, R ¹ and R ² respectively represent the same contents as described above. p and q represent integers of 0 to 2. r represents an integer of 0 to 3).

The alkoxydecane containing an organofunctional group represented by the above formula (4) is preferably an alkoxydecane containing a mercapto group represented by the following formula (12).

(R ² O) _3-p R ¹ _p Si-R ⁸ -SH (12) (wherein R ¹ , R ² , R ⁸ and p respectively represent the same contents as described above. R ⁸ is carbon A divalent hydrocarbon group having an atomic number of 1 to 10, preferably 1 to 6 alkylene groups.

The above formula (12) represents a mercapto-containing alkoxydecane, particularly using 3-mercaptopropyltrimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyltriethoxylate At least one selected from the group consisting of decane and 3-mercaptopropylmethyldiethoxy decane is preferred.

The alkoxysilane having a polyether group represented by the above formula (5) is preferably a polyether group-containing alkoxydecane represented by the following formula (13).

(wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , f, g, h, i, q each represent the same as described above).

The compound represented by the above formula (13) has a structure in which an organic group containing a polyether group represented by the above formula (2) is bonded to an alkoxyalkylene group.

In the above formula (13), when g=0, the structure represented by the following formula (14) is adopted.

(wherein R ¹ , R ² , R ³ , R ⁵ , R ⁶ , h, i, and q each represent the same content as described above).

The alkoxysilane having a polyether group represented by the above formula (14) can be represented by the following formula (16) by alkoxysilane having a ≡Si-H group represented by the following formula (15). A compound containing a polyether group and a reactive double bond is produced by hydrosilylation reaction in the presence of a platinum catalyst.

(R ² O) _3-p R ¹ _p Si-H (15) (wherein R ¹ , R ² and p respectively represent the same contents as described above).

(wherein R ⁵ , R ⁶ , h, and i each represent the same content as described above. R ⁹ represents a single bond or a divalent hydrocarbon group such as an alkylene group having 1 to 8 carbon atoms).

Specifically, for example, a compound containing a polyether group and a reactive double bond represented by the following formula (18) which is represented by the following formula (17) and containing a methoxy-Si-H group; The hydroquinonelation reaction is carried out in the presence of a platinum catalyst to produce trimethoxydecane containing various organic functional groups represented by the following formula (19).

(CH ₂ O) ₃ Si-H (17) CH ₂ =CH-CH ₂ -O(CH ₂ CH ₂ O) ₁₁ CH ₃ (18) (CH ₃ O) ₃ Si-C ₃ H ₆ -O(CH ₂ CH ₂ O) ₁₁ CH ³ (19)

In the above formula (13), when g=1, a structure in which a polyether group and an alkoxyalkylene group are bonded to each other with a linking group having an -S- bond therebetween is employed. When f=0, the structure represented by the following formula (20) is adopted, and when f=1, the structure represented by the following formula (21) is obtained.

(wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , h, i, q each represent the same as described above).

(wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , h, i, and q each represent the same content as described above. However, R ⁴ here means a carbon number of 1 to 3 Divalent hydrocarbon group).

The compound represented by the above formula (20) can be represented by the following formula (16) by alkoxysilane having a mercapto group represented by the following formula (12). A compound containing a polyether group and a reactive double bond is produced by an addition reaction in the presence of a radical generator.

(R ² O) _3-p R ¹ _p Si-R ⁸ -SH (12) (wherein R ¹ , R ² , R ⁸ and p respectively represent the same contents as described above).

(wherein R ⁵ , R ⁶ , R ⁹ , h, i each represent the same content as described above).

Specifically, for example, a trimethoxy decane containing a mercapto group represented by the following formula (22) and a compound containing a polyether group and a reactive double bond represented by the following formula (23) may be present in the radical generating agent. The addition reaction is carried out to produce a polyether group-containing trimethoxynonane represented by the following formula (24).

(CH ₃ O) ₃ Si-C ₃ H ₆ -SH (22) CH ₂ =CH-CH ₂ -O(CH ₂ CH ₂ O) ₁₁ CH ₃ (23) (CH ₃ O) ₃ Si -C ₃ H ₆ -SC ₃ H ₆ -O(CH ₂ CH ₂ O) ₁₁ CH ₃ (24)

The compound represented by the above formula (21) can be represented by the following formula (25) by the alkoxysilane having a mercapto group represented by the above formula (12). A compound containing a polyether group and a reactive double bond is produced by an addition reaction in the presence of a radical generator.

(wherein R ⁵ , R ⁶ , h, i each represent the same content as described above. R ¹⁰ represents a hydrogen atom or a methyl group).

Specifically, for example, a compound containing a mercapto group and a compound having a polyether group and a reactive double bond represented by the following formula (26), which is represented by the above formula (22), may be used as a radical generating agent. The addition reaction is carried out in the presence of a polyether group-containing trimethoxydecane represented by the following formula (27).

The alkoxy decane containing a polyether group represented by the above formulas (20) and (21) is not caused by a platinum catalyst as compared with the compound represented by the above formula (14) because no platinum catalyst is used in the production process. The color of the media can be obtained with less color. Therefore, it is mixed with an alkoxy decane containing an organic functional group represented by the above formula (4) and an alkoxy decane represented by the above formula (6), and partially co-hydrolyzed and polycondensed. Organic alkane, also Can become a lesser shade.

Further, the alkoxydecane represented by the above formula (6), specifically, the alkoxydecane of r = 0, tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, Tetraisopropoxy decane, tetrabutoxy decane, tetraisobutoxy decane, etc.; as alkoxydecane of r=1, a methyl group, an ethyl group, a propyl group, an isopropyl group, and a 1-methyl group are mentioned. Trimethoxy decane, triethoxy decane, tripropoxy oxypropyl, butyl, isobutyl, t-butyl, hexyl, octyl, phenyl, tolyl, benzyl, phenylethyl, etc. Base decane, triisopropoxy decane, tributoxy decane, triisobutoxy decane, etc.; as the alkoxy decane of r=2, dimethyldimethoxydecane, dimethyldiethyl can be exemplified. Oxydecane, dimethyldipropoxydecane, dimethyldibutoxydecane, methylethyldimethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane, etc. .

Further, from the viewpoint of availability of the raw material or cost, it is preferred to use p in the above general formula (4) to be 0, that is, a trialkoxy decane having an organic functional group; and the above general formula (5) Wherein q is 0, that is, a trialkoxy decane containing a polyether group; and R ¹ in the above general formula (6) is a methyl group, r is 1 and/or 0, that is, methyltrialkoxide Base decane, tetraalkoxy decane.

The blend ratio of the above-mentioned organofunctional group-containing alkoxydecane, polyether group-containing alkoxydecane, and alkoxydecane is not particularly limited, but an alkoxysilane having an organic functional group and a poly-containing When the blend ratio of the ether-based alkoxydecane is too small, the inherent properties of the organopolysiloxane are not exhibited, and it is necessary to have at least one organic function in one molecule. Base and polyether base. Therefore, the molar ratio of the three components in terms of Si atom is preferably in the range of 1 to 99:1 to 99:0 to 98, more preferably in the range of 10 to 90:10 to 90:0 to 90.

Further, the order of mixing or mixing of the various raw materials, and the method of performing partial co-hydrolysis and polycondensation are not particularly limited, and may be based on a conventionally known method, for example, by the above-mentioned alkoxydecane having an organic functional group. a mixture of a polyether-containing alkoxy decane and an alkoxy decane, which is obtained by adding water to carry out partial co-hydrolysis and polycondensation in the presence of a hydrolysis or condensation reaction catalyst. Use a suitable organic solvent.

As the catalyst for the hydrolysis and condensation reaction to be used, various materials known in the art can be used. Specific examples thereof include organic acids such as acetic acid, trifluoroacetic acid, butyric acid, oxalic acid, maleic acid, citric acid, methanesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid; hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, and the like. Inorganic acids; basic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, sodium acetate, potassium acetate, ammonia, ammonium hydroxide, triethylamine, etc.; potassium fluoride, ammonium fluoride, etc. Fluorine-containing compounds; organometallic compounds such as tetraisopropyl titanate, tetrabutyl titanate, dioctyltin dilaurate, aluminum tongs, and the like. The catalyst may be used singly or in combination, and the amount of the catalyst used is preferably in the range of 0.0001 to 10 mol%, more preferably 0.001%, based on the number of moles of Si atoms present in the entire raw material. 3% of the range of moles.

As described above, the degree of polymerization of each of the organopolysiloxanes of the present invention is as long as it is from a dimer of two atoms to a few hundred atoms. The polymer can be used, and the average degree of polymerization is determined by the amount of water used for partial hydrolysis and polycondensation. When water is excessively added, the alkoxy group corresponding thereto is hydrolyzed, and the resin structure having a large branched structure is obtained, and the desired polyoxyalkyloxy oligomer is not obtained. Therefore, the amount of hydrolyzed water must be strictly determined. For example, when all of the alkoxydecane raw materials used are one monomer of a halogen atom, in order to prepare an organopolyoxyalkylene having an average degree of polymerization Z, it is used as long as it is relative to the alkoxydecane raw material of Z mole. -1) Moir water can be used for partial hydrolysis and polycondensation.

In this case, an organic solvent such as an alcohol, an ether, an ester or a ketone may be used as needed. Specific examples of such organic solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, and propylene glycol monomethyl ether; ethers such as diethyl ether and dipropyl ether; and methyl acetate. An ester of ethyl acetate, ethyl acetate or the like; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or ethyl acetonate; diacetone alcohol. Further, a nonpolar solvent such as hexane, toluene or xylene may be used in combination with the above solvent. In particular, a ketone such as methyl ethyl ketone, methyl isobutyl ketone or acetonitrile acetone is preferred, and diacetone alcohol is particularly preferred.

The amount of the organic solvent to be used may be in the range of 0 to 1,000 parts by mass based on 100 parts by mass of the total of the alkoxysilane as a raw material, a partial hydrolyzate thereof, and a condensate thereof, and when the amount of use is small, the hydrolysis starts. The reaction system may not be uniform, and if it is too much, it is not only impossible to see the above additive effect, but the pot yield is lowered, which is unfavorable for cost, and therefore is more preferably in the range of 10 to 500 parts by mass. It is in the range of 20 to 200 parts by mass.

The actual operation in the partial (co)hydrolysis and polycondensation reaction is preferably carried out by dropping a specific amount of water or a mixed solution of water/organic solvent in a mixed system composed of alkoxydecane raw materials, a catalyst and an organic solvent. Or, a mixed solution of a specific amount of water/catalyst or a mixed solution of water/catalyst/organic solvent is added dropwise to a mixed system composed of an alkoxydecane raw material and an organic solvent. Each reaction can be carried out at a temperature ranging from 0 to 150 ° C, but in general, at a temperature lower than room temperature, the reaction proceeds slowly, so it is not practical, and when it is too high temperature, an epoxy group is also generated. The thermal decomposition of a mercapto group or the like, or the thermal polymerization of an acryloxy group, has an adverse effect on the organic functional group, and therefore it is preferably in the range of 20 to 130 °C. After the reaction, a neutralization, adsorption, filtration, or the like removal operation of the used catalyst may be performed, or a purification step of distilling off the used organic solvent, by-product alcohol, and low-boiling substance may be performed to obtain a target. The organopolyoxane of the present invention.

The organic polysiloxane of the present invention can be suitably used as a resin modifier, a paint modifier, an adhesive between materials, a surface treatment agent for fibers, a surface treatment agent for inorganic materials, and the like. Further, the organopolysiloxane of the present invention can be used in a resin composition containing a resin composition, for example, an acrylic polymer as a base resin.

For example, as a resin modifier, it is used in organic materials such as rubber or plastic; with metals or cerium oxide, quartz, talc, clay, zinc oxide, iron oxide, titanium oxide, aluminum oxide, calcium carbonate, and aluminum hydroxide. In addition, inorganic materials such as inorganic fillers such as mica and carbon black can be obtained by reinforcing plastics or high-strength elastomers having high weather resistance and heat resistance. Further, as a paint modifier, it is blended with a polyester resin or an acrylic resin. The coating resin can be applied to metals, wood, concrete, and the like with excellent weather resistance, durability, and heat resistance. Further, as the surface modifier of the fiber, the material may be natural fibers such as wool, crepe, hemp, wood wool, asbestos; recycled fibers of strontium, copper ammonium cerium, acetate, etc.; polyester, polyester Any of various fibers such as organic synthetic fibers such as ether, polyacrylonitrile, vinylon, polyvinylidene chloride, vinyl chloride, polyethylene, and polypropylene; inorganic synthetic fibers such as glass fibers and carbon fibers, and which are woven fabrics, knitted fabrics, and the like. Any form of grease such as a non-woven fabric or a resin-treated cloth can be treated on the surface of the fiber to impart weather resistance, durability, and the like to the fiber.

Further, the organopolysiloxane of the present invention is suitably used as an adhesive modifier between an organic material and an inorganic material. For example, the resin composition containing the organic siloxane of the present invention is suitably used as a pressure-sensitive adhesive composition for a liquid crystal element, and can be used for adhesion, durability, and rework in the liquid crystal cell and the polarizing plate. Sex. The resin composition used herein is not particularly limited, and is particularly preferably an acrylic polymer. Usually, a (co)polymer formed of an acrylic monomer such as (meth) acrylate or an acrylic monomer containing a functional group is used. For example, examples of the (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylic acid. 2-ethylhexyl ester, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, methoxyethyl (meth)acrylate, and (meth)acrylic acid Oxyethyl ester and the like. This can be used alone or in combination.

The acrylic polymer used in the present invention is usually present in an amount of 60 to 99% by mass, preferably 80 to 98% by mass. The repeating unit derived from the acrylate. Further, examples of the functional group-containing acrylic monomer include acrylic acid, methacrylic acid, β-carboxyethyl acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. Base) chloro-2-hydroxypropyl acrylate, diethylene glycol mono(meth) acrylate, dimethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate. This can be used alone or in combination.

The acrylic polymer used in the present invention usually has a repeating unit derived from the functional group-containing acrylic monomer in an amount of from 1 to 20% by mass, preferably from 2 to 10% by mass. The acrylic polymer used in the present invention may have a repeating unit derived from a monomer other than the (meth) acrylate and the functional group-containing acrylic monomer, and examples of such an example include benzene. A repeating unit derived from a vinyl monomer and a repeating unit derived from a vinyl monomer. Examples of the styrene monomer include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, and propyl benzene. Alkyl styrenes such as ethylene, butyl styrene, hexyl styrene, heptyl styrene and octyl styrene; halogenated fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene and iodine styrene Styrene; more preferred are nitrostyrene, ethyl styrene styrene, and methoxy styrene. Further, examples of the vinyl monomer include vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, divinyl benzene, vinyl acetate, and acrylonitrile; butadiene, isoprene, and chloroprene. The conjugated diene monomer; a halogenated ethylene such as vinyl chloride or vinyl bromide; a vinylidene halide such as vinylidene chloride or the like. These monomers may be used singly or in combination.

In the acrylic polymer used in the present invention, the repeating unit derived from the other monomer described above is usually contained in an amount of from 0 to 20% by mass, preferably from 0 to 10% by mass. In particular, the acrylic polymer used in the present invention preferably has at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, a glycidyl group, and a decyl group. The acrylic polymer having such a group has good reactivity with a polymer type decane coupling agent constituting the composition of the adhesive of the present invention or a crosslinking agent which is blended as desired. The above acrylic polymer used in the present invention usually has a weight average molecular weight of from 100,000 to 1,500,000, preferably from 300,000 to 800,000.

In addition, the resin composition containing the acrylic polymer as the base resin is preferably used in an amount of 0.001 to 5 parts by mass, particularly preferably 0.001 to 1 part by mass, based on 100 parts by mass of the acrylic polymer. Organic polyoxane.

[Examples]

The present invention is exemplified by the following examples and comparative examples, but the present invention is not limited by the following examples.

Further, the analysis of the organopolysiloxane obtained in the synthesis example was carried out by the method shown below.

(1) The average degree of polymerization of the organopolyoxane is determined by gel permeation chromatography (GPC) analysis from the weight average molecular weight determined from a calibration curve prepared from a polystyrene standard sample. Calculated.

(2) Alkoxy group content in organic polyoxane, which is alkali cracked-gas phase Determination of the above average composition formula (1), (2) by chromatography (GC) analysis (alkali cracking gas-chromatography) [refer to the cesium-oxygen guide, 792-793 (issued by Nikkan Kogyo Shimbun)] d.

(3) The structural analysis of the organopolyoxane is carried out by 矽 nuclear magnetic resonance spectrum ( ²⁹ Si-NMR) analysis and proton nuclear magnetic resonance spectrum ( ¹ H-NMR) analysis, and the average composition formula is obtained from the measurement results. The coefficients a, b, c, and e of (1) and (2).

(4) The thiol equivalent of organic polyoxane is based on acetic acid/potassium iodide/potassium iodate addition-sodium thiosulfate solution titration method [Refer to Analytical Chemistry Handbook, Revised Second Edition, 432~433 pages (Maruzen Co., Ltd. issued) )] to determine.

[Example 1] (Synthesis of polyether-modified methoxy oxirane containing fluorenyl group-1)

In a flask having a capacity of 1 L equipped with a stirring device, a cooling condenser, a thermometer, and a dropping funnel, 25.0 g (12.7×10 ^-2 mol) of 3-mercaptopropyltrimethoxydecane was fed, and the following formula (19) was used. 28.8 g (4.25 × 10 ^-2 mol) of a polyether group-containing trimethoxy decane and 17.0 g of diacetone alcohol were added, and while stirring at an internal temperature of 20 to 30 ° C, a 0.05 N hydrochloric acid aqueous solution of 2.67 was added dropwise for 30 minutes. g (water: 14.8 × 10 ^-2 mol, hydrochloric acid: 1.34 × 10 ^-4 mol), further aging for 2 hours.

(CH ₃ O) ₃ Si-C ₃ H ₆ -O(CH ₂ CH ₂ O) ₁₁ CH ₃ (19)

Then, 1.91 g (sodium acetate: 2.33 × 10 ^-4 mol) of a 1% methanol solution of sodium acetate was added, and the mixture was heated to 70 ° C for 2 hours of aging.

Thereafter, the mixture was heated under reduced pressure at 100 ° C and 10 mmHg for 2 hours, and the residual alcohol component and the low-boiling component were distilled off, and then filtered to obtain a liquid organooxane 1 having a nonvolatile content of 99.0% (yield: 42.7 g, yield: 91%).

In the above-mentioned average composition formula (1), Y is a 3-mercaptopropyl group, and Z is an organic group containing a polyether group represented by the following formula (28), and an R ¹ -methyl group.

[Chem. 31]-C ₃ H ₆ -O(CH ₂ CH ₂ O) ₁₁ CH ₃ (28)

Table 1 shows the weight average molecular weight, the average degree of polymerization, the respective coefficients in the above average composition formula (1), and the fluorenyl equivalent, which were obtained from the above analysis results.

[Embodiment 2] (Synthesis of polyether-modified methoxy oxirane containing fluorenyl group-2)

In a flask having a capacity of 1 L equipped with a stirring device, a cooling condenser, a thermometer, and a dropping funnel, 12.5 g (6.36 × 10 ^-2 mol) of 3-mercaptopropyltrimethoxydecane and the following formula (23) were fed. After adding 35.4 g (6.36 × 10 ^-2 mol) of the allylated polyether, PERBUTYL-O [manufactured by Nippon Oil Co., Ltd.: t-butylperoxy-2 hexanoate] was added while stirring. -ethyl ester] 0.5 g, aging at 65 ° C for 2 hours.

[Chem. 32] CH ₂ =CH-CH ₂ -O(CH ₂ CH ₂ O) ₁₁ CH ₃ ( ²³ )

The liquid produced above was measured by GPC (Gel Permeation Chromatography) under a THF solvent. As a result, the peak of the product was confirmed in the range of 28 minutes to 34 minutes. Further, the peak derived from 3-mercaptopropyltrimethoxydecane substantially disappeared in the range of 36 minutes to 38 minutes. Further, ¹ H-NMR measurement was performed on the liquid produced above. As a result, in the range of 4.7 to 6.0 ppm, the peak of the allyl group derived from the allylated polyether represented by the above formula (23) disappeared before the reaction. It is presumed that a polyether group-containing alkoxydecane represented by the following formula (29) is produced.

(CH ₃ O) ₃ Si-C ₃ H ₆ -SC ₃ H ₆ -O(C ₂ H ₄ O) ₁₁ CH ₃ (29)

Next, 37.5 g (19.1 × 10 ^-2 mol) of 3-mercaptopropyltrimethoxydecane, 17.4 g of methyltrimethoxydecane (12.8 × 10 ^-2 mol), and diacetone were added to the total amount of the above liquid. 44.0 g of alcohol, while stirring at an internal temperature of 20 to 30 ° C, it took 30 minutes to drip 6.3 g of 0.05 N aqueous hydrochloric acid (water: 35.0 × 10 ^-2 mol, hydrochloric acid: 3.15 × 10 ^-4 mol). Matured for 2 hours. Thereafter, 4.50 g (sodium acetate: 5.49 × 10 ^-4 mol) of a 1% methanol solution of sodium acetate was added, and the temperature was raised to 70 ° C, followed by aging for 2 hours.

Thereafter, at 100 ° C, 10 mmHg, 2 hours reduction After heating under pressure, the residual alcohol component and the low-boiling component were distilled off, and the mixture was filtered to obtain a liquid organooxane 2 having a nonvolatile content of 98.9% (yield: 77.1 g, yield: 90%).

In the above-mentioned average composition formula (1), Y is a 3-mercaptopropyl group, Z is an organic group containing a polyether group represented by the following formula (30), and an R ¹ -methyl group.

[Chem. 34]-C ₃ H ₆ -SC ₃ H ₆ -O(C ₂ H ₄ O) ₁₁ CH ₃ (30)

Table 1 shows the weight average molecular weight, the average degree of polymerization, the respective coefficients in the above average composition formula (1), and the fluorenyl equivalent, which were obtained from the above analysis results.

[Example 3] (Synthesis of polyether-modified methoxy oxirane containing fluorenyl-3)

In addition to the synthesis example 2, 35.4 g (6.36 × 10 ^-2 mol) of the allylated polyether represented by the above formula (23) was changed to methyl polyethylene glycol monoacrylic acid represented by the following formula (31). The same operation as above was carried out, except that the ester was 31.6 g (6.37 × 10 ^-2 mol), to obtain an organic oxirane 3 (yield: 72.1 g, yield: 88%) having a nonvolatile content of 99.1%.

[Chem. 35] CH ₂ = CCO(CH ₂ CH ₂ O) ₉ CH ₃ (31)

Table 1 shows the weight average molecular weight determined from the above analysis results, The average degree of polymerization, each of the above average composition formulas (1), and the thiol group equivalent.

[Comparative Example 1] Synthesis-4 of thiol-containing polyether modified methoxy oxirane

Into a flask having a stirring apparatus, a cooling condenser, and a thermometer having a capacity of 1 L, 98.2 g (0.50 mol) of 3-mercaptopropyltrimethoxydecane and 60.0 g of tetramethyltetrahydrocyclotetraoxane (0.25 mol) were fed. After that, 0.08 g of trifluoromethanesulfonic acid was added while stirring, and the mixture was equilibrated at room temperature for 4 hours. After the end of the equilibration, Mg ₆ Al ₂ (OH) ₁₆ CO ₃ was added to the system. 0.57 g of a solid alkaline neutralizing agent represented by 4H ₂ O, stirred for 2 hours, neutralized with trifluoromethanesulfonic acid, and then subjected to filtration and purification to obtain a liquid product A (methyl hydroxyl group containing a mercapto group) Base oxane) (yield: 150 g, yield: 95%).

Here, the product A was subjected to GPC measurement under a toluene solvent. As a result, the peak of the product was confirmed in the range of 28 minutes to 38 minutes. Further, the peak derived from 3-mercaptopropyltrimethoxydecane substantially disappeared in the range of 37 minutes to 39 minutes. Further, in the range of 35 minutes to 37 minutes, the peak derived from tetramethyltetrahydrocyclotetraoxane substantially disappeared.

Next, the thiol equivalent of the product A was measured. As a result, a value approximately 307 g/mol (set value: 316 g/mol) which is approximately close to the set value was obtained.

Next, follow the measurement method described below. The content of ≡Si-H group in the product A1g was measured. As a result, a value approximately 6.25 × 10 ^-3 mol/g (set value: 6.32 × 10 ^-3 mol/g) which is approximately close to the set value was obtained.

<Measurement method>

To 10 g of the sample, 10 g of butanol was added, and while stirring, 20 g of a 20% by mass aqueous NaOH solution was added. The amount of ≡SiH was calculated from the amount of hydrogen (≡SiH+H ₂ O→≡SiOH+H ₂ ↑) generated at this time.

From the above results, the methyl hydroxy methoxy oxane containing a mercapto group of the product A was estimated to have an average composition of the following formula (32).

Then, 176 g (31.7 × 10 ^-2 mol) of the allylated polyether represented by the above formula (23) was fed to the product A50g (15.8 × 10 ^-2 mol), and then chlorinated while stirring 1.00 g of a platinum solution toluene solution (Pt concentration: 0.5% by mass) was heated to 90 ° C for 3 hours to obtain a product B.

Here, the amount of the ≡Si-H group contained in 1 g of the sample was measured before and after the reaction. The results are shown below.

(Before reaction) 1.39×10 ^-3 mol/g

(after reaction) 1.34×10 ^-3 mol/g

The amount of the ≡Si-H group contained in the sample 1g was only about 4% reduction before and after the reaction.

Here, the GPC measurement of the product B in a toluene solvent was performed. As a result, no significant change was observed in the peaks appearing as compared with the pre-reaction.

From the above, it is presumed that in the presence of a platinum catalyst, the hydroquinonelation reaction of the methylhydromethoxymethoxyoxane containing a mercapto group and the allylated polyether represented by the above formula (23) hardly proceeds.

[Comparative Example 2] Synthesis of thiol-containing polyether modified methoxy oxirane-5

In addition, in Comparative Example 1, 176 g (31.7 × 10 ^-2 mol) of the allylated polyether represented by the above formula (23) was changed to 244 g (31.8 ×) of the allylated polyether represented by the following formula (33). The same operation as described above was carried out except for 10 ^{- 2} mol.

[Chem. 37] CH ₂ =CH-CH ₂ -O(CH ₂ CH ₂ CH ₂ O) ₁₂ CH ₃ (33)

In the same manner as in Comparative Example 1, the sample 1g was contained in the sample 1g before and after the reaction between the product A (methyl hydroxy methoxy oxane containing fluorenyl group) and the allylated polyether represented by the above formula (33). The amount of ≡Si-H groups. The results are shown below.

(Before reaction) 1.07×10 ^-3 mol/g

(after reaction) 1.04×10 ^-3 mol/g

The amount of the ≡Si-H group contained in the sample 1g was only about 3% of the amount before and after the reaction.

Here, the sample after the reaction was subjected to GPC measurement under a toluene solvent. As a result, compared with the pre-reaction, the peaks appearing did not appear significant. The change.

From the above, it is presumed that in the presence of a platinum catalyst, the hydroquinonelation reaction of the methylhydromethoxymethoxyoxane containing a mercapto group and the allylated polyether represented by the above formula (33) hardly proceeds.

Claims (11)

An organic oxane, which is represented by the following average composition formula (1), and contains an organic functional group, a polyether group, and an alkoxy group in one molecule, and is represented by Y _a Z _b R ¹ _c Si ( OR ² ) _d (OH) _e O _(4-abcde)/2 (1) (wherein Y represents a group selected from a mercapto group, an epoxy group, a (meth) propylene methoxy group, an alkenyl group, and an amine group. At least one organic group; Z represents an organic group having a polyether group represented by the following formula (2); and R ¹ represents a substituted or unsubstituted carbon atom having 1 to 8 carbon atoms which does not have an aliphatic unsaturated bond. a hydrocarbon group; R ² represents an alkyl group having 1 to 4 carbon atoms; a, b, c, d, and e represent 0.01≦a<1, 0.01≦b<1, 0≦c<1, 0.1≦d≦2, 0 ≦e≦1, and satisfy the number of 0.1≦d+e≦2 and 1<a+b+c+d+e≦3); (wherein R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms; R ⁴ represents a divalent hydrocarbon group having 2 to 10 carbon atoms; and R ⁵ represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or An organic group represented by the following formula (3); R ⁶ represents a hydrogen atom or a hydroxyl group; f represents an integer of 0 or 1; g is 1; h, i represents an integer of 0 or more; and, at least one of h, i is An integer greater than 1); (wherein R ⁷ represents a one-valent hydrocarbon group having 1 to 4 carbon atoms). The organic oxirane of claim 1, wherein Y in the above average composition formula (1) is an organic group containing a mercapto group. A resin composition containing the organic oxirane of claim 1 or 2. A resin composition containing 0.001 to 5 parts by mass of the organic oxirane of claim 1 or 2, based on 100 parts by mass of the acrylic polymer. A method for producing an organic oxoxane according to claim 1 or 2, characterized in that at least one of the alkoxy decane having an organofunctional group represented by the following general formula (4) is at least one of the following The alkoxy decane having a polyether group represented by the general formula (5) and at least one of the alkoxy decane represented by the following general formula (6), which are optionally subjected to partial co-hydrolysis and polycondensation, YR ¹ _p Si(OR ² ) _3-p (4) ZR ¹ _q Si(OR ² ) _3-q (5) R ¹ _r Si(OR ² ) _4-r (6) (wherein Y, Z R ¹ and R ² respectively represent the same contents as described above; p and q represent integers of 0 to 2; r represents an integer of 0 to 3). The method for producing an organooxane of the above-mentioned item 5, wherein the alkoxy decane having an organofunctional group represented by the above formula (4) is an alkoxy decane having a mercapto group represented by the following formula (7). 5](R ² O) _3-p R ¹ _p Si-R ⁸ -SH (7) (wherein R ¹ , R ² and p respectively represent the same contents as above; R ⁸ represents a carbon number of 1 to 10 Divalent hydrocarbon group). The method for producing an organic alkane having the polyether group represented by the above formula (5), which is a compound having a structure represented by the following formula (8), (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , f, g, h, i, q represent the same as described above). The method for producing an organic oxoxane according to claim 5 or 6, which is subjected to partial co-hydrolysis and polycondensation in a ketone solvent. The method for producing an organic oxoxane according to claim 5 or 6, which is subjected to partial co-hydrolysis and polycondensation in diacetone alcohol. The organic oxime of claim 1 or 2, which is used as a resin modifier, a paint modifier, an adhesive between materials, a surface treatment agent for fibers, or a surface treatment agent for inorganic materials. The resin composition of claim 3 or 4 is used as a pressure-sensitive adhesive composition for a liquid crystal element.