KR101524530B1 - Organopolysiloxanes containing organic functional groups and multiple kinds of alkoxy groups having different carbon numbers - Google Patents

Abstract

There is provided a novel organopolysiloxane capable of arbitrarily changing the hydrolytic reactivity of an alkoxysilyl group depending on the purpose of use.

An organopolysiloxane containing an organic functional group represented by the following formula (1) and a plurality of alkoxy groups differing in the number of carbon atoms.

(Formula 1)

^{_{Y a R 1 b Si (OCH}} 3) c (OC 2 H 5) d (OR 2) e (OH) f O (4-abcdef) / 2

(Y is a mercapto group, an epoxy group, (meth) acryloxy group, an alkenyl group, a haloalkyl group and / or amino group-containing organic group, R ¹ is group an unsubstituted one having no aliphatic unsaturated bond, a hydrocarbon, R ² is a carbon atom 1, 0? B? 2, 0? C? 2, 0? D? 2, 0 <e? 2, 0? F? 1, c + d? 0 , 0.1? C + d + e? 2.5, 2? A + b + c + d + e +

Organopolysiloxane, hydrolysis, alkoxy.

Description

FIELD OF THE INVENTION [0001] The present invention relates to organopolysiloxanes containing an organic functional group and a plurality of alkoxy groups having different carbon atom numbers. &Lt; RTI ID = 0.0 &gt; [0002] &lt;

The present invention relates to an organopolysiloxane containing an organic functional group and a plurality of alkoxy groups having different carbon atom numbers, and more particularly to an organopolysiloxane having an organic functional group having a high reaction activity, a methoxy group and / or an ethoxy group having a high hydrolysis- The present invention relates to a novel organopolysiloxane which can arbitrarily change the hydrolytic reactivity of an alkoxysilyl group because it contains an alkoxy group having 3 and / or 4 carbon atoms in the same molecule.

A silicone alkoxy oligomer having a relatively low molecular weight silicone resin in which a molecular end is blocked with an alkoxysilyl group has been applied to various applications such as paints and coatings since it has good storage stability and can be dumped without need for maintenance and maintenance.

Among them, types having an organic functional group such as an epoxy group, a mercapto group, a (meth) acryloxy group, an alkenyl group, a haloalkyl group and an amino group in the same molecule can be positioned as a so-called oligomer type silane coupling agent, Compared with the silane coupling agent, it has a low volatility during use, has a small alcohol by-product amount, and is capable of multifunctional structuring. Therefore, it has become a useful material for use in resin modification and the like.

For example, it is possible to react an organic resin having reactivity with an organic functional group contained therein to introduce an alkoxysilyl group, and modify the organic resin into a moisture-curing type. The silanol group formed by the hydrolysis of the alkoxysilyl group is hydrophilic. If the structure is selected, scratch resistance, weather resistance, chemical resistance and antifouling property can be imparted to the cured coating composed of the organic resin-based coating (for example, Patent Document 1 , 2 and 3: Japanese Patent Application Laid-Open No. 09-040908, Japanese Laid-Open Patent Publication No. 09-040911, Japanese Laid-Open Patent Publication No. 09-111188).

Recently, a silicone alkoxy oligomer having an epoxy group, a mercapto group, a (meth) acryloxy group, or an alkenyl group has been widely used as an adhesion enhancer, a primer composition, a pressure sensitive adhesive composition, a photocurable type optical functional imparting film, Resin compositions and the like.

As the application range is enlarged as described above, the hydrolytic reactivity of the alkoxysilyl group becomes a problem in some cases. Silicon alkoxy oligomers currently used have a methoxy group and / or an ethoxy group as an alkoxy group. Since they have a relatively high hydrolytic reactivity, there are cases where desired properties are not obtained by unintended hydrolysis have.

The present applicant has proposed an organopolysiloxane containing such an organic functional group and a hydrolyzable group and a process for producing the organopolysiloxane and a process for producing the organopolysiloxane (for example, see Patent Documents 4 and 5: Japanese Patent Application Laid-Open No. Hei 07-292108, Japanese Patent Application Laid- In the above-mentioned patent documents, the hydrolyzable group is generally an alkoxy group having 1 to 4 carbon atoms, and may contain a plurality of kinds of hydrolysable groups. However, a plurality of kinds of hydrolyzable groups There is no description about intentionally introducing an alkoxy group to control the hydrolytic reactivity.

Patent Document 1: Japanese Patent Application Laid-Open No. 09-040908

Patent Document 2: Japanese Patent Application Laid-Open No. 09-040911

Patent Document 3: Japanese Patent Application Laid-Open No. 09-111188

Patent Document 4: Japanese Patent Application Laid-Open No. 07-292108

Patent Document 5: JP-A-08-134219

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a novel organopolysiloxane containing a plurality of alkoxy groups having different numbers of carbon atoms from an organic functional group and capable of arbitrarily changing the hydrolytic reactivity of alkoxysilyl groups .

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted intensive investigations to achieve the above object. As a result, it has been found that, in the organopolysiloxane containing an organic functional group and a hydrolyzable group having high reactivity, a methoxy group or an ethoxy group having high hydrolysis- It has been found that the hydrolytic reactivity of a silicon alkoxy oligomer product can be arbitrarily changed by containing an alkoxy group having 3 and / or 4 carbon atoms such as propoxy or butoxy groups in the same molecule.

Particularly, in the case of a silicone alkoxy oligomer having a mercapto group or an epoxy group, which has high affinity for water as an organic functional group and promotes hydrolysis of the alkoxysilyl group, It is possible to improve storage stability and application characteristics by containing a plurality of kinds of alkoxy groups having different hydrolytic reactivities. Thus, the present invention has been completed.

Accordingly, the present invention provides the following organopolysiloxanes.

[1] An organopolysiloxane containing, in one molecule, an organic functional group represented by the following average formula (Formula 1) and a plurality of alkoxy groups having different carbon atoms.

^{_{Y a R 1 b Si (OCH}} 3) c (OC 2 H 5) d (OR 2) e (OH) f O (4-abcdef) / 2

(Wherein Y is an organic group having at least one kind selected from a mercapto group, an epoxy group, a (meth) acryloxy group, an alkenyl group, a haloalkyl group and an amino group, R ¹ is an organic group having at least one aliphatic unsaturated bond A, b, c, d, e, and f are each independently selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms and an unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, R ² is an alkyl group having 3 and / 2, 0? C? 2, 0? D? 2, 0 <e? 2, 0? F? 1, c and d are not 0 at the same time and 0.1? C + d + e? 2? A + b + c + d + e + f? 3.

[2] The organopolysiloxane according to [1], wherein Y in the average composition formula (Formula 1) is an organic group containing a mercapto group or an epoxy group.

[3] The organopolysiloxane according to [1] or [2], wherein b in the average composition formula (Formula 1) is an integer, R ¹ is a methyl group, and R ² is a propyl group or an isopropyl group.

[4] The organopolysiloxane according to any one of [1] to [3], wherein in the average composition formula (Formula 1), c and d are simultaneously integers.

At least one alkoxysilane having an organic functional group represented by the following formula (2) and / or a partial hydrolyzate thereof, at least one alkoxy group-containing silane compound represented by the following formula (3), a partial hydrolyzate thereof and a condensation product thereof The organopolysiloxane according to any one of [1] to [4], wherein the organopolysiloxane is obtained by partially hydrolyzing and polycondensing a mixture of one or more kinds of water.

^{_{YR 1 m Si (OCH 3)}} n (OC 2 H 5) 3-mn

R ¹ _p Si (OCH ₃ ) _q (OC ₂ H ₅ ) _r (OR ² ) _4-pqr

M is an integer of 0 to 2, n is an integer of 0 to 3, and m + n is an integer in the range of 0 to 3, and R &^lt; ² &gt; p is an integer of 0 to 2, q is an integer of 0 to 4, r is an integer of 0 to 4, provided that p + q + r is an integer in the range of 0 to 4. The alkoxy group- One or more components having ^two groups.

[6] The organopolysiloxane according to [5], wherein m in the formula (2) is 0, R ¹ in the formula (3) is a methyl group, and p is 0 and / or 1.

[7] The organic functional group-containing alkoxysilane represented by the above formula (2) is at least one selected from the group consisting of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the compound represented by the formula Wherein the alkoxy group-containing silane compound represented by Formula (3) is at least one selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, methyltriisobutoxysilane, At least one selected from silane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane and tetraisobutoxysilane (provided that methyltripropoxysilane, methyltriisopropoxysilane, Tetrabutoxysilane, tetraisobutoxysilane, tetraisobutoxysilane, methyltriisobutoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and tetraisobutoxysilane as essential components). Or the organopolysiloxane described in [6].

[8] The organopolysiloxane according to any one of [1] to [7], which has an average degree of polymerization of 3 to 100.

Since the organopolysiloxane of the present invention contains an organic functional group and a plurality of alkoxysilyl groups in the molecule, the organopolysiloxane can be used as a crosslinking agent such as a coating material, a coating material, an adhesive agent, a sealing material or the like which can be cured by reacting with an organic functional group, .

As the oligomer type silane coupling agent, a conventional monomer type silane coupling agent can be used as a reinforcing property improving agent for a composite material composed of an organic resin and an inorganic material, and various functional materials using an organic functional group or an alkoxysilyl group- And the hydrolytic reactivity as a silicon alkoxy oligomer product can be arbitrarily changed in any application field depending on the purpose of use, and thus its utility value is high.

(Best Mode for Carrying Out the Invention)

Hereinafter, the present invention will be described in detail.

The organopolysiloxane containing the organic functional group and plural kinds of alkoxy groups of different carbon atoms in the present invention in one molecule of the present invention is represented by the following average compositional formula (Formula 1).

(Formula 1)

^{_{Y a R 1 b Si (OCH}} 3) c (OC 2 H 5) d (OR 2) e (OH) f O (4-abcdef) / 2

Here, Y is an organic group having at least one kind selected from a mercapto group, an epoxy group, a (meth) acryloxy group, an alkenyl group, a haloalkyl group and an amino group. Of these functional groups, a mercapto group, an epoxy group, a (meth) acryloyloxy group, and an amino group are usually bonded to a silicon atom via a linking group. Examples of such linking groups include an ether bond (-O-), an imino group (-NH-) , And alkylene-arylene-alkylene groups, which may have a hetero atom such as methylene, ethylene, trimethylene, hexamethylene, decamethylene, etc. A divalent hydrocarbon group having an aromatic ring therebetween including alkylene, methylphenylethyl and the like, and a divalent aliphatic group having an oxygen atom in between, such as methoxymethyl, methoxyethyl, methoxypropyl, etc. . The alkenyl group or haloalkyl group may be bonded to a silicon atom through a linking group or may be directly bonded to a silicon atom. Specifically, mercapto methyl group, 3-mercaptopropyl group, 6-mercaptosyl group, 10-mercaptodecyl group, (4-mercaptomethyl) phenylethyl group and the like are exemplified as an organic group having a mercapto group Epoxy group, a glycidoxymethyl group, a 3-glycidoxypropyl group, a 5,6-epoxyhexyl group, a 9,10-epoxydecyl group, a 2- (3,4-epoxycyclohexyl) - (3,4-epoxy-4-methylcyclohexyl) propyl group, and the like, and examples of the organic group having a (meth) acryloxy group include an acryloxymethyl group, a 3-acryloxypropyl group, a 6-acryloxyhexyl group, Methacryloxypropyl group, 6-methacryloxyhexyl group, 10-methacryloyldecyl group, and the like. Examples of the organic group having an alkenyl group include a vinyl group, allyl group, Hexenyl group, 9-decenyl group, 3-vinyloxypropyl group, p-styryl group, cyclohexenylethyl group and the like, and haloalkyl Chlorodecyl, 10-chlorodecyl, bromomethyl, and 3-bromopropyl groups. Examples of the organic group having an amino group include aminomethyl group, 3-chloropropyl group, Aminopropyl group, N-methyl-3-aminopropyl group, N, N-dimethyl- Aminopropyl group, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl group and the like.

In the organopolysiloxane of the present invention, when the organic functional group is an organic group having a mercapto group, an epoxy group or a (meth) acryloxy group, the organopolysiloxane is preferable in various applications because of its high reactivity. In particular, It is more desirable because it has high utility value.

R ¹ is an unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms which does not have at least one aliphatic unsaturated bond and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a 1-methylpropyl group An alkyl group, an aryl group or an aralkyl group such as a methyl group, an ethyl group, a butyl group, an isobutyl group, a t-butyl group, a hexyl group, an octyl group, a phenyl group, a tolyl group, a benzyl group or a phenylethyl group. From the standpoint of the effect of disruption and cost, it is particularly preferable to use methyl group.

R ² is an alkyl group having 3 and / or 4 carbon atoms, and specific examples thereof include a propyl group, an isopropyl group, a 1-methylpropyl group, a butyl group, an isobutyl group and a t- Methoxypropyl is included as one capable of achieving an equivalent effect, but from the standpoints of suitably lowering the hydrolytic reactivity and the effect of increasing the volume of the alkyl group on the content (equivalent) of the organic functional group, Or an isopropyl group.

2, 0? C? 2, 0? D? 2, 0 <e? 2, 0? f? 1, c and d are not 0 at the same time, and 0.1? c + d + e? 2.5 and 2? a + b + c + d + e + f?

Here, the coefficient a is a numerical value showing the degree of substitution of the organic functional group with respect to the silicon atom. When the organopolysiloxane is used in an excessively small amount, the characteristic due to the reactivity of the organic functional group to be originally used is not exhibited, It is necessary to have one organofunctional group in the molecule. On the other hand, it is necessary to set the degree of substitution of the organic functional group larger than 1, since it is difficult in terms of synthesis method and cost, Is in the range of 0.1? A? 1, more preferably in the range of 0.1? A? 0.8.

The coefficient b is a numerical value representing the substitution degree of an unsubstituted monovalent hydrocarbon group of 1 to 8 carbon atoms having no aliphatic unsaturated bond to a silicon atom. When this is 0 or less, the content of the alkoxy group is relatively increased Thereby increasing the contribution rate to the hydrolysis reaction and the silylation reaction, and in some cases, the affinity to the number of organopolysiloxanes is improved. On the other hand, when this value is large, depending on the type of the monovalent hydrocarbon group, hydrophobicity is imparted to the organopolysiloxane (such as an alkyl group), compatibility with the organic compound or organic resin is improved (phenyl group, etc.) (Methyl group) in which flexibility and releasability are imparted to the cured product of the cured product, but since the content of the alkoxy group is relatively reduced, it becomes unsuitable for applications utilizing the reactivity of the alkoxysilyl group. Therefore, it is necessary to set the range of 0? B <2 according to the purpose of use, preferably 0? B? 1, more preferably 0? B?

C is the substitution degree of the methoxy group, d is the substitution degree of the ethoxy group, e is the number of carbon atoms Represents the substitution degree of the alkoxy group of the number 3 and / or 4. C and d representing the methoxy group and the ethoxy group having high hydrolysis reactivity and e representing the content of the alkoxy group having 3 and / or 4 carbon atoms such as propoxy and butoxy groups having low hydrolysis reactivity are respectively From the object of the present invention in which a plurality of kinds of alkoxy groups having different hydrolysis reactivity are present in the same molecule, 0? C? 2, 0? D C &quot; and &quot; d &quot; denote the range of 0 &lt; e &lt; 2 and the total substitution degree of the alkoxy group, . Preferably, at least one of 0? C? 1.8 and 0? D? 1.8, where at least one of c and d is 0.1 or more, 0.1? E? 1.8 and 0.2? C + d + e? Preferably, the ranges are 0.1? C? 1.8, 0.1? D? 1.8, 0.1? E? 1.8, 0.5? C + d + e?

The coefficient f is a numerical value indicative of the degree of substitution of the hydroxyl group with respect to the silicon atom, that is, the content of the silanol group, and this silanol group can participate in the silylation reaction or the condensation reaction and has an effect of imparting hydrophilicity to the organopolysiloxane , And it is preferable to make the organopolysiloxane as small as possible in terms of securing the storage stability of the organopolysiloxane. Therefore, it is necessary to set the range of 0? F? 1, preferably 0? F? 0.5, more preferably 0? F? 0.2.

The sum a + b + c + d + e + f of the respective coefficients described above determines [4- (a + b + c + d + e + f)] / 2 indicating the degree of condensation of the organopolysiloxane , And it is necessary to set the range of 2? A + b + c + d + e + f? 3. The degree of polymerization of the organopolysiloxane can be in the range from two dimers of silicon atoms to a polymer of several hundreds of silicon atoms. However, when the average degree of polymerization is 2, the content of monomers in the produced organopolysiloxane increases, If the intended use of the silicone alkoxy oligomer is impaired and the average degree of polymerization is excessively high, it becomes difficult to handle because it becomes a high viscosity product, paste or solid phase. Therefore, the average degree of polymerization is preferably in the range of 3 to 100, To 50% by weight. From this point of view, it is also preferable that the range of 2 + a + b + c + d + e + f +2.67, more preferably 2 + a + b + b + c + d + e + f? 2.67.

The organopolysiloxane containing an organic functional group and a plurality of alkoxy groups of different carbon atoms in the present invention in one molecule of the present invention may be any of those represented by the above average composition formula (Formula 1), a to f each satisfying the above range, Chain, branched, cyclic, and a combination thereof.

Next, the organopolysiloxane containing the organic functional group and plural kinds of alkoxy groups of different carbon atoms of the present invention in one molecule can be obtained by conventionally known various formulations, and as general means, (A) the organic functional group and (B) an alkoxysilane containing an organic functional group and an alkoxysilane containing an alkoxy group having a different number of carbon atoms and having an organic functional group, and a method of partially hydrolyzing and polycondensing the alkoxysilane containing a plurality of alkoxy groups having different numbers of carbon atoms (C) a method of partial hydrolysis and polycondensation of an alkoxysilane containing no methoxy group and / or an ethoxy group obtained by the same partial hydrolysis and polycondensation operation, and It is also possible to adopt an ester exchange reaction of an organopolysiloxane and an alcohol having 3 or 4 carbon atoms.

In the present invention, from the viewpoint of the degree of freedom in the structural design of the organopolysiloxane and easiness of obtaining the raw material, based on the above-mentioned (B) recipe, at least one organic functional group-containing alkoxysilane represented by the following general formula (2) Or a partial hydrolyzate thereof and at least one alkoxy group-containing silane compound represented by the following general formula (3), a partially hydrolyzed product thereof and a condensate thereof is subjected to partial cohydrolysis and polycondensation of an organopolysiloxane .

(2)

^{_{YR 1 m Si (OCH 3)}} n (OC 2 H 5) 3-mn

(Formula 3)

R ¹ _p Si (OCH ₃ ) _q (OC ₂ H ₅ ) _r (OR ² ) _4-pqr

M is an integer of 0 to 2, n is an integer of 0 to 3, provided that m + n is an integer in the range of 0 to 3, and Y, R ¹ , and R ² have the same meanings as defined above, p is an integer of 0 to 2, q is an integer of 0 to 4, r is an integer of 0 to 4, provided that p + q + r is an integer in the range of 0 to 4, OR &lt; ^{2 &gt;} group.

Specific examples of the organic functional group-containing alkoxysilane represented by the general formula (2) include a mercapto methyl group, a 3-mercaptopropyl group, a 6-mercaptosyl group, a 10-mercaptodecyl group, (3-glycidoxypropyl group, 5,6-epoxyhexyl group, 9,10-epoxydecyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 2- Acryloxyethyl group, a 3-acryloxypropyl group, a 6-acryloxyhexyl group, a 10-acryloxydecyl group, a methacryloxy methyl group, a 3-methacryloxy group Methacryloyloxydecyl, vinyl, allyl, 5-hexenyl, 9-decenyl, 3-vinyloxypropyl, p-styryl, A chloromethyl group, a 3-chloropropyl group, a 6-chlorohexyl group, a 10-chlorodecyl group, a bromomethyl group, a 3-bromopropyl group, an aminomethyl group, Aminopropyl group, N-methyl-3-aminopropyl group, N, N-dimethyl- Aminopropyl groups, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl groups and the like, triethoxysilane compounds having tri A silane compound, a silane compound, a silane compound, a silane compound, a silane compound, a silane compound, a silane compound, a silane compound, a silane compound, a silane compound, Compounds, ethoxydimethoxysilane compounds, methoxydiethoxysilane compounds and the like.

Specific examples of the alkoxy group-containing silane compound represented by the general formula (3) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxy Examples of the alkoxysilane of p = 1, such as silane and tetraisobutoxysilane, include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 1-methylpropyl group, a butyl group, an isobutyl group, P = 2, such as trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, triisobutoxysilane, etc. having a phenyl group, a tolyl group, a benzyl group, Examples of the alkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, methylethyldimethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane.

From the viewpoint of availability and cost of raw materials, it is preferable that m is 0, n is 3 or 0, that is, trimethoxysilane, triethoxysilane or a partial hydrolyzate thereof containing an organic functional group in the formula (2) It is preferable that R ¹ in the general formula (3) is a methyl group, p is 1 and / or 0, that is, methyltrialkoxysilane, tetraalkoxysilane, partial hydrolyzate thereof or a condensate thereof. Further, more preferably an alkoxy group-containing silane compound in which q and r are both 0, a partial hydrolyzate thereof or a condensate thereof as essential components.

Particularly, as the organic functional group-containing alkoxysilane represented by the general formula (2), 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- At least one selected from propyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane is used, Examples of the alkoxy group-containing silane compound represented by the general formula (3) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, methyltriisobutoxysilane, At least one member selected from the group consisting of methyltriethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane and tetraisobutoxysilane, At least one member selected from propoxysilane, methyltributoxysilane, methyltriisobutoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane and tetraisobutoxysilane is used as an essential component) is used Is particularly preferable.

The organic functional group-containing alkoxysilane or the partial hydrolyzate thereof, the alkoxy group-containing silane compound, the partial hydrolyzate thereof, or the condensate thereof may be used in combination of plural species, Or a partial hydrolyzate thereof, it is preferable to use an organic functional group of the same species. In order to arbitrarily design the ratio of the methoxy group, the ethoxy group and the alkoxy group of 3 or 4 carbon atoms in the organopolysiloxane, the alkoxy group-containing silane compound represented by the general formula (3), the partial hydrolyzate thereof or the condensation thereof As the water, it is preferable to use two or more kinds of alkoxy groups different from each other in combination.

The mixing ratio of the organic functional group-containing alkoxysilane and / or the partial hydrolyzate thereof to the alkoxy group-containing silane compound, the partial hydrolyzate thereof or the condensate thereof is not particularly limited, but if the mixing ratio of the former is too small, It is necessary to use at least one organic functional group in at least one molecule without exhibiting characteristics due to the reactivity of the organic functional group that should be inherent in the use of the polysiloxane. , More preferably in the range of 10:90 to 80:20.

The method of mixing these raw materials and the mixing method, and the method of carrying out the partial hydrolysis and polycondensation are not particularly limited, and the organic functional group-containing alkoxysilane and / Or partial hydrolysis and polycondensation reaction is carried out by adding water to the mixture of the partial hydrolyzate and the alkoxy group-containing silane compound, partial hydrolyzate thereof or condensate thereof in the presence of a hydrolysis and condensation reaction catalyst And at this time, it is also possible to use an appropriate organic solvent as necessary.

As the hydrolysis and condensation reaction catalyst to be used, various conventionally known catalysts can be used. Specific examples 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, inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, , Basic compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, sodium acetate, potassium acetate, ammonia, ammonium hydroxide and triethylamine, fluorinated compounds such as potassium fluoride and ammonium fluoride, tetraisopropyl titanate, tetra Butyl titanate, dioctyl tin dilaurate, aluminum chelates, and the like. The amount of the catalyst to be used is preferably in the range of 0.0001 to 10 mol%, more preferably in the range of 0.001 to 3 mol% based on the number of moles of Si atoms present in the entire raw material, More preferably in the range of

As described above, the degree of polymerization of the organopolysiloxane of the present invention may be from 2 dimers of silicon atoms to a polymer of about several hundred silicon atoms, but the average degree of polymerization is determined by the amount of water used for partial hydrolysis and polycondensation . If the water is added in excess, the amount of the alkoxy group is hydrolyzed to become a resin body having a large branched structure, and the desired silicon alkoxy oligomer can not be obtained. Therefore, the amount of the hydrolyzed water needs to be strictly determined. For example, in the case where all of the alkoxysilane raw materials to be used are monomers having one silicon atom, in order to prepare an organopolysiloxane having an average degree of polymerization Z, water of (Z-1) mols is preferably used for the Z-mole alkoxysilane raw material Partial hydrolysis and polycondensation may be performed.

At this time, organic solvents such as alcohols, ethers, esters, and ketones may be used if necessary. Specific examples of these organic solvents include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol and propylene glycol monomethyl ether, ethers such as diethyl ether and dipropyl ether, methyl acetate, ethyl acetate and ethyl acetoacetate , Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and the like. In addition, a non-polar solvent such as hexane, toluene, or xylene may be used together with the solvent. Particularly, it is preferable to use alcohols such as methanol, ethanol and isopropyl alcohol.

The amount of the organic solvent to be used may be in the range of 0 to 1000 parts by mass based on 100 parts by mass of the total amount of the alkoxysilane, partial hydrolyzate thereof and condensates thereof to be used as raw materials. However, if the amount is small, It is preferable that the amount is not more than 10 to 500 parts by mass, more preferably not more than 20 to 200 parts by mass, Is more preferable.

As a practical operation in the partial (co) hydrolysis and polycondensation reaction, a mixed solution of a predetermined amount of water or a water / organic solvent is added dropwise to a mixed system comprising an alkoxysilane raw material, a catalyst and an organic solvent, It is preferable to drop a mixed solution of water / catalyst or a mixed solution of water / catalyst / organic solvent in a predetermined amount of the mixing system made of an organic solvent. At this time, an alkoxysilane raw material having a methoxy group or an ethoxy group with high hydrolysis reactivity and an alkoxysilane raw material having an alkoxy group having 3 and / or 4 carbon atoms such as a propoxy group or a butoxy group having a low hydrolysis reactivity It is also possible to carry out a polycondensation reaction after hydrolysis, mixing the two components and, if necessary, further partial hydrolysis. Each reaction may be carried out at a temperature in the range of 0 to 150 占 폚. However, in general, the reaction progresses slowly at a temperature lower than room temperature, which is not practical and even when the temperature is too high, thermal decomposition or decomposition of an epoxy group or a mercapto group It is preferable to set the temperature within the range of 20 to 130 占 폚 because adverse effects on organic functional groups such as thermal polymerization of acryloxy group occur. After the reaction, the purification of the used catalyst by neutralization, adsorption, filtration, or the like, or a purification process by distillation or the like of the used organic solvent and by-product alcohol and low-boiling point product is carried out to obtain the desired organopolysiloxane of the present invention.

(Example)

Hereinafter, the present invention will be described in more detail by way of examples, which are merely intended to be illustrative of the present invention. The present invention is not limited by the following examples unless it exceeds the gist of the present invention. The analysis of the organopolysiloxane obtained in each example was carried out by the following method.

(1) The average degree of polymerization of the organopolysiloxane was calculated from the weight average molecular weight determined based on the calibration curve prepared from the polystyrene standard sample by gel permeation chromatography (GPC) analysis.

(2) The alkoxy group content in the organopolysiloxane was measured by an alkali cracking-gas chromatography (GC) analysis method (see Silicon Handbook, 792-793 (published by Nikkan Kogyo Segment) The coefficients c, d, and e were obtained.

(3) The structural analysis of the organopolysiloxane was carried out by a silicon nuclear magnetic resonance spectrum ( ²⁹ Si-NMR) analysis and a proton nuclear magnetic resonance spectrum ( ¹ H-NMR) The coefficients a, b, and f were obtained.

(4) The organic functional equivalent of the organopolysiloxane was measured by the following analysis.

(i) a mercapto group equivalent

(See Analytical Chemistry Manual, 2nd Ed., 432-433 (published by Maruzen Co., Ltd.)), which was prepared by adding potassium acetate / potassium iodide / sodium iodate solution - sodium thiosulfate solution.

(ii) epoxy equivalent weight

(Produced by chlorohydrin) by hydrochloric acid-sodium hydroxide solution titration (see Analytical Chemistry Manual, 2nd Ed., 334-335 (Maruzen Co., Ltd.)).

(iii) methacryl group equivalent

Was calculated from the above-described silicon nuclear magnetic resonance spectrum ( ²⁹ Si-NMR) analysis and proton nuclear magnetic resonance spectrum ( ¹ H-NMR) analysis.

(5) The viscosity of the organopolysiloxane was measured according to JIS Z 8803 at 25 캜.

[Example 1] Synthesis of organopolysiloxane 1

(0.3 mole) of tetraethoxysilane, 52.9 g (0.2 mole) of tetrapropoxysilane, 62.5 g of ethanol and 52.9 g of isopropyl alcohol were placed in a 1 L flask equipped with a stirrer, a cooling condenser, a thermometer and a dropping funnel And the mixture was heated in an oil bath while stirring and mixing to raise the internal temperature to 50 캜. While stirring the flask, 0.1N aqueous hydrochloric acid solution 7.2g ^- by (water: 0.4 moles of hydrochloric acid 7.2 × 10 ⁴ mol) of 2 hours a mixture of 7.2g of ethanol under reflux over 10 minutes by dropwise addition, more elevated temperature aging To obtain a preliminary hydrolysis reaction mixture A.

Separately, a mixed solution of 39.3 g (0.2 mol) of 3-mercaptopropyltrimethoxysilane, 40.9 g (0.3 mol) of methyltrimethoxysilane and 80.2 g of methanol was added at a temperature of 20 to 30 DEG C and 0.1 N 7.2g aqueous solution of hydrochloric acid (water 0.4 mol, of hydrochloric acid: 7.2 × 10 ^{- 4} mol) of methanol and a mixture of 7.2g was dropped over 10 minutes, and the internal temperature for 30 minutes to pre-aged at 20~30 ℃ hydrolysis Liquid B was obtained.

After the addition of pre-hydrolysis of the reaction solution B during the preliminary hydrolysis of the reaction solution A and mixed stirring, 0.1N hydrochloric acid aqueous solution at an inner temperature of 20~30 ℃ 1.8g (water 0.1 mol, of hydrochloric acid: 1.8 × 10 ^{- 4} Mol) and 1.8 g of ethanol were added, and the mixture was heated in an oil bath and aged for 2 hours under reflux. Then, 1% ethanol solution of potassium fluoride ^{9.3g (KF: 1.6 × 10 -} 3 moles) was added, and further aged for 2 hours at reflux the reaction was carried ball portion hydrolysis, polycondensation.

Subsequently, the alcohol component was distilled off under elevated temperature to an internal temperature of 80 캜 under atmospheric pressure, and the temperature was raised to an internal temperature of 100 캜 under a reduced pressure of 30 Torr to distill off the remaining alcohol component and the low boiling point component, Thereby obtaining liquid organopolysiloxane 1 (yield: 127.5 g, yield: 92%).

The organopolysiloxane 1 is obtained by reacting the organopolysiloxane 1 in which Y is a 3-mercaptopropyl group, R ¹ is a methyl group and R ² is a propyl group in the average composition formula (Formula 1), the molar ratio of each raw material (other than the organic solvent) Table 1 shows the weight average molecular weight, the average degree of polymerization, the respective coefficients in the above average composition formula (Formula 1), the viscosity (mm 2 / s) and the mercapto group equivalent obtained from the results.

[Example 2] Synthesis of organopolysiloxane 2

(0.2 mole) of tetraethoxysilane, 79.3 g (0.3 mole) of tetrapropoxysilane, 41.7 g of ethanol, and 79.3 g of isopropyl alcohol were placed in a 1 L flask equipped with a stirrer, a cooling condenser, a thermometer and a dropping funnel And the mixture was heated in an oil bath while stirring and mixing to raise the internal temperature to 50 캜. While stirring the flask, 0.5N aqueous hydrochloric acid solution, 7.2g (water 0.4 mol, of hydrochloric acid: 3.6 × 10 ^{- 3} mol) and a mixed solution of 7.2g of ethanol was added dropwise over 10 minutes, to two hours and more elevated temperature aging under reflux To obtain a preliminary hydrolysis reaction solution A.

Separately, a mixed solution of 47.7 g (0.2 mole) of 3-mercaptopropyltriethoxysilane, 40.9 g (0.3 mole) of methyltrimethoxysilane, 40.9 g of methanol and 47.7 g of ethanol was added to a mixed solution of 20 to 30 0.5N hydrochloric acid solution in ℃ 7.2g (water 0.4 mol, of hydrochloric acid 23.6 × 10 ^{- 3} moles) of the pre-hydrolysis was added dropwise over 10 minutes to a mixture of 7.2g of methanol, and further aged for 30 minutes at an inner temperature of 20~30 ℃ Decomposition reaction solution B was obtained.

A preliminary hydrolysis reaction liquid B was added to the above-mentioned prehydrolysis reaction liquid A and stirred and mixed. Then, 1.8 g of a 0.5N hydrochloric acid aqueous solution (water: 0.1 mol, hydrochloric acid: 9 10 ^-4 mol ) And 1.8 g of ethanol was added, and the mixture was heated in an oil bath and aged for 2 hours under reflux. Subsequently, 9.3 g (KF: 8 x 10 ^-3 mol) of a 5% ethanol solution of potassium fluoride was added and further aged for 2 hours under reflux for partial hydrolysis and polycondensation reaction.

Subsequently, the alcohol component was distilled off under elevated temperature to an internal temperature of 80 캜 under atmospheric pressure, and the temperature was raised to an internal temperature of 100 캜 under a reduced pressure of 30 Torr to distill off the remaining alcohol component and the low boiling point component, Thereby obtaining a liquid organopolysiloxane 2 (yield: 136.7 g, yield: 94%).

The organopolysiloxane 2 is obtained by reacting the organopolysiloxane 2 in which Y is a 3-mercaptopropyl group, R ¹ is a methyl group and R ² is a propyl group in the average composition formula (Formula 1), the molar ratio of each raw material (other than an organic solvent) Table 1 shows the weight average molecular weight, the average degree of polymerization, the respective coefficients in the above average composition formula (Formula 1), the viscosity (mm 2 / s) and the mercapto group equivalent obtained from the analysis results.

[Example 3] Synthesis of organopolysiloxane 3

132.2 g (0.5 mol) of tetrapropoxysilane and 132.2 g of isopropyl alcohol were charged into a 1 L flask equipped with a stirrer, a cooling condenser, a thermometer and a dropping funnel, and heated in an oil bath with stirring to obtain an internal temperature of 50 Lt; 0 &gt; C. While stirring the flask, 1N hydrochloric acid solution 7.2g (water 0.4 mol, of hydrochloric acid: 7.2 × 10 ^{- 3} mol) and aged for 2 hours a mixture of 7.2g of isopropyl alcohol under reflux over 10 minutes by dropwise addition, more elevated temperatures To obtain a preliminary hydrolysis reaction solution A.

Separately, 19.6 g (0.1 mole) of 3-mercaptopropyltrimethoxysilane, 23.8 g (0.1 mole) of 3-mercaptopropyltriethoxysilane, 13.6 g (0.1 mole) of methyltrimethoxysilane, triethoxy silane 35.7g (0.2 mol), 33.2g of methanol, and into a mixture of 59.5g of ethanol, 1N hydrochloric acid solution at an inner temperature of 20~30 ℃ 7.2g (water 0.4 mol, of hydrochloric acid: 7.2 × 10 ^{- 3} moles) And ethanol (7.2 g) was added dropwise over 10 minutes, and further aged at an internal temperature of 20 to 30 DEG C for 30 minutes to obtain a prehydrolysis reaction liquid (B).

The prehydrolysis reaction liquid B was added to the above-mentioned prehydrolysis reaction liquid A, and the mixture was stirred and mixed. Then, 1.8 g of a 1N hydrochloric acid aqueous solution (water: 0.1 mol, hydrochloric acid: 1.8 x 10 ^-3 mol) And 1.8 g of isopropyl alcohol was added thereto, followed by heating in an oil bath and aging for 2 hours under reflux. Then, potassium fluoride ^{0.94g (KF: 1.62 × 10 -} 2 mol) was added and allowed to react further aged for 2 hours portions ball hydrolysis, polycondensation under reflux.

Subsequently, the alcohol component was distilled off under elevated temperature to an internal temperature of 80 캜 under atmospheric pressure, and the temperature was raised to an internal temperature of 100 캜 under a reduced pressure of 30 Torr to distill off the remaining alcohol component and the low boiling point component, To obtain a liquid organopolysiloxane 3 (yield: 139.0 g, yield: 91%).

The organopolysiloxane 3 is a mixture of the organopolysiloxane 3 and the organopolysiloxane 3 in which Y is a 3-mercaptopropyl group, R ¹ is a methyl group, and R ² is a propyl group in the average composition formula (Formula 1) Table 1 shows the weight average molecular weight, the average degree of polymerization, the respective coefficients in the above average composition formula (Formula 1), the viscosity (mm 2 / s) and the mercapto group equivalent obtained from the analysis results.

[Example 4] Synthesis of organopolysiloxane 4

(0.2 mole) of methyltriisopropoxysilane, 96.2 g (0.3 mole) of tetrabutoxysilane and 140.3 g of isopropyl alcohol were charged into a 1 L flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel And heated in an oil bath while stirring and mixing to raise the internal temperature to 50 캜. While stirring the flask, 1.5N aqueous hydrochloric acid solution 7.2g ^- under (water: 0.4 moles of hydrochloric acid 1.08 × 10 ² mole) and isopropyl alcohol and a mixture of 7.2g was added dropwise over 10 minutes, further raised to reflux 2 The solution was pre-hydrolyzed by time aging.

Separately, a mixed solution of 71.5 g (0.3 mole) of 3-mercaptopropyltriethoxysilane, 44.1 g (0.2 mole) of methyltriisopropoxysilane, 71.5 g of ethanol and 44.1 g of isopropyl alcohol was added dropwise at an internal temperature 1N aqueous hydrochloric acid solution at 20~30 ℃ 7.2g (water 0.4 mol, of hydrochloric acid: 7.2 × 10 ^{- 3} moles) of isopropyl alcohol and a mixture of 7.2g was added dropwise over 10 minutes, 30 also at an inner temperature of 20~30 ℃ Minute aging to obtain a preliminary hydrolysis reaction liquid B.

The prehydrolysis reaction liquid B was added to the above-mentioned prehydrolysis reaction liquid A, and the mixture was stirred and mixed. Then, 1.8 g of a 1N hydrochloric acid aqueous solution (water: 0.1 mol, hydrochloric acid: 1.8 x 10 ^-3 mol) And 1.8 g of isopropyl alcohol was added thereto, followed by heating in an oil bath and aging for 2 hours under reflux. Then, potassium fluoride ^{1.27g (KF: 2.18 × 10 -} 2 mol) was added to, and 2 more hours aging under reflux and reacted ball portion hydrolysis, polycondensation.

Subsequently, the alcohol component was distilled off under elevated temperature to an internal temperature of 80 캜 under atmospheric pressure, and the temperature was raised to an internal temperature of 120 캜 under a reduced pressure of 30 Torr to distill off the remaining alcohol component and the low boiling point component, Thereby obtaining a liquid organopolysiloxane 4 (yield: 165.1 g, yield: 96%).

The organopolysiloxane 4 is obtained by reacting the respective raw materials (other than the organic solvent) of the used raw materials (except for the organic solvent) in which Y is a 3-mercaptopropyl group, R ¹ is a methyl group, R ² is an isopropyl group and a butyl group in the average composition formula Table 1 shows the weight average molecular weight, the average polymerization degree, the respective coefficients in the average composition formula (Formula 1), the viscosity (mm 2 / s) and the mercapto group equivalent obtained from the above analysis results.

[Example 5] Synthesis of organopolysiloxane 5

(0.2 mol) of 3-glycidoxypropyltrimethoxysilane, 66.1 g (0.3 mol) of methyltriisopropoxysilane, 0.1 g of tetra (tert-butoxycarbonyl) methyltriethoxysilane was added to a 1 L flask equipped with a stirrer, a cooling condenser, a thermometer and a dropping funnel. a silane 104.2g (0.5 mol), methanol 47.3g, 104.2g of ethanol, isopropyl alcohol and 66.1g 1% ethanol solution of 17.4g of potassium fluoride (KF: ³ × 10 ^- 3 moles) added to, and mixed with stirring Heated in an oil bath to raise the internal temperature to 50 캜.

While stirring in the flask, a mixed solution of 16.2 g (0.9 mole) of ion-exchanged water and 16.2 g of ethanol was added dropwise over 30 minutes, and the mixture was further heated and refluxed for 4 hours for partial hydrolysis and polycondensation reaction. Subsequently, the alcohol component was distilled off under elevated temperature to an internal temperature of 80 캜 under atmospheric pressure, and the temperature was raised to an internal temperature of 100 캜 under a reduced pressure of 30 Torr to distill off the remaining alcohol component and the low boiling point component, Thereby obtaining a liquid organopolysiloxane 5 (yield: 137.5 g, yield: 91%).

The organopolysiloxane 5 is a mixture of the organopolysiloxane 5 and the organopolysiloxane 5 in such a manner that Y is a 3-glycidoxypropyl group, R ¹ is a methyl group, and R ² is an isopropyl group in the average composition formula (Formula 1) Table 1 shows the weight average molecular weight, the average degree of polymerization, the respective coefficients in the average composition formula (Formula 1), the viscosity (mm 2 / s) and the epoxy equivalent weight obtained from the above analysis results.

[Example 6] Synthesis of organopolysiloxane 6

In a 1 L flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel were added 28.4 g (0.12 mol) of 3-glycidoxypropyltrimethoxysilane, 10 parts of a partial hydrolyzate comprising an average dimer of methyltrimethoxysilane , 9.5 g of the condensate (in terms of silicon atom: 0.08 mol), and 68.5 g of Silicate 35 (trade name, manufactured by Tamagaku Kogyo Co., Ltd.) as a partial hydrolysis-condensation product of an average dimer of tetraethoxysilane ), 37.5g of methanol, 68.5g of ethanol and 1% ethanol solution of 19.8g (of potassium fluoride KF: 3.4 × 10 ^- in a ³ mole), while stirring the flask at room temperature for 20~30 ℃, 6.1g ion-exchanged water (0.34 mol) and 6.1 g of ethanol was added dropwise over 10 minutes, and the mixture was further stirred at an internal temperature of 20 to 30 DEG C for 30 minutes.

85.3 g of a partially hydrolyzed condensate composed of an average dimer of tetrapropoxysilane (silicon atom: 0.4 mol), 85.3 g of isopropyl alcohol and 11.6 g of a 1% ethanol solution of potassium fluoride (KF: 2 x 10 ^{- 3} mol) were added, and the mixture was heated in an oil bath while stirring and mixing to raise the internal temperature to 50 캜.

While stirring in the flask, a mixed solution of 3.6 g (0.2 mol) of ion-exchanged water and 3.6 g of ethanol was added dropwise over a period of 10 minutes, the temperature was further raised, and the mixture was aged for 4 hours under reflux for partial hydrolysis and polycondensation reaction. Subsequently, the alcohol component was distilled off under elevated temperature to an internal temperature of 80 캜 under atmospheric pressure, and the temperature was raised to an internal temperature of 100 캜 under a reduced pressure of 30 Torr to distill off the remaining alcohol component and the low boiling point component, Thereby obtaining a liquid organopolysiloxane 6 (yield: 139.8 g, yield: 93%).

The organopolysiloxane (6) is a mixture of the organopolysiloxane (6) and the organopolysiloxane (6), wherein Y is a 3-glycidoxypropyl group, R ¹ is a methyl group and R ² is a propyl group in the average composition formula Table 2 shows the weight average molecular weight, the average degree of polymerization, the respective coefficients in the average composition formula (Formula 1), the viscosity (mm 2 / s) and the epoxy equivalent weight obtained from one analysis result.

[Example 7] Synthesis of organopolysiloxane 7

(0.75 mol) of 3-glycidoxypropyltrimethoxysilane, 26.0 g (0.125 mol) of tetraethoxysilane, 0.1 g of tetrapropoxy (trimethylsilane) and 20.0 g of tetraethoxysilane were placed in a 1 L flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel silane 33.1g (0.125 mole), 177.2g of methanol, 26.0g of ethanol, isopropyl alcohol and 33.1g 1% ethanol solution of 11.6g of potassium fluoride (KF: 2 × 10 ^{- 3} moles) added to, and mixed with stirring in an oil bath And the internal temperature was raised to 50 캜.

While stirring in the flask, a mixed solution of 13.5 g (0.75 mol) of ion-exchanged water and 13.5 g of isopropyl alcohol was added dropwise over 20 minutes, the temperature was further raised, and the reaction mixture was agitated for 4 hours under reflux for partial hydrolysis and polycondensation . Subsequently, the alcohol component was distilled off under atmospheric pressure while raising the internal temperature to 80 deg. C, and the temperature was raised to an internal temperature of 90 deg. C under reduced pressure of 30 Torr to distill off the remaining alcohol component and low boiling point component, Thereby obtaining a liquid organopolysiloxane 7 (yield: 172.7 g, yield: 89%).

The organopolysiloxane 7 is obtained by reacting the respective raw materials (except for the organic solvent) in which Y is a 3-glycidoxypropyl group, R ¹ is absent (b = 0) and R ² is a propyl group in the above average composition formula Average molecular weight, each coefficient in the average composition formula (Formula 1), viscosity (mm 2 / s), and epoxy equivalent weight are shown in Table 2.

[Example 8] Synthesis of organopolysiloxane 8

(0.5 mole) of 3-methacryloxypropyltrimethoxysilane, 44.6 g (0.25 mole) of methyltriethoxysilane, 0.10 mole of methyltriethoxysilane, and 0.10 mole of methyltriethoxysilane were charged in a 1 L flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 55.1 g (0.25 mol) of isopropoxysilane, 124.2 g of methanol, 44.6 g of ethanol and 55.1 g of isopropyl alcohol were charged and heated in an oil bath with stirring to raise the internal temperature to 50 캜.

While stirring in the flask, a mixed solution of 17.1 g of a 0.2N hydrochloric acid aqueous solution (water: 0.95 mol, hydrochloric acid: 3.4 x 10 ^-3 mol) and isopropyl alcohol (17.1 g) was added dropwise over 30 minutes and further heated to reflux for 2 hours Aged. Then, 0.86g of sodium hydrogen carbonate ^was reacted addition of (1.02 × 10 ² mol) for 2 hours to decompose more ripening ball portion singer at reflux, the polycondensation.

Subsequently, 0.1 g of 4-methoxyphenol as a polymerization inhibitor was added, and the alcohol component was distilled off under the atmospheric pressure while raising the internal temperature to 80 캜. The internal temperature was raised to 90 캜 under reduced pressure of 20 Torr, And a low-boiling point component were distilled off, followed by filtration to obtain a colorless transparent liquid organopolysiloxane 8 (yield: 154.1 g, yield: 95%).

The organopolysiloxane 8 is a mixture of the organopolysiloxane 8 and the organopolysiloxane 8, wherein Y is a 3-methacryloxypropyl group, R ¹ is a methyl group, and R ² is an isopropyl group in the average composition formula (Formula 1) Table 2 shows the weight average molecular weight, the average degree of polymerization, the respective coefficients in the average composition formula (Formula 1), the viscosity (mm 2 / s) and the methacryloxy group equivalent obtained from the above analysis results.

[Comparative Example 1] Synthesis of organopolysiloxane 9

(0.2 mole) of 3-mercaptopropyltrimethoxysilane, 40.9 g (0.3 mole) of methyltrimethoxysilane, 0.10 mole of tetraethoxy (meth) acrylate were added to a 1 L flask equipped with a stirrer, a cooling condenser, a thermometer and a dropping funnel. (Water: 0.9 mole, hydrochloric acid: 1.6 x 10 &lt; ^- &gt;) was added while stirring the flask at an internal temperature of 20 to 30 DEG C, ³ mol) and methanol (16.2 g) was added dropwise over 30 minutes, the temperature was further raised, and the mixture was aged for 2 hours under reflux.

Then, 1% ethanol solution of potassium fluoride ^{9.3g (KF: 1.6 × 10 -} 3 moles) was added, and further aged for 2 hours at reflux the reaction was carried ball portion hydrolysis, polycondensation. Subsequently, the alcohol component was distilled off under elevated temperature to an internal temperature of 80 캜 under atmospheric pressure, and the temperature was raised to an internal temperature of 100 캜 under a reduced pressure of 30 Torr to distill off the remaining alcohol component and the low boiling point component, To obtain a liquid organopolysiloxane 9 (amount: 117.0 g, yield: 90%).

The organopolysiloxane 9 was obtained in the same manner as in the above average composition formula (Formula 1) except that Y was a 3-mercaptopropyl group, R ¹ was a methyl group, no OR ² (e = 0), the molar ratio of each raw material (other than an organic solvent) Table 2 shows the weight average molecular weight, the average degree of polymerization, the respective coefficients in the average composition formula (Formula 1), the viscosity (mm 2 / s) and the mercapto group equivalent obtained from the above analysis results.

[Comparative Example 2] Synthesis of organopolysiloxane 10

47.7 g (0.2 mole) of 3-mercaptopropyltriethoxysilane, 53.5 g (0.3 mole) of methyltriethoxysilane, and 0.10 mole of tetraethoxy silane were added to a 1 L flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel silane 104.2g (0.5 moles), and put into 205.4g of ethanol and, while stirring the flask at an internal temperature 20~30 ℃, 0.1N aqueous hydrochloric acid solution 16.2g (water: 0.9 mol, of hydrochloric acid: 1.6 × 10 ^{- 3} moles) and And ethanol (16.2 g) was added dropwise over a period of 30 minutes, and the mixture was further heated and aged for 2 hours under reflux.

Then, 1% ethanol solution of potassium fluoride ^{9.3g (KF: 1.6 × 10 -} 3 moles) was added, and further aged for 2 hours at reflux the reaction was carried ball portion hydrolysis, polycondensation. Subsequently, the alcohol component was distilled off under elevated temperature to an internal temperature of 80 캜 under atmospheric pressure, and the temperature was raised to an internal temperature of 100 캜 under a reduced pressure of 30 Torr to distill off the remaining alcohol component and the low boiling point component, To obtain a liquid organopolysiloxane 10 (yield: 129.5 g, yield: 94%).

The organopolysiloxane 10 is obtained by reacting each of the raw materials (other than the organic solvent) having no 3-mercaptopropyl group, R ¹ with a methyl group, OR ² (e = 0) Table 2 shows the weight average molecular weight, the average polymerization degree, the respective coefficients in the average composition formula (Formula 1), the viscosity (mm 2 / s) and the mercapto group equivalent obtained from the above analysis results.

* The various alkoxysilane raw materials in Tables 1 and 2 are represented by the following compounds.

MP-TMS: 3-mercaptopropyltrimethoxysilane

MP-TES: 3-mercaptopropyltriethoxysilane

GP-TMS: 3-glycidoxypropyltrimethoxysilane

MAP-TMS: 3-methacryloxypropyltrimethoxysilane

M-TMS: methyltrimethoxysilane

M-TMS-dimer: a partially hydrolyzed condensate composed of an average dimer of methyltrimethoxysilane (molar ratio is expressed in terms of silicon atom)

M-TES: methyltriethoxysilane

M-TPS: methyl triisopropoxysilane

TEOS: tetraethoxysilane

TEOS-dimer: a partially hydrolyzed condensate (average molar ratio expressed in terms of silicon atom) composed of an average dimer of tetraethoxysilane;

TPOS: tetrapropoxysilane

TPOS-dimer: a partially hydrolyzed condensate (average molar ratio expressed in terms of silicon atom) of an average dimer of tetrapropoxysilane;

TBOS: tetrabutoxysilane

(6) Evaluation of hydrolysis property of organopolysiloxane

The hydrolyzability of the organopolysiloxanes 1, 2, 3, 9, and 10 obtained in Examples 1 to 3 and Comparative Examples 1 and 2 was evaluated by the following method. 10 parts by mass of organopolysiloxane and 10 parts by mass of acetone were uniformly dissolved in a 50 ml glass bottle and then 1 part by mass of ion-exchanged water was added. After the stopper was closed without leakage, the mixture was dispersed by shaking for 1 hour. After the dispersion was allowed to stand at 25 占 폚 for 20 hours or at 60 占 폚 for 15 hours, anhydrous sodium sulfate was added thereto and dehydrated, and the weight average molecular weight was measured by gel permeation chromatography (GPC) analysis. The results are shown in Table 3.

As is clear from the results shown in Table 3, the organopolysiloxane of the present invention is inhibited from hydrolytic reactivity and is advantageous in terms of storage stability and stability in a mixed composition with a water-containing raw material.

Claims (18)

Wherein the organopolysiloxane contains, in one molecule, an organic functional group represented by the following average formula (Formula 1) and a plurality of alkoxy groups having different carbon atoms. (Formula 1) ^{_{Y a R 1 b Si (OCH}} 3) c (OC 2 H 5) d (OR 2) e (OH) f O (4-abcdef) / 2 (Wherein Y represents a mercapto methyl group, a 3-mercaptopropyl group, a 6-mercaptosyl group, a 10-mercaptodecyl group, a (4-mercaptomethyl) phenylethyl group, a glycidoxymethyl group, (3, 4-epoxy-4-methylcyclohexyl) propyl group, a 2-ethylhexyl group, an isopropyl group, Acryloxymethyl group, 3-acryloxypropyl group, 6-acryloxyhexyl group, 10-acryloxydecyl group, methacryloxymethyl group, 3-methacryloxypropyl group, 6-methacryloxyhexyl group and 10- R ¹ is an unsubstituted alkyl group having 1 to 8 carbon atoms which does not have at least one aliphatic unsaturated bond, R ² is an alkyl group having 3 or 4 carbon atoms B, c, d, e and f satisfy the relationships 0.01? A? 1, 0 b <2, 0? C? 2, 0? D? 2, 0 <e? 2, 0? , c and d are not simultaneously 0, and 0.1? c + d + e? 2.5 And 2? A + b + c + d + e + f? 3. The positive resist composition according to claim 1, wherein Y in the average composition formula (1) is a mercapto methyl group, a 3-mercaptopropyl group, a 6-mercaptosyl group, a 10- An ethyl group; (3-glycidoxypropyl group, 5,6-epoxyhexyl group, 9,10-epoxydecyl group, 2- (3,4-epoxycyclohexyl) ethyl group and 2- -4-methylcyclohexyl) propyl group. The organopolysiloxane is characterized in that it is an organic group containing at least one member selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, The organopolysiloxane according to claim 1 or 2, wherein b in the average composition formula (Formula 1) is an integer, R ¹ is a methyl group, and R ² is a propyl group or an isopropyl group. 3. The organopolysiloxane according to claim 1 or 2, wherein in the average composition formula (1), c and d are simultaneously integers. 4. The organopolysiloxane according to claim 3, wherein in the average composition formula (1), c and d are simultaneously integers. At least one organic functional group-containing alkoxysilane represented by the following formula (2) and / or a partial hydrolyzate thereof, at least one alkoxy group-containing silane compound represented by the following formula (3), a partial hydrolyzate thereof and a condensate thereof Or a mixture of two or more of them is partially hydrolyzed and polycondensed to obtain an organopolysiloxane. (2) ^{_{YR 1 m Si (OCH 3)}} n (OC 2 H 5) 3-mn (Formula 3) R ¹ _p Si (OCH ₃ ) _q (OC ₂ H ₅ ) _r (OR ² ) _4-pqr (Wherein Y represents a mercapto methyl group, a 3-mercaptopropyl group, a 6-mercaptosyl group, a 10-mercaptodecyl group, a (4-mercaptomethyl) phenylethyl group, a glycidoxymethyl group, (3, 4-epoxy-4-methylcyclohexyl) propyl group, a 2-ethylhexyl group, an isopropyl group, Acryloxymethyl group, 3-acryloxypropyl group, 6-acryloxyhexyl group, 10-acryloxydecyl group, methacryloxymethyl group, 3-methacryloxypropyl group, 6-methacryloxyhexyl group and 10- R ¹ is an unsubstituted alkyl group having 1 to 8 carbon atoms which does not have at least one aliphatic unsaturated bond, R ² is an alkyl group having 3 or 4 carbon atoms M is an integer of 0 to 2, n is an integer of 0 to 3, m + n is an integer in the range of 0 to 3, p is an integer of 0 to 2, q is an integer of 0 to 4, An integer of 0 to 4, provided that p + q + r An integer ranging from 0 to 4, and includes at least one component having an OR ² as an alkoxy group-containing silane compound of formula (3).) The organopolysiloxane according to claim 6, wherein m in the formula (2) is 0, R ¹ in the formula (3) is a methyl group, and p is 0 or 1. The organic electroluminescent device according to claim 6, wherein the organic functional group-containing alkoxysilane represented by Formula 2 is 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 At least one member selected from glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane , The alkoxy group-containing silane compound represented by the general formula (3) is at least one selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, methyltriisobutoxysilane, At least one member selected from tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane and tetraisobutoxysilane (provided that at least one member selected from the group consisting of methyltripropoxysilane, At least one member selected from the group consisting of fluorosilane, methyltributoxysilane, methyltriisobutoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and tetraisobutoxysilane) Characterized by the organopolysiloxane. The organopolysiloxane of claim 1, wherein the organopolysiloxane has an average degree of polymerization of 3 to 100. The organopolysiloxane according to claim 6, wherein the organopolysiloxane has an average degree of polymerization of 3 to 100. At least one organic functional group-containing alkoxysilane represented by the following formula (2) and / or a partial hydrolyzate thereof, at least one alkoxy group-containing silane compound represented by the following formula (3), a partial hydrolyzate thereof and a condensate thereof Or an organopolysiloxane containing, in one molecule, an organic functional group represented by the following average formula (1) and a plurality of alkoxy groups having different carbon atom numbers, which is characterized by partially hydrolyzing and polycondensing a mixture of two or more kinds of organopolysiloxane &Lt; / RTI &gt; (Formula 1) ^{_{Y a R 1 b Si (OCH}} 3) c (OC 2 H 5) d (OR 2) e (OH) f O (4-abcdef) / 2 (Wherein Y represents a mercapto methyl group, a 3-mercaptopropyl group, a 6-mercaptosyl group, a 10-mercaptodecyl group, a (4-mercaptomethyl) phenylethyl group, a glycidoxymethyl group, (3, 4-epoxy-4-methylcyclohexyl) propyl group, a 2-ethylhexyl group, an isopropyl group, Acryloxymethyl group, 3-acryloxypropyl group, 6-acryloxyhexyl group, 10-acryloxydecyl group, methacryloxymethyl group, 3-methacryloxypropyl group, 6-methacryloxyhexyl group and 10- R ¹ is an unsubstituted alkyl group having 1 to 8 carbon atoms which does not have at least one aliphatic unsaturated bond, R ² is an alkyl group having 3 or 4 carbon atoms B, c, d, e and f satisfy the relationships 0.01? A? 1, 0 b <2, 0? C? 2, 0? D? 2, 0 <e? 2, 0? , c and d are not simultaneously 0, and 0.1? c + d + e? 2.5 And 2? A + b + c + d + e + f? 3. (2) ^{_{YR 1 m Si (OCH 3)}} n (OC 2 H 5) 3-mn (Formula 3) R ¹ _p Si (OCH ₃ ) _q (OC ₂ H ₅ ) _r (OR ² ) _4-pqr M is an integer of 0 to 2, n is an integer of 0 to 3, and m + n is an integer in the range of 0 to 3, and R &^lt; ² &gt; p is an integer of 0 to 2, q is an integer of 0 to 4, r is an integer of 0 to 4, provided that p + q + r is an integer in the range of 0 to 4. The alkoxy group- One or more components having ^two groups. 12. The method according to claim 11, wherein m in Formula 2 is 0, R ¹ in Formula 3 is a methyl group, and p is 0 or 1. The method of claim 11, wherein the organic functional group-containing alkoxysilane represented by Formula 2 is 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 At least one member selected from glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane , The alkoxy group-containing silane compound represented by the general formula (3) is at least one selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, methyltriisobutoxysilane, At least one member selected from tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane and tetraisobutoxysilane (provided that at least one member selected from the group consisting of methyltripropoxysilane, At least one member selected from the group consisting of propoxysilane, methyltributoxysilane, methyltriisobutoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane and tetraisobutoxysilane) &Lt; / RTI &gt; wherein R &lt; 1 &gt; The positive resist composition according to claim 1, wherein Y in the average composition formula (1) is a mercapto methyl group, a 3-mercaptopropyl group, a 6-mercaptosyl group, a 10- (3, 4-epoxycyclohexyl) ethyl group, 2- (3,4-epoxycyclohexyl) ethyl group, Acryloxymethyl group, 3-acryloxypropyl group, 6-acryloxyhexyl group, 10-acryloxydecyl group, methacryloxy methyl group, 3-methacryloxypropyl group, 6-methacryloxyhexyl group, and 10-methacryloyldecyl group. The organopolysiloxane is preferably an organopolysiloxane. The organic electroluminescent device according to claim 1, wherein R ¹ in the average composition formula (Formula 1) is a methyl group, an ethyl group, a propyl group, an isopropyl group, a 1-methylpropyl group, a butyl group, an isobutyl group, An octyl group, and an octyl group. [12] The method according to claim 11, wherein the organic functional group-containing alkoxysilane and / or its partial hydrolyzate represented by Chemical Formula 2 and the alkoxy group-containing silane compound represented by Chemical Formula 3, partial hydrolyzate thereof, Wherein the blend ratio of the two or more species is 1: 99 to 99: 1 in terms of molar ratio in terms of silicon atom. The method for producing an organopolysiloxane according to claim 11, wherein the organic functional group-containing alkoxysilane represented by the general formula (2) and / or the partial hydrolyzate thereof are used in combination of two or more kinds having the same organic functional group. The organopolysiloxane according to claim 11, wherein the alkoxy group-containing silane compound represented by the formula (3), the partial hydrolyzate thereof and the condensate thereof are used in combination of two or more kinds having different alkoxy groups Way.