JPH09176322A - Isocyanate group-containing polysilsesquioxane, its production and resin modifying agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new isocyanate group-containing polysilsesquioxane excellent in solubility in a wide variety of solvents, capable of giving excellent characteristics of a polyorganosiloxane such as low frictional properties to various resins and useful as a coating modifying agent by reacting a specific polysilsesquioxane with a diisocyanate-based compound. SOLUTION: In this isocyanate group-containing polysilsesquioxane, a side chain organic group consists of one or more groups selected from among an alkyl, alkenyl, aralkyl, etc., and an isocyanate-based group of formula I (R<1> and R<2> are each an alkylene; X<1> is a single bond or an ester bond or the like; X<2> is a single bond or a urethane bond; R<3> is a single bond or an alkylene), a terminal group of the main chain is a trialkyl and the number average molecular weight is 500-100,000. The objective polymer is obtained by reacting the side chain organic group with a hydroxyl group-containing polysilsesquioxane of formula II and an isocyanate-based compound (preferably, isophorone diisocyanate).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an isocyanate group-containing polysilsesquioxane, a method for producing the same, and a resin modifier, and more specifically, a polysil having an isocyanate group in its side chain, which is suitable as a polymer modifying material or an additive material. The present invention relates to a polysilsesquioxane (polyorganosiloxane) having a sesquioxane structure as a main structural unit, a method for producing the same, and a resin modifier comprising the polymer.

[0002]

2. Description of the Related Art Since polyorganosiloxane is excellent in water resistance, weather resistance, water repellency, etc., it has hitherto been possible to use a polyorganosiloxane having a reactive isocyanate group as a modifier for various resins. Attempts have been made to obtain a resin (composition) to which the characteristics of this polyorganosiloxane are imparted.

For example, in JP-A-63-161013, an isocyanate group-containing modified polyorganosiloxane is used as a modifier for a resin containing active hydrogen which reacts with the isocyanate group in the polyorganosiloxane. It is described that properties such as low friction, water repellency and oil repellency can be imparted to the resin.

Japanese Patent Laid-Open No. 5-320578 discloses that
It is described that a coating film having improved stain resistance and chemical resistance can be obtained by using a coating composition containing a polyorganosiloxane having an isocyanate group.

However, the polyorganosiloxanes described in these publications are all polymers having polydimethylsiloxane as a main skeleton. Such a polyorganosiloxane having a main skeleton of polydimethylsiloxane has low solubility in a solvent and is soluble only in a limited solvent such as hexane or chloroform.

Therefore, even if the above-mentioned polyorganosiloxane having an isocyanate group is mixed with a general resin composition to be modified containing various solvents, it is often dispersed uniformly in the solvent system. However, even if the above-mentioned polyorganosiloxane having an isocyanate group is added to the paint, the solution undergoes phase separation and "repellency" occurs in the resulting coating film, making it suitable for a wide variety of paints. On the other hand, there is a problem that it cannot be used as an additive. In addition, since polyorganosiloxane having a polydimethylsiloxane skeleton has low solubility in a solvent, it can be added to various resins even in an extremely small amount, and therefore has properties such as low friction, water repellency, and oil repellency. There is a problem that it is difficult to obtain the applied resin (composition).

[0007]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and is excellent in solubility in a wide variety of solvents and added to various resins. It is an object of the present invention to provide an isocyanate group-containing polysilsesquioxane capable of imparting various resins with excellent properties of polyorganosiloxane such as low friction, water repellency, and oil repellency.

[0008]

SUMMARY OF THE INVENTION In the isocyanate group-containing polysilsesquioxane according to the present invention, (i) the side chain organic group is at least one selected from an alkyl group, an alkenyl group, an aralkyl group and a substituted or unsubstituted phenyl group. Consisting of at least one group and an isocyanate group represented by the following formula [I], (ii) the main chain terminal group is trialkylsilylated, and (iii) the number average molecular weight is 500 to 100,000. Is characterized by.

-R ¹ -X ¹ -R ² -X ² -R ³ -NCO ... [I] {In the formula [I], R ¹ may have a substituent, Represents an alkylene group which may contain O and S atoms (eg, —C ₃ H ₆ —S—CH ₂ CH (CH ₃ ) —), preferably about 1 to 10 carbon atoms, and particularly 2 carbon atoms. ~ 8 is an alkylene group containing a thioether bond, R ² represents an alkylene group which may have a substituent and may contain O or S of a hetero atom, or a single bond, preferably carbon. An alkylene group of about 1 to 10 or a single bond is shown, and X ¹ is any ^one of a single bond, an ester bond, a sulfide bond, an amide bond, a urethane bond, a urea bond, a thiourethane bond, an ether bond and a carbonyl bond. , Preferably an ester bond (-COO- or -OCO
-) Or a carbonyl bond (-C (O)-), X
² represents a single bond or a urethane bond, R ³ represents a single bond, an alkylene group, a cycloalkylene group, a phenylene group, or a group consisting of any two or more of these groups (excluding a single bond). Any of these is shown, and these groups may have a substituent and may contain O or S as a hetero atom. In the method for producing an isocyanate group-containing polysilsesquioxane according to the present invention, the side chain organic group is at least one group selected from an alkyl group, an alkenyl group, an aralkyl group, and a substituted or unsubstituted phenyl group. And a hydroxyl group-containing group represented by the following formula [II], the main chain terminal group is trialkylsilylated, and a hydroxyl group-containing polysilsesquioxane having a number average molecular weight of 500 to 100,000 and diisocyanate. It is characterized by reacting with a system compound.

-R ¹ -X ¹ -R ² -OH ... [II] (In the formula [II], R ¹ may have a substituent, and the heteroatoms O and S may be substituted. Represents an alkylene group which may be contained, R ² represents an alkylene group which may have a substituent and may contain O or S of a hetero atom or a single bond, and X ¹ represents a single bond. Bond, ester bond, sulfide bond, amide bond, urethane bond, urea bond, thiourethane bond, ether bond, or carbonyl bond.) In the present invention, the diisocyanate compound is
It is preferably isophorone diisocyanate.

In the method for producing an isocyanate group-containing polysilsesquioxane according to the present invention, the side chain organic group is at least one selected from an alkyl group, an alkenyl group, an aralkyl group and a substituted or unsubstituted phenyl group. And a mercapto group-containing group represented by the following formula [III]: -R ¹ -SH ... [III] (in the formula [III], R ¹ represents an alkylene group). The main chain end group is trialkylsilylated, and the number average molecular weight is 500.
It is characterized in that a mercapto group-containing polysilsesquioxane having a molecular weight of ˜100,000 is reacted with an α, β-ethylenically unsaturated group-containing isocyanate compound represented by the following formula [IV].

[0012]

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(In the formula [IV], R ⁴ represents hydrogen or a methyl group, Y represents a single bond,

[0014]

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Represents a substituted or unsubstituted phenylene group, and R ⁵ represents an alkylene group. ) In the present invention, α, β-represented by the above formula [IV]
The ethylenically unsaturated group-containing isocyanate compound is 2
-Isocyanate Ethyl methacrylate or methacryloyl isocyanate is preferred.

The above-mentioned isocyanate group-containing polysilsesquioxane according to the present invention is an acrylic type having a functional group capable of reacting with an isocyanate group (eg, hydroxyl group, amino group, phenolic hydroxyl group, carboxylic acid, mercapto group, etc.). The resin 10 as a modifier for various resins such as resins, polyester resins, polyamide resins, and phenol resins.
It can be used in an amount of about 0.001 to 50 parts by weight with respect to 0 parts by weight, and in that case, a wide variety of solvents inert to such functional groups can be used.

The isocyanate group-containing polysilsesquioxane according to the present invention has excellent solubility in a wide variety of solvents, and when added to various resins, it has low friction properties, water repellency, and
The excellent properties of polyorganosiloxane such as oil repellency can be imparted to various resins.

[0018]

DETAILED DESCRIPTION OF THE INVENTION The isocyanate group-containing polysilsesquioxane and the method for producing the same according to the present invention will be specifically described below.

[Isocyanate Group-Containing Polysilsesquio ]
Xan] The isocyanate group-containing polysilsesquioxane according to the present invention has, for example, a structure represented by the following formula (A), wherein R ^m and R ⁿ are side chain organic groups,
-O-R ^q , -O-R ^r , -O-R ^s , -O-R ^t are terminal groups of the main chain, and p is a repeating unit.

[0020]

[Chemical 6]

In the isocyanate group-containing polysilsesquioxane according to the present invention, this (ii) main chain terminal group (in the formula (A), —O—R ^q , —O—R ^r , —O—R ^s , -O-R ^t ) is trialkylsilylated to give a trialkylsilyloxy group (-O-
SiR ¹ R ² R ³ : R ¹ , R ² and R ³ are the same or different alkyl groups. ).

Further, (i) a side chain organic group (in the formula (A), R ^m ,
A plurality of R ⁿ ) are present in the isocyanate group-containing polysilsesquioxane, and these side chain organic groups include
Each selected from an alkyl group, an alkenyl group, an aralkyl group, and a substituted or unsubstituted phenyl group
Both (a) and (b) comprising an isocyanate group represented by the following formula [I] ((a) (b)) are present.
Such an isocyanate group [I] is usually contained in the isocyanate group-containing polysilsesquioxane in an amount of 0.001 to 100%, preferably 1% of the total number of side chain organic groups.
It is preferably present in an amount of -20%. [I]: -R ¹ -X ¹ -R ² -X ² -R ³ -NCO ... [I] In the formula [I], R ¹ represents an alkylene group, and the alkylene group is a substituent. May be included, and O and S of heteroatoms may be included as an ether bond and a thioether bond, respectively. For example, a chain-like, branched, or cyclic alkylene group having about 1 to 10 carbon atoms, a thioether, etc. Bond-containing alkylene group [Example: "-C ₃ H ₆ -S-CH ₂ CH (CH
₃ )-"and the like, in which two alkylene chains" -C ₃ H _6- "and" -CH ₂ CH (CH ₃ )-"are bonded via a thioether bond], containing an ether bond And an alkylene group [eg: one in which two alkylene chains are bonded via an ether bond such as "-C ₃ H ₆ -O-CH ₂ CH (CH ₃ )-"] and the like are preferred. Examples thereof include thioether bond-containing alkylene groups, particularly thioether bond-containing alkylene groups having about 2 to 8 carbon atoms.

R ² may have a substituent (eg, an alkyl group having about 1 to 3 carbon atoms, etc.), and may contain O or S as a hetero atom. ,
Alternatively, it represents a single bond, and preferably has 1 to 1 carbon atoms.
It is preferably about 0 alkylene group or a single bond.

X ¹ is a single bond, ester bond, sulfide bond, amide bond, urethane bond, urea bond, thiourethane bond, ether bond, carbonyl bond [-C
(O)-], preferably an ester bond or a carbonyl bond.

X ² represents a single bond or a urethane bond. R ³ is a single bond, an alkylene group similar to the above,
A cycloalkylene group, a phenylene group, or a group consisting of any two or more of these groups (excluding a single bond) (eg, aromatic hydrocarbon group-containing alkylene group, cycloalkylene group-containing chain alkylene group) Either of them may be substituted, and the hetero atom may contain O or S.

Of such isocyanate group [I], it is preferable that R ¹ is a thioether bond-containing alkylene group having 1 to 10 carbon atoms, and X ¹ is an ester bond or a carbonyl bond. The following are preferable examples.

[0027]

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[0028]

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[0029]

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The number average molecular weight of the isocyanate group-containing polysilsesquioxane according to the present invention is 500.
１００100,000. Such an isocyanate group-containing polysilsesquioxane according to the present invention has excellent solubility in a wide variety of solvents and has low friction, water repellency, and oil repellency when added as a resin modifier to various resins. The excellent properties of polyorganosiloxane can be imparted to various resins.

As such various modifiable resins,
Generally, there is no particular limitation as long as it is a resin having a functional group capable of reacting with an isocyanate group in the isocyanate group-containing polysilsesquioxane according to the present invention, for example, a hydroxyl group which is a functional group capable of reacting with the isocyanate group. Examples include acrylic resins, polyester resins, polyamide resins, and phenol resins having functional groups such as amino groups, phenolic hydroxyl groups, carboxyl groups, and mercapto groups. The isocyanate group-containing polysilsesquioxane is usually used in an amount of about 0.5 to 1.5 times the equivalent of the functional group equivalent of these resins (in other words, 0. 001 to 50 parts by weight).

The solvent used when mixing the above-mentioned isocyanate group-containing polysilsesquioxane with the above various resins dissolves the above resin and does not react with the isocyanate group of the isocyanate group-containing polysilsesquioxane. You can choose an (inert) solvent.

Specific examples of such a solvent include heptane, diethyl ether, cyclopentane,
Cyclohexane, propyl chloride, carbon tetrachloride, diethyl sulfide, ethyl acetate, ethyl bromide, xylene, toluene,
Chloroform, tetrahydrofuran, methyl acetate, benzene, tetracleethylene, acetone, dichloromethane, chlorobenzene, dichloroethane, methyl benzoate, dioxane, methyl iodide, bromobenzene, carbon disulfide, benzonitrile, nitromethane, nitrobenzene, N, N -Dimethylformamide, acetonitrile,
Examples thereof include dimethyl sulfoxide and propylene carbonate. There is no particular limitation on the amount of such a solvent to be blended with the resin or the isocyanate group-containing polysilsesquioxane.

[Isocyanate Group-Containing Polysilsesquio ]
Production of Xane] Such an isocyanate group-containing polysilsesquioxane according to the present invention can be preferably produced by, for example, the following first or second method. [First Method] In the first method, an isocyanate group-containing polysilsesquioxane is produced by reacting a specific hydroxyl group-containing polysilsesquioxane as described below with a diisocyanate compound. There is.

In this hydroxyl group-containing polysilsesquioxane, the side chain organic group is at least one group selected from an alkyl group, an alkenyl group, an aralkyl group and a substituted or unsubstituted phenyl group, and the following formula [ II] and a hydroxyl group-containing group, the main chain terminal group is trialkylsilylated, and the number average molecular weight is 500 to 10
0000. [II]: -R ¹ -X ¹ -R ² -OH ... [II] (In the formula [II], R ¹ may have a substituent, and is a heteroatom O, S. Represents an alkylene group which may contain, R ² represents an alkylene group which may have a substituent, and which may contain a heteroatom O or S, or a single bond, and X ¹ represents Indicates a single bond, an ester bond, a sulfide bond, an amide bond, a urethane bond, a urea bond, a thiourethane bond, an ether bond, or a carbonyl bond.) In the production of such an isocyanate group-containing polysilsesquioxane The hydroxyl group-containing polysilsesquioxane used is first a reaction between a non-trialkylmercapto group-containing polysilsesquioxane as described below and a trialkylsilylating agent, and then the obtained mercapto group-containing polysilsesquioxane. It can be obtained by reacting an oxane with an α, β-ethylenically unsaturated group-containing alcoholic compound. First, the hydroxyl group-containing polysilsesquioxy compound used in the preparation of the isocyanate group-containing polysilsesquioxane is first described. The sun will be described along with the preparation process. <Mercapto Group-Containing Polysilsesquioxane> In the mercapto group-containing polysilsesquioxane, the side chain organic group is at least selected from an alkyl group, an alkenyl group, an aralkyl group, and a substituted or unsubstituted phenyl group. It comprises at least one group and a mercapto group-containing group represented by the following formula [III], and has a number average molecular weight of 500 to 1
00000 and the main chain end group is prepared by preparing a mercapto group-containing polysilsesquioxane in which the main chain end group is not trialkylsilylated, and the mercapto group-containing polysilsesquioxane in which the trialkylsilylation is not carried out, and Obtained by reacting with a trialkylsilylating agent. [III]: -R ¹ -SH ... [III] (In the formula [III], R ¹ represents an alkylene group.) <Containing a mercapto group which is not trialkylsilylated
Polysilsesquioxane> trialkylsilicide-containing mercapto group-containing polysilsesquioxane is a mercapto group-containing trialkoxysilane and / or trichlorosilane, and an alkyl group, an alkenyl group, an aralkyl group, or a substituted or unsubstituted group. It can be produced by hydrolysis condensation with trialkoxysilane and / or trichlorosilane having a phenyl group.

Specific examples of the trialkoxysilane and / or trichlorosilane having a mercapto group include, for example, mercaptopropyltrimethoxysilane,
Examples thereof include mercaptopropyltriethoxysilane, mercaptopropyltrichlorosilane, and mercaptobutyltrichlorosilane.

Specific examples of the trialkoxysilane and / or trichlorosilane having an alkyl group, an alkenyl group, an aralkyl group, and a substituted or unsubstituted phenyl group include, for example, methyltrimethoxysilane,
Methyltriethoxysilane, methylethoxydimethoxysilane, methyldiethoxymethoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethylethoxydimethoxysilane, ethyldiethoxymethoxysilane, ethyltrichlorosilane, propyltrimethoxysilane, Propyltriethoxysilane, propylethoxydimethoxysilane, propyldiethoxymethoxysilane, propyltrichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, butylethoxydimethoxysilane, butyldiethoxymethoxysilane, butyltrichlorosilane, phenyltrimethoxysilane, Phenyltriethoxysilane,
Examples thereof include phenylethoxydimethoxysilane, phenyldiethoxymethoxysilane and phenyltrichlorosilane. Among these, mercaptopropyltrimethoxysilane, methyltriethoxysilane and phenyltrimethoxysilane are preferably used.

The water for the hydrolytic condensation is generally used in an amount of 2 to 4 times the molar amount of 1 mol of the polysilsesquioxane-producing monomer selected from trialkoxysilane and / or trichlorosilane. . If the amount of water is less than 2 times the molar amount, the rate of the hydrolytic condensation reaction will be slow and it will take a long time to complete the reaction, or the reaction will be insufficient and gelation will tend to occur. Further, even if the amount of water exceeds 4 times the mole, the reaction completion time is not shortened any more.

As the catalyst for hydrolysis and condensation, when trialkoxysilane is used as a reaction raw material as described above, an acid catalyst is generally used, for example, inorganic acid, organic acid and / or a combination thereof is selected. However, since the higher the acid strength, the shorter the condensation reaction time, an acid having a high acid strength is generally used.

Specific examples of the inorganic acid include hydrochloric acid, sulfuric acid and nitric acid, and the organic acid includes formic acid and
Examples thereof include acetic anhydride and acetic acid. Also, as a reaction raw material,
When trichlorosilane is used, it is not necessary to add a catalyst to carry out the hydrolytic condensation, since the hydrochloric acid produced during the hydrolysis of the trichlorosilane has a hydrolytic condensation catalytic action.

Such an acid catalyst is generally used in an amount of 0.1 mol per mol of the trialkoxysilane (total).
The amount is 005 to 0.05 times, and more preferably 0.005.
007 to 0.04 times the molar amount, particularly preferably 0.0
It is used in an amount of 1 to 0.03 times the molar amount. If the amount of this acid catalyst is less than 0.005 times the molar amount of 1 mole of trialkoxysilane, the hydrolysis-condensation reaction will not be carried out quickly, and the alcohol by-produced by the condensation reaction will be the silylation reaction rate of polysilsesquioxane. Tends to decrease.
Further, if the amount of this acid catalyst exceeds 0.05 times mol with respect to 1 mol of trialkoxysilane, the reaction tends to be too fast, and it tends to be difficult to control the molecular weight within a desired range.

The temperature condition for such a hydrolysis condensation reaction is not particularly limited and may be appropriately selected. The heat of reaction generated during the reaction, the desired silsesquioxane structure formed (constructed) by the reaction, etc. In consideration of the above, as the reaction initiation temperature, a low temperature of −20 to + 50 ° C. is desirable, and further considering the shortening of the reaction time and the construction of the desired silsesquioxane structure, further −10 to + 30 ° C. It is particularly preferably -5 to + 15 ° C. With the generation of reaction heat due to the hydrolysis condensation reaction, the solution changes from a state in which it is separated into two layers to a homogeneous solution, and the solution temperature is usually 30 to 50 lower than the reaction start temperature (eg, a low temperature of -20 to + 50 ° C).
Although it rises by about ℃, if the solution temperature is continuously cooled, the solution temperature will gradually drop to the above-specified temperature.
To proceed the condensation reaction further, the solution temperature is usually 20 to 1
00 ° C, preferably 30 to 95 ° C, more preferably 5
It is desirable to keep the temperature at 0 to 90 ° C. to continue the reaction. Performing the reaction at such a temperature can shorten the reaction time,
Moreover, it tends to form a desired silsesquioxane structure. <Trialkylsilylating agent> The trialkylsilylating agent does not contain halosilane and is not easily affected by the excess amount of water required for the hydrolysis, or the trialkylsilylating agent itself is hydrolyzed under an acidic atmosphere. What is decomposed to become a silylating agent is used.

As such a trialkylsilylating agent (also referred to as a silylating agent), the following formula (i):

[0044]

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(In the formula (i), R ^a , R ^b and R ^c have 1 carbon atoms.
The above-mentioned unsubstituted or substituted hydrocarbon groups are shown, and these may be the same or different. A is
Shows a hydroxyl group or a hydrolyzable group. )) Are preferred.

The hydrolyzable group A in the formula (i) means a group which is hydrolyzed with excess water required for hydrolytically condensing the above-mentioned monomer. Is, for example, hydrogen, mercapto group, halogen, hydroxy group, vinyl group, amino group, glycidyl group, carboxyl group, unsubstituted or substituted hydrocarbon group-containing oxy group (eg: aralkyloxy group, aryloxy group). Group), an amino group, an unsubstituted or substituted hydrocarbon group-containing carbonyloxy group, or the following formula (ii): (ii):

[0047]

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(In the formula (ii), R ^e , R ^f and R ^g represent an unsubstituted or substituted hydrocarbon group having 1 or more carbon atoms, which may be the same or different from each other. Good.
B represents an ether oxygen or an amino group. And the like.

Specific examples of such a trialkylsilylating agent include the following compounds. That is, trimethylsilanol, methoxytrimethylsilane, 2-chloroethoxytrimethylsilane, chloromethyldimethylethoxysilane, ethoxytrimethylsilane, 2-propynyloxytrimethylsilane, dimethylethoxyethynylsilane, 1-chloromethyl-2.
-Chloroethoxytrimethylsilane, allyloxytrimethylsilane, ethoxydimethylvinylsilane, isopropeneoxytrimethylsilane, 3-chloropropyltrimethylsilane, allyloxydimethylvinylsilane,
1-chloromethylethoxydimethylvinylsilane, te
rt-butoxytrimethylsilane, 1-methylpropyloxytrimethylsilane, isobutoxytrimethylsilane, butoxytrimethylsilane, 3-aminopropyldimethylethoxysilane, furfuryloxytrimethylsilane, trimethylpentyloxysilane, isopentyloxytrimethylsilane, 2, 4-dichlorophenyloxytrimethylsilane, chloromethyldimethylphenoxysilane, 2-chlorophenoxytrimethylsilane, 4
-Nitrophenoxytrimethylsilane, hydroxyphenoxytrimethylsilane, dimethylfurfuryloxyvinylsilane, 2-hydroxyphenoxytrimethylsilane, 1-chlorohexenyloxytrimethylsilane, cyclohexyloxytrimethylsilane, hexyloxytrimethylsilane, butyl-2-hydroxyethylthiomethyl Dimethylsilane, dimethylethynyl-2,4,5
-Trichlorophenoxysilane, 2,4-dichlorophenoxyethynyldimethylsilane, trimethylsilylbenzoate, benzyloxychloromethyldimethylsilane, 3-aminophenoxydimethylvinylsilane, dimethylethoxy-3-glycidoxypropylsilane, dimethyl-2-[(2 -Ethoxyethoxy) ethoxy] vinylsilane, methoxytripropylsilane, dimethyl-3
-Methyl-4-chlorophenoxyvinylsilane, dimethyl-2-methyl-4-chlorophenoxyvinylsilane,
Chloromethyldimethyl-2-phenylethoxysilane,
Benzyldimethylethoxysilane, dimethyl-2-piperidinoethoxyvinylsilane, 2-ethylhexyloxytrimethylsilane, octyltrimethylsilane, triethylsilylbenzoate, benzylidene-3-ethoxydimethylsilylpropylamine, diphenylethoxymethylsilane, dodecyloxytrimethylsilane, Diphenylethoxyvinylsilane, acetyltriphenylsilane, ethoxytriphenylsilane, triphenylsilanol, trimethylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol,
Pentamethyldisiloxane, 1,3-diethynyl-1,
1,3,3-tetramethyldisiloxane, N, O-Bi
s (trimethylsilyl) trifluoroacetamide,
1,3-divinyl 1,1,3,3-tetramethyldisiloxane, Bis (trimethylsilyl) uracil, Bis
(Trimethylsilyl) tyrosine, 1,3-Bis (acetoxymethyl) tetramethyldisiloxane, 1- (N,
N-dimethylthiocarbamoylthiomethyl) -1,1,
3,3-tetramethyl-3-vinyldisiloxane, 1,
3-Bis (3-chloropropyl) tetramethyldisiloxane, 1,3-Bis (3-mercaptopropyl) tetramethyldisiloxane, 1,3-Bis (3-hydroxypropyl) -1,1,3,3- Tetramethyldisiloxane, 1,3-Bis (3-aminopropyl) tetramethyldisiloxane, 1,3-Bis (2-aminoethylaminomethyl) -1,1,3,3-tetramethyldisiloxane, 3- Methylpiperidinomethylpentamethyldisiloxane, 4-methylpiperidinomethylpentamethyldisiloxane, hexaethyldisiloxane, 1,3-dibutyl-1,1,3,3-tetramethyldisiloxane,
1- (2-methylpiperidinomethyl) -1,1,3,3
-Tetramethyl-3-vinyldisiloxane, 1- (3-
Methylpiperidinomethyl) -1,1,3,3-tetramethyl-3-vinyldisiloxane, pentamethyl-3-piperidinopropyldisiloxane, 1,3-Bis (3-
Acetoxypropyl) tetramethyldisiloxane, 1,
3-Bis [3- (N-methylcarbamoyloxypropyl) tetramethyldisiloxane, 3- (4-methylpiperidinopropyl) pentamethyldisiloxane, 3-
(2-Methylpiperidinopropyl) pentamethyldisiloxane, 1,3-diphenyl-1,1,3,3-tetramethyldisiloxane, 1,3-Bis (dioxyanylethyl) -1,1,3 , 3-Tetramethyldisiloxane, 1,3-Bis (3-glycidoxypropyl)-
1,1,3,3-tetramethyldisiloxane, hexapropyldisiloxane, 1,3-dimethyl-1,1,3
3-tetraphenyldisiloxane, 1,1,3,3-tetraphenyl-1,3-divinylsiloxane, allyldimethylsilane, diethylmethylsilane, triethylsilane, butyldimethylsilane, dimethylphenylsilane,
Methylphenylvinylsilane, tripropylsilane, diphenylmethylsilane, triphenylsilane, 1-piperidinomethyl-1,1,3,3-tetramethyl-3-vinyldisiloxane, 1,3-divinyl-1,1,3,3
-Tetramethyldisilazane, pentamethylpiperidinomethyldisiloxane, 4-trimethylsiloxyphenyltrimethylsilane, hexamethyldisiloxane, 3- (3
-Methylpiperidinopropyl) pentamethyldisiloxane and the like.

Among such trialkylsilylating agents, hexaethyldisiloxane and hexamethyldisiloxane are preferably used. <Mercapto group-containing polysilsesquioxane> The non-trialkylsilylated mercapto group-containing polysilsesquioxane obtained as described above is reacted with a trialkylsilylating agent (terminal blocking agent). And a mercapto group-containing polysilsesquioxane is obtained,
Such a reaction is carried out by adding a trialkylsilylating agent to the non-trialkylsilylated mercapto group-containing polysilsesquioxane solution obtained as described above.

This trialkylsilylating agent (eg, hexamethyldisiloxane) is usually used in an amount of about 1.2 to 5 times with respect to one terminal silanol group. Further, such a trialkylsilylation reaction is carried out at the same temperature as above, that is, usually 20 to 100 ° C., preferably 30 to
It is carried out at 95 ° C, more preferably 50 to 90 ° C.
In order to stop such a reaction, for example, a methanol solution of potassium hydroxide is used.

The mercapto group-containing polysilsesquioxane thus obtained (that is, the side chain organic group is at least one selected from an alkyl group, an alkenyl group, an aralkyl group, and a substituted or unsubstituted phenyl group) The above-mentioned group and the mercapto group-containing group represented by the above formula [III], and the main chain terminal group is trialkylsilylated, the trialkylsilylated mercapto group-containing polysilsesquioxane) has a number average of Molecular weight is 500-10
It is 0000. If the number average molecular weight is less than 500, the properties as a silicone (water resistance, weather resistance, water repellency, etc.) are poor, and if the number average molecular weight is more than 100,000, the viscosity becomes too high and it becomes difficult to handle, and the obtained isocyanate The processability of the group-containing polysilsesquioxane tends to decrease.

[Preparation of hydroxyl-containing polysilsesquioxane
Production] In the present invention, a mercapto group-containing polysilsesquioxane obtained as described above and an α, β-ethylenically unsaturated group-containing alcoholic compound as described below are usually used as a catalyst (polymerization). A hydroxyl group-containing polysilsesquioxane is prepared by reacting (mercaptulation) in the presence of an initiator) and a solvent. This reaction is a reaction in which the mercapto group of the mercapto group-containing polysilsesquioxane is added to the ethylenically unsaturated group of the α, β-ethylenically unsaturated group-containing alcoholic compound (mercaptulation), which is the so-called sulfide. It is a reaction that forms a bond.

Specific examples of the α, β-ethylenically unsaturated group-containing alcoholic compound include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, and 3-hydroxypropyl methacrylate.
-Hydroxypropyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, glycerol monomethacrylate, 2-hydroxy-3-phenoxypropyl acrylate, polyethylene glycol monomethacrylate (ex: NOF Corporation Blemmer PE series, PE- 90, PE-200,
PE-350), polypropylene glycol monomethacrylate (Example: Bremmer PP series manufactured by NOF CORPORATION, PP-1000, PE-500, PE-800),
Polyethylene glycol polypropylene glycol monomethacrylate (Example: Bremmer PE manufactured by NOF CORPORATION)
P series, 70PEP-370B), polyethylene glycol polytetramethylene glycol monomethacrylate (Example: Bremmer 55PET-8 manufactured by NOF CORPORATION)
00), polypropylene glycol polytetramethylene glycol monomethacrylate (Example: Bremmer NKH-5050 manufactured by NOF Corporation), polypropylene glycol monoacrylate (Example: Bremmer AP-400 manufactured by NOF Corporation), polyethylene glycol monoacrylate ( Example: Bremmer AE-35 manufactured by NOF CORPORATION
0) and the like. Among such α, β-ethylenically unsaturated group-containing alcoholic compounds, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate and the like are preferably used.

As the catalyst used in the reaction (mercaptulation) of such an α, β-ethylenically unsaturated group-containing alcoholic compound with the mercapto group-containing polysilsesquioxane, sulfuric acid, tritium Examples include fluoroboron, azo-based polymerization initiators, peroxide-based polymerization initiators, amines and the like. To carry out such a reaction under mild conditions, an azo-based polymerization initiator or a peroxide-based polymerization reaction may be used. An initiator is preferably used.

Specific examples of the azo-based polymerization initiator include:
For example, 2,2′-azobis (isobutylnitrile),
2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2-cyano-2-propylazo-formamide, dimethyl 2,2'-azobis (2-methylpropionate), 2,2 Examples thereof include'-azobis (2-hydroxymethylpropionitrile) and dimethyl 2,2'-azobisisobutyrate. Specific examples of the peroxide-based polymerization initiator include isobutyl peroxide and 2,4- Examples thereof include dichlorobenzoyl peroxide, benzoyl peroxide, t-butyl peroxide, t-butyl cumyl peroxide, t-butyl hydroperoxide and lauroyl peroxide.

In the present invention, one or two of these may be used.
It can be used in combination of more than one kind. There is no particular limitation on the concentration of the catalyst used when performing such a mercaption reaction, but in view of the convenience of the treatment after the reaction, ensuring the mild conditions of the reaction, etc., the above catalyst is
Usually, it is 0.01 to 0.01 with respect to lauroyl peroxide.
It is desirable to use in an amount of 20% by weight, preferably 0.05 to 10% by weight.

The reaction temperature varies depending on the type of catalyst and is not generally determined, but when sulfuric acid or trifluoroboron is used, it is generally 0 to 150 ° C, preferably 30 to 120 ° C.

When an azo type polymerization reaction initiator or a peroxide type polymerization reaction initiator is used as a catalyst, it is not particularly limited as long as it can maintain a temperature sufficient for the polymerization reaction initiator to be cleaved by heat.

A mercapto group which is a functional group in the reaction system,
The proportion of the hydroxyl group in the α, β-ethylenically unsaturated group-containing alcoholic compound is α, more than the mercapto group content when the α, β-ethylenically unsaturated group-containing alcoholic compound is added to the mercapto group. When the number of moles of the alcohol compound having a β-ethylenically unsaturated group (α, β-ethylenically unsaturated group-containing alcoholic compound) is larger,
Excessive α and β after completion of mercaption reaction
-Since the ethylenically unsaturated group-containing alcoholic compounds may be polymerized with each other, a mercapto group and α, β-
Ethylenically unsaturated group-containing alcoholic compound means an amount of about 0.95 to 1.05 mol (eg, 1 mol) of α, β-ethylenically unsaturated group-containing alcoholic compound with respect to 1 mol of mercapto group. Is preferably present.

The reaction solvent is not limited in kind as long as it is inert to the reaction system. However, the hydroxyl group-containing polysilsesquioxane obtained by the above reaction is reacted with a diisocyanate compound, In preparing the isocyanate group-containing polysilsesquioxane, it is desirable to select a solvent that does not react with the isocyanate group.

Specific examples of such a solvent include hydrocarbon solvents such as benzene, toluene, xylene and cyclohexane; ester solvents such as ethyl acetate, butyl acetate and amyl acetate; acetone, methyl ethyl ketone and methyl isobutyl. Examples thereof include ketone solvents such as ketone and cyclohexanone; ether solvents such as tetrahydrofuran and 1,4-dioxane.

[Isocyanate Group-Containing Polysilsesquio ]
Preparation of Xane] In the present invention, a hydroxyl group-containing polysilsesquioxane obtained as described above and a diisocyanate compound are usually reacted in the presence of a catalyst, a solvent and the like (urethane reaction) to give an isocyanate. A group-containing polysilsesquioxane is being prepared. In this reaction, the hydroxyl group in the hydroxyl group-containing polysilsesquioxane reacts with the isocyanate group of the diisocyanate compound to form a urethane bond.

The diisocyanate-based compound has 2 in the molecule.
A compound having two isocyanate groups, as such a diisocyanate-based compound, specifically, for example, tolylene diisocyanate, diphenylmethane diisocyanate, dianisidine diisocyanate, diphenyl ether diisocyanate, pytolylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, Examples thereof include isophorone diisocyanate, lysine diisocyanate methyl ester, metaxylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isopropylidene bis (4-cyclohexyl isocyanate), cyclohexylmethane diisocyanate dimer.

In the present invention, blocked isocyanates obtained by blocking (protecting) these isocyanate groups with alcohols, phenols, oximes, lactams and the like can also be used. Among these diisocyanate compounds, isophorone diisocyanate is preferably used from the viewpoint of high reactivity with hydroxyl group-containing polysilsesquioxane and the purity of the obtained isocyanate group-containing polysilsesquioxane (product).

As the catalyst, those generally used as catalysts for urethane reaction can be used. However, when the above-mentioned blocked isocyanate is used, it is not necessary to add it because a catalyst is not particularly required.

Specific examples of the catalyst include amine-based (eg, 1,4-diazabicyclo92,2,2) octane, PMDETA (compound name: N, N, N ', N ",
N "-pentamethyldiethylenetriamine), N, N-
Dimethylcyclohexylamine, N-methyldicyclohexylamine, N, N, N ', N'-tetramethyl 1,
3-butanediamine, N, N, N ', N'-tetramethylpropylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N-ethylmorpholine,
N-methylmorpholine, N, N-dimethylethanolamine, triethylamine), DBU system (eg 1,8-diaza-bicyclo [5,4,0] undecene-7 and its salts), metal system (eg Stannas) Octoate, dibutyltin dilaurate, trimethyltin hydroxide, dimethyltin dichloride, tin octate), as well as butadiene sulfonic acid, inorganic acid, oxy acid, phosphoric acid ester, boric acid ester, monobutyl phthalate, p-toluene sulfonic acid, etc. And preferably,
Metallic dibutyltin dilaurate or the like is used.

The catalyst concentration is determined by the activity of the catalyst used and is not generally determined. However, considering that the catalyst used remains in the reaction system, it is preferable to add it in the smallest possible amount. The reaction catalyst for the diisocyanate compound is usually 0.0
It is used in an amount of 1 to 20% by weight, preferably 0.05 to 10% by weight.

The reaction temperature for carrying out the urethanization reaction is not particularly limited, but it is desirable to carry out the reaction under heating in order to complete the reaction in a short time. Although the reaction temperature varies depending on the solvent used, it is usually 20 to 20.
The temperature is preferably 0 ° C, preferably 30 to 150 ° C.

When the diisocyanate-based compound is added to the hydroxyl group, the proportion of the hydroxyl group which is a functional group in the reaction system to the isocyanate group is such that one isocyanate group content in the diisocyanate-based compound is smaller than the hydroxyl group content. However, the residual hydroxyl group reacts with the isocyanate group not involved in the reaction to form a high molecular weight polymer, which is not preferable. When the content of one isocyanate group in the diisocyanate-based compound is higher than the content of the hydroxyl group, an excess amount of the diisocyanate-based compound is recovered by distilling with the solvent and can be reused. There is no particular reason for setting an upper limit,
Usually, the diisocyanate compound is used in an amount such that the equivalent number of one isocyanate group in the diisocyanate compound (compound having two isocyanates in the molecule) does not exceed 3 with respect to the equivalent number of hydroxyl groups.

The reaction solvent for carrying out the urethanization reaction is not particularly limited as long as it is inert to the reaction system, and it is usually the same as the catalyst used in the above mercaption reaction. Things are used. <Other Preparation Method of Hydroxyl Group-Containing Polysilsesquioxane > In the above description, the hydroxyl group-containing polysilsesquioxane is a mercapto group-containing polysilsesquioxane which is not trialkylsilylated, and a trialkylsilylating agent. The mercapto group-containing polysilsesquioxane obtained by the reaction of and the embodiment obtained by the mercaptation reaction of the α, β-ethylenically unsaturated group-containing alcoholic compound have been described. A hydroxyl group-containing polysilsesquioxane is disclosed in Japanese Patent Application No. 6-25119.
A vinyl group-containing polysilsesquioxane described in No. 6,
It can also be obtained by reacting with a hydroxyl group-containing mercaptan.

That is, in the vinyl group-containing polysilsesquioxane described in Japanese Patent Application No. 6-251196, 50 to 99.9 mol% of side chain organic groups are methyl groups, and 25 mol% is a vinyl group or an organic group having a vinyl group as a substituent, the balance is an alkyl group having 2 or more carbon atoms, a substituted or unsubstituted phenyl group, a number average molecular weight of 500 to 100,000, and a terminal It is also possible to obtain the above-mentioned hydroxyl group-containing polysilsesquioxane by subjecting a polysilsesquioxane, which is trialkylsilylated with a silylating agent, to a hydroxyl group-containing mercaptan.

The hydroxyl group-containing mercaptan is not particularly limited in its structure as long as it is a mercaptan having a hydroxyl group, and specific examples thereof include mercaptomethanol, mercaptoethanol, mercaptopropanol and mercaptobutanol.

The mercaptation reaction between the vinyl group-containing polysilsesquioxane and the hydroxyl group-containing mercaptan is carried out by the mercapto group-containing polysilsesquioxane and the α, β-ethylenically unsaturated group-containing alcoholic compound. It is carried out under the same conditions as the mercaptylation reaction with the compound. [Second Method] Next, a second method for producing an isocyanate group-containing polysilsesquioxane according to the present invention will be described.

In the second method, the mercapto group-containing polysilsesquioxane as described above is reacted with an α, β-ethylenically unsaturated group-containing isocyanate compound as described below to give an isocyanate group. The containing polysilsesquioxane is produced.

As described above, the mercapto group-containing polysilsesquioxane has a side chain organic group which is an alkyl group,
At least one or more groups selected from an alkenyl group, an aralkyl group, a substituted or unsubstituted phenyl group,
The following formula [III]: -R ¹ -SH ... [III] (in the formula [III], R ¹ represents an alkylene group) and a mercapto group-containing group, and a main chain terminal group. Is trialkylsilylated and has a number average molecular weight of 500
˜100,000 (100,000).

The α, β-ethylenically unsaturated group-containing isocyanate compound is represented by the following formula [IV]. [IV]:

[0078]

Embedded image

(In the formula [IV], R ⁴ represents hydrogen or a methyl group, Y represents a single bond,

[0080]

Embedded image

Represents a substituted or unsubstituted phenylene group, and R ⁵ represents an alkylene group. ) Specific examples of the α, β-ethylenically unsaturated group-containing isocyanate compound [IV] (isocyanate compound) include, for example, methacryloyl isocyanate, 2-isocyanate ethyl methacrylate, 2-isocyanate methyl methacrylate, 2 -Isocyanate ethyl acrylate, 2-isocyanate propyl methacrylate, 2-isocyanate propyl acrylate, 2-isocyanate octyl acrylate, p-isopropenyl-α, α-dimethylbenzyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, p -Ethylenyl-α, α-dimethylbenzyl isocyanate, vinyl isocyanate and the like can be mentioned.

Among such α, β-ethylenically unsaturated group-containing isocyanate compounds [IV], methacryloyl isocyanate and 2-isocyanate ethyl methacrylate are preferably used from the viewpoint of high reactivity with active hydrogen.

The isocyanate group-containing polysilsesquioxane is produced by subjecting such an α, β-ethylenically unsaturated group-containing isocyanate compound to the mercapto group-containing polysilsesquioxane. In this case, the same conditions (catalyst, amount of catalyst, reaction temperature, reaction solvent, etc.) as in the case of the mercaption reaction may be adopted.

The isocyanate group-containing polysilsesquioxane obtained by the above-mentioned first or second production method is, as described above, a functional group capable of reacting with an isocyanate group (eg, hydroxyl group, amino group, phenol). It can be used as a modifier for various resins such as acrylic resins, polyester resins, polyamide resins, phenolic resins, etc., which have a hydrophilic hydroxyl group, carboxylic acid, mercapto group, etc.) A wide variety of various solvents can be used.

[0085]

Industrial Applicability The isocyanate group-containing polysilsesquioxane according to the present invention is a novel reactive polymer having an isocyanate group, has excellent solubility in a wide variety of solvents, and should be added to various resins. Can give various resins the excellent properties of polyorganosiloxane such as low friction, water resistance, weather resistance, water repellency, and oil repellency, and are useful as paint modifiers, fiber modifiers, industrial resin additives, etc. is there.

[0086]

EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples.

[0087]

[Synthesis Example 1] < Synthesis of polysilsesquioxane having a mercapto group
> In a 300 cc flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a reflux condenser, 7.76 g (39.5 mmo) of 3-mercaptopropyltrimethoxysilane
l), 77.4 g of methyltriethoxysilane (434 m
mol), 2.42 g of phenyltrimethoxysilane (1
2.2 mmol) and 26.3 g of pure water (1460 mm)
ol) was charged and the temperature of the solution was kept at 5 ° C. with stirring under a nitrogen stream. 5% 10% aqueous hydrochloric acid with stirring
After g was added dropwise over 30 minutes, the solution temperature was kept at 10 ° C. for 1 hour. Next, after raising the temperature of the solution to 70 ° C. and reacting for 3 hours, 19.1 g of hexaethyldisiloxane (7
7.5 mmol) was added and stirring was continued at 70 ° C. for 3 hours. The solution temperature was lowered to 40 ° C., 5.5 g of a 5% potassium hydroxide solution in methanol was added, and the mixture was allowed to stand at room temperature for 1 hour.
Left for 2 hours. After extracting the lower layer portion and adding 80 g of butyl acetate, the mixture was concentrated with stirring at 40 ° C. under a reduced pressure of 200 mmHg, 80 g of the liquid was distilled off, and 170 g of butyl acetate was further added at normal pressure to give 1 Stir for a period of time. The obtained solution was filtered and then concentrated under reduced pressure to obtain 38.9 g of a colorless transparent viscous liquid. The number average molecular weight of the obtained liquid polymer A) was 3300 as measured by GPC.

When IR spectrum and Raman spectrum were measured, absorption based on mercapto group appeared at around 2560 cm ^-1 . The obtained polymer is called "polymer A".

[0089]

[Synthesis Example 2] < Synthesis of polysilsesquioxane having a hydroxyl group> 40.0 g of the mercapto obtained in Example 1 was placed in a 200 cc flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a reflux condenser. Group-containing polysilsesquioxane (Polymer A), 5.48 g of 2-hydroxyethyl methacrylate, 80 g of toluene and 0.68 g of lauroyl peroxide were charged, and the solution temperature was 50 ° C while stirring under a nitrogen stream. It was kept for 1 hour and reacted for 1 hour. The temperature was further raised, and stirring was continued at 60 ° C. for 1 hour and at 70 ° C. for 1 hour. After completion of the reaction, the mixture is cooled, the solvent is distilled off under reduced pressure,
Further, it was dried under reduced pressure for 8 hours to obtain 45.1 g of a viscous colorless transparent liquid (polymer B). The number average molecular weight of this product was 3,500 when measured by GPC. IR
2 of the methacrylic group around 1640 cm ^-1 from the spectrum
It was confirmed that the absorption due to the heavy bond disappeared. The obtained polymer is called "polymer B".

[0090]

[Synthesis Example 3] < Synthesis of polysilsesquioxane having a hydroxyl group> In a 300 cc flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a reflux condenser, 9.8 g of 3-methacryloxypropyltrimethoxysilane ( 39.5 mmol),
Methyltriethoxysilane 77.4g (434mmo
l), 2.42 g of phenyltrimethoxysilane (12.
2 mmol) and 26.3 g of pure water (1460 mmo)
1) was charged and the temperature of the solution was kept at 5 ° C. while stirring under a nitrogen stream. 5 g of 10% aqueous hydrochloric acid solution with stirring
Was added dropwise over 30 minutes, and the solution temperature was kept at 10 ° C. for 1 hour. Next, after raising the temperature of the solution to 70 ° C. and reacting for 3 hours, 19.1 g of hexaethyldisiloxane (77.
5 mmol) was added and stirring was continued at 70 ° C. for 3 hours. The solution temperature was lowered to 40 ° C., 5.5 g of a 5% potassium hydroxide methanol solution was added, and the mixture was allowed to stand at room temperature for 12 hours. After extracting the lower layer portion and adding 80 g of butyl acetate, the mixture was concentrated with stirring at 40 ° C. under a reduced pressure of 200 mmHg, 80 g of the liquid was distilled off, and 170 g of butyl acetate was further added at normal pressure to give 1 Stir for a period of time. The obtained solution was filtered and then concentrated under reduced pressure to obtain 38.0 g of a colorless transparent viscous liquid. The number average molecular weight of this liquid (polymer C-1) was 3200 as measured by GPC. As a result of measuring the IR spectrum of the polymer, absorption based on the double bond of the methacryl group appeared at around 1640 cm ^-1 . The polymer thus obtained is referred to as "Polymer C-1".

Further, in a 200 cc flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a reflux condenser, 3
8.0 g of the above-mentioned “polymer C-1”, 3.73 g of mercaptoethanol, 0.78 g of lauroyl peroxide and 41.7 g of toluene were charged, and the solution temperature was raised to 50 ° C. while stirring under a nitrogen stream. It was kept and reacted for 1 hour. The temperature was further raised, and stirring was continued at 60 ° C. for 1 hour and at 70 ° C. for 1 hour. After completion of the reaction, the mixture was cooled, the solvent was distilled off under reduced pressure, and further dried under reduced pressure for 8 hours.
1 g of a viscous colorless transparent liquid (polymer C-2) was obtained. When the number average molecular weight of this liquid was measured by GPC, it was 3300. 1640 cm ^-1 from IR spectrum
It was confirmed that the absorption due to the double bond of the methacrylic group in the vicinity disappeared, and the absorption due to the hydroxyl group near 3500 cm ⁻¹ appeared. The obtained polymer was designated as "Polymer C-
2 ".

[0092]

Example 1 <Synthesis of Polysilsesquioxane Having Isocyanate Group> 17.2 g of Synthesis Example 2 was obtained in a 200 cc flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. Hydroxyl-containing polysilsesquioxane (Polymer B), 4.79 g of isophorone diisocyanate, 8.6 mg of dibutyltin dilaurate and 6
6 g of toluene was charged and the solution temperature was kept at 60 ° C. for 3 hours while stirring under a nitrogen stream. After completion of the reaction, the mixture was cooled, the solvent was distilled off under reduced pressure, and further dried under reduced pressure for 8 hours to obtain a viscous colorless transparent liquid (Polymer D).
2.0 g was obtained. The number average molecular weight of this liquid was 3,800 as measured by GPC. 22 from IR spectrum
80cm absorption appears based on the isocyanate group near ^-1, in the vicinity of 1730 cm ^-1 and near 1530 cm ^-1 appeared absorption based on urethane bond.

The solubility of this polymer was examined. As a result, heptane, diethyl ether, cyclopentane, cyclohexane, propyl chloride, carbon tetrachloride, diethyl sulfide, ethyl acetate, ethyl bromide, xylene, toluene, chloroform, tetrahydro. Furan, methyl acetate, benzene, tetrachloroethylene, acetone, dichloromethane, chlorobenzene, dichloroethane, methyl benzoate, dioxane, methyl iodide, bromobenzene, carbon disulfide, benzonitrile, nitromethane, nitrobenzene, N, N-dimethylformamide, Acetonitrile,
It was soluble in solvents such as dimethyl sulfoxide and propylene carbonate. The obtained polymer is referred to as "Polymer D".
And

The amount of isocyanate in this polymer D was
When measured by titration with di-normal butylamine, it was found that the average per molecule was 8%.

[0095]

Example 2 <of polysilsesquioxane having isocyanate group
Synthesis> In a 200 cc flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 15.0 g of the polysilsesquioxane having a mercapto group (polymer A) obtained in Example 1 was used. 05 g 2-isocyanatoethyl methacrylate, 30 g toluene and 0.
16 g of lauroyl peroxide was charged, and the solution temperature was maintained at 50 ° C. with stirring under a nitrogen stream and the reaction was carried out for 1 hour. The temperature was further raised, and stirring was continued at 60 ° C. for 1 hour and at 70 ° C. for 1 hour. After completion of the reaction, the mixture was cooled, the solvent was distilled off under reduced pressure, and further dried under reduced pressure for 8 hours to obtain 16.7 g of a viscous colorless transparent liquid (Polymer E). When the number average molecular weight of this liquid was measured by GPC, it was 3500.
Met. Absorption based on the mercapto group disappears from the IR spectrum and Raman spectrum in the vicinity of 2560cm ^-1, absorption based on an isocyanate group appeared in the vicinity of 2280 cm ^-1.

Further, when the solubility of this polymer was examined, heptane, diethyl ether, cyclopentane, cyclohexane, propyl chloride, carbon tetrachloride, diethyl sulfide, ethyl acetate, ethyl bromide, xylene, toluene, chloroform, tetrahydrofuran. , Methyl acetate, benzene, tetrachloroethylene, acetone, dichloromethane, chlorobenzene, dichloroethane, methyl benzoate, dioxane, methyl iodide, bromobenzene, carbon disulfide, benzonitrile, nitromethane, nitrobenzene, N, N-dimethylformamide, acetonitrile ,
It was soluble in solvents such as dimethyl sulfoxide and propylene carbonate. The obtained polymer is referred to as "Polymer E".
And

The amount of isocyanate in this "polymer E" was measured by titration using di-normal butylamine, and it was found that the average per molecule was 8%.

[0098]

Example 3 <of polysilsesquioxane having isocyanate group
Synthesis> The same reaction as in Example 2 was carried out except that 1.68 g of methacryloyl isocyanate was used instead of the 2-isocyanate ethyl methacrylate used in Example 2, to obtain a viscous colorless transparent liquid (polymer F). 16.5 g was obtained. The number average molecular weight of this polymer is determined by GPC
It was 3400 when measured by. Absorption based on the mercapto group disappears from the IR spectrum and Raman spectrum in the vicinity of 2560cm ^-1, absorption based on an isocyanate group appeared in the vicinity of 2280 cm ^-1.

When the solubility of this polymer was examined, heptane, diethyl ether, cyclopentane, cyclohexane, propyl chloride, carbon tetrachloride, diethyl sulfide, ethyl acetate, ethyl bromide, xylene, toluene, chloroform, tetrahydrofuran were added. , Methyl acetate, benzene, tetrachloretin, acetone, dichloromethane,
Chlorobenzene, dichloroethane, methyl benzoate, dioxane, methyl iodide, bromobenzene, carbon disulfide, benzonitrile, nitromethane, nitrobenzene,
It was soluble in solvents such as N, N-dimethylformamide, acetonitrile, dimethylsulfoxide and propylene carbonate. The polymer thus obtained is referred to as "Polymer F".

The amount of isocyanate in this "Polymer F" was measured by titration with di-normal butylamine and found to be 8% on average per molecule.

[0101]

[Test Example 1] <Synthesis of acrylic polyol resin and evaluation of water repellency> In a 300 cc flask equipped with a thermometer, a stirrer, a nitrogen introduction tube and a reflux condenser, 33.7 g of 2-hydroxyethyl methacrylate, 17. 3 g of methyl methacrylate, 49.1 g of n-butyl methacrylate, 1
5.9 g 2-ethylhexyl acrylate, 2.18
g of acrylic acid and 2.44 g of dodecyl mercaptan were added, and the mixture was stirred under a nitrogen stream for 30 minutes. The solution thus prepared is called a "mixed monomer".

In a 300 cc flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a reflux condenser, 26.6 g was added.
55.0 g of butyl acetate were added, and the mixture was stirred for 30 minutes under a nitrogen stream at room temperature. Then, 12.4 g of a butyl acetate solution of 7.9% by weight of dimethyl 2,2′-azobisisobutyrate was added to the flask, the temperature was raised with stirring under a nitrogen stream, and the temperature was kept at 80 ° C. for 30 minutes. , And another 106 g of "mixed monomer" was added over 3 hours.
Again, 6.4 g of 7.9 wt% dimethyl 2,2'-azobisisobutyrate in butyl acetate was added to the flask, and 9
The reaction was continued at 0 ° C for 3 hours. Then, after cooling the flask contents to room temperature, 195 g of a colorless transparent solution was obtained. The weight average molecular weight of this solution (polymer) is 2500.
It was 0. The polymer thus obtained is called "acrylic polyol".

To 55 parts by weight of this acrylic polyol was added the polysilsesquioxane having an isocyanate group obtained in Examples 1 to 3 (polymers D to F).
1, 0.5, 1.0 and 3.0 parts by weight of polyfunctional aliphatic isocyanate compound (Sumijour N-35) was added.
00, 12 parts by weight of Sumitomo Bayer Urethane Co., Ltd. and 15 parts by weight of xylene were added and uniformly mixed to prepare a coating composition.

50 of these coating compositions were applied on a glass substrate.
When applied to a thickness of micron, a smooth coating film with no repellency visually observed was obtained.
Cured for 1 hour. When the contact angle (degree) with water of the obtained cured coating film was measured, the contact angle with water of the coating film to which the polymers D, E and F were added was as shown in Table 1. The contact angle of water on the surface of the coating film was measured using a contact angle meter CA-DT • A type manufactured by Kyowa Interface Science Co., Ltd.

[0105]

Comparative Example 1 A 200 cc flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser tube was charged with a carbinol-modified polydimethylsiloxane having one end and X-22-17.
OB (manufactured by Shin-Etsu Chemical Co., Ltd.) (120 g) and dibutyltin dilaurate (139 mg) were added, and the mixture was stirred at 15 ° C. Then, 9.2 g of isophorone diisocyanate was added to 2
After slowly adding to the flask over 0 minutes, the solution temperature was raised to 60 ° C. and the reaction was continued for another 1.5 hours. Then, after cooling to room temperature, 127 g of dimethylsiloxane having an isocyanate group (Polymer G) was obtained.
This polymer is referred to as "polymer G".

A coating film was prepared in the same manner as in Test Example 1 except that Polymer G was added in place of Polymers D to F in Test Example 1. The obtained coating film had repellency. Table 1 shows the contact angle of the coating film with water.

[0107]

[Table 1]

Claims (6)

[Claims] 1. (i) The side chain organic group is represented by the following formula [I] and at least one group selected from an alkyl group, an alkenyl group, an aralkyl group and a substituted or unsubstituted phenyl group. An isocyanate group, (ii) a main chain terminal group is trialkylsilylated, and (iii) a number average molecular weight of 500 to 100,000. Isocyanate group-containing polysilsesquioxane: R ¹ -X ¹ -R ² -X ² -R ³ -NCO ... [I] {In the formula [I], R ¹ may have a substituent, and a hetero atom of O, Represents an alkylene group which may contain S, R ² represents an alkylene group which may have a substituent, and which may contain O or S of a hetero atom, or a single bond, and X ¹ represents , Single bond, ester bond, sulfide bond, amide bond, urea Down bond, urea bond, thiourethane bond,
Represents an ether bond or a carbonyl bond, X ² represents a single bond or a urethane bond, R ³ represents a single bond, an alkylene group, a cycloalkylene group,
A phenylene group or a group consisting of two or more of any of these groups (excluding a single bond) is shown, and these groups may have a substituent, , S may be included. ｝ 2. The side chain organic group is at least one group selected from an alkyl group, an alkenyl group, an aralkyl group and a substituted or unsubstituted phenyl group, and a compound represented by the following formula [I
[I] and a hydroxyl group-containing group, the main chain terminal group is trialkylsilylated, a hydroxyl group-containing polysilsesquioxane having a number average molecular weight of 500 to 100,000, and a diisocyanate compound, Method for producing an isocyanate group-containing polysilsesquioxane characterized by reacting: -R ¹ -X ¹ -R ² -OH ... [II] (wherein R ¹ is a substituent Represents an alkylene group which may have a heteroatom O or S, R ² may have a substituent, and may include a heteroatom O or S An alkylene group or a single bond which may be present, X ¹ is a single bond, an ester bond, a sulfide bond, an amide bond, a urethane bond, a urea bond, a thiourethane bond,
Indicates either an ether bond or a carbonyl bond. ) 3. The method according to claim 2, wherein the diisocyanate compound is isophorone diisocyanate. 4. The side chain organic group is at least one group selected from an alkyl group, an alkenyl group, an aralkyl group and a substituted or unsubstituted phenyl group, and a compound represented by the following formula [II:
And a mercapto group-containing group represented by the formula [I], the main chain terminal group is trialkylsilylated, and a mercapto group-containing polysilsesquioxane having a number average molecular weight of 500 to 100,000 and the following formula [IV] A method for producing an isocyanate group-containing polysilsesquioxane, which comprises reacting an α, β-ethylenically unsaturated group-containing isocyanate compound represented by: (In the formula [III], R ¹ represents an alkylene group.) (In the formula [IV], R ⁴ represents hydrogen or a methyl group, and Y
Is a single bond, , A substituted or unsubstituted phenylene group, R
⁵ represents an alkylene group. ) 5. The method according to claim 4, wherein the α, β-ethylenically unsaturated group-containing isocyanate compound represented by the formula [IV] is 2-isocyanatoethyl methacrylate or methacryloyl isocyanate. 6. A resin modifier comprising the isocyanate group-containing polysilsesquioxane according to claim 1.