JP2002265609A - Boron-containing polyorganosilsesquioxane and adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a boron-containing polyorganosilsesquioxane excellent in heat resistance, weather resistance and the like, and useful as an adhesive component in a moisture curing adhesive composition which is excellent in the adhesivity to an adherend, and an adhesive composition using the same. SOLUTION: The boron-containing polyorganosilsesquioxane has a structure in which a part of intramolecular silicon atoms are bonded to silicon atoms via oxygen atoms. The adhesive composition contains the boron-containing polyorganosilsesquioxane as adhesive component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a boron-containing polyorganosilsesquioxane and an adhesive composition.
More specifically, the present invention provides a boron-containing polyorganosilsesquioki which is excellent in heat resistance and weather resistance and is useful as an adhesive component in a moisture-curable adhesive composition having good adhesion to an adherend. The present invention relates to a sun and an adhesive composition having the above-mentioned properties and containing the same as an adhesive component.

[0002]

2. Description of the Related Art Conventionally, water glass is known as a typical inorganic adhesive. However, since this water glass is strongly basic, it is generally used for bonding inorganic materials to each other. I have. As an organic-inorganic composite-based adhesive, a silicone resin-based adhesive is known.
Generally, ultraviolet rays are often radiated or heat is required at the time of curing, and it is also necessary to consider the wettability to the adherend in order to improve the adhesion to the adherend. As a special type of the silicone resin-based adhesive, a moisture-curable type using an alkoxysilane is known. However, since these react with water slowly and have poor reactivity (slow curing speed), an acid or base catalyst is usually added. On the other hand, polysilsesquioxane, which is a kind of silicone resin, is known to be a material having excellent heat resistance and weather resistance. Among these polysilsesquioxanes, polyorganosilsesquioxanes in which an organic group is bonded to a silicon atom are, for example, trifunctional silanes such as trichlorosilane and trialkoxysilane in which one non-hydrolyzable organic group is bonded. Can be produced by hydrolysis and condensation of This polyorganosilsesquioxane is used as a binder in an inorganic material layer when an inorganic material layer is formed on an inorganic or organic substrate. By using a group containing a functional group such as an epoxy group, a hydroxyl group, or a thiol group as the non-hydrolyzable organic group in the polyorganosilsesquioxane, the adhesion between the base material and the inorganic material layer can be improved. It is planned. By the way, in recent years, the application development of adhesives has been further diversified, and adhesives have been used in various fields such as industrial fields such as packaging and bookbinding, civil engineering and construction, electronic and electrical equipment, automobiles, optical components, and general consumer fields. Is used. As the adhesive, epoxy-based, urethane-based, acrylic-based, silicone-based, rubber-based, vinyl acetate-based, inorganic-based and the like are generally used, and among these adhesives, a moisture-curable type is used. It cures at room temperature due to moisture in the atmosphere, and has excellent heat resistance and weather resistance, and also has an organic material—an inorganic material, an organic material—an organic material and an inorganic material—
The application of inorganic materials with good adhesion has an extremely wide industrial application.

[0003]

Under these circumstances, the present invention is excellent in heat resistance and weather resistance, etc., and has good adhesion between organic material-inorganic material, organic material-organic material and inorganic material-inorganic material. It is an object of the present invention to provide a novel polyorganosilsesquioxane useful as an adhesive component or the like in a moisture-curable adhesive composition that can be adhered, and an adhesive composition having the above-mentioned properties containing this as an adhesive component. Is what you do.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, it has been found that polyorganosilsesquioxane wherein a part of silicon atoms in the molecule is an oxygen atom It has been found that a compound having a structure bonded to a boron atom through is a novel compound and can be suitable for the purpose. The present invention has been completed based on such findings. That is, the present invention provides a boron-containing polyorganosilsesquioxane having a structure in which a part of a silicon atom in a molecule is bonded to a boron atom via an oxygen atom, preferably (1) (a) general formula ^{(I) R 1 -B-R} 2 2 ······ (I) ( wherein, R ¹ is a hydroxyl group, an alkoxyl group or a chlorine atom 1 to 4 carbon atoms, R ² is a hydroxyl group, the number of carbon atoms Represents an alkoxyl group of 1 to 4, a hydrocarbon group of 1 to 12 carbon atoms or a chlorine atom, and two R ^{2 s} may be the same or different from each other;
Further, they may combine with each other to form a mono- or polycyclo ring. A boron compound represented by), (b) the general formula ^{(II) R 3 -Si-R} 4 3 ······ (II) ( wherein, R ³ is an organic group, R ⁴ is a hydrolyzable Represents a halogen atom or an alkoxyl group having 1 to 4 carbon atoms, and three R ^{4 s} may be the same or different from each other.) The boron-containing polyorganosilsesquis obtained by condensing a silicon compound represented by the formula: Oxane, and (2) a boron compound represented by the general formula (I), (b) a silicon compound represented by the general formula (II), and (c) a H-Si- Table with R ⁵ ₃ · · · · · · (III) (wherein, R ⁵ represents an alkoxyl group or a chlorine atom 1 to 4 carbon atoms, the three R ⁵ may be the same or different.) during the the silane compound by condensation, addition (d) general formula _{(IV) CH 2 = CH-} R 6 ······ (IV) ( wherein, R ⁶ . Of a hydrocarbon group having 1 to 10 carbon atoms having a functional group) represented by be comprised by an addition of vinyl compounds, -CH ₂ CH ₂ in a part of the silicon atoms -
A boron-containing polyorganosilsesquioxane into which an R ⁶ group (R ⁶ is as defined above) is introduced, and

(3) In the general formula (II) of the component (b), the organic group represented by R ³ is a hydrocarbon group having 1 to 12 carbon atoms or a hydrocarbon group having 1 to 12 carbon atoms having a functional group. A boron-containing polyorganosilsesquioxane of the above (1) or (2), wherein R ⁴ is an alkoxyl group having 1 to ⁴ carbon atoms, and (4) a component of the general formula (IV) Has a carbon number of 1 to 10 having a functional group represented by R ^6.
The boron-containing polyorganosilsesquioxane according to the above (2) or (3), wherein the hydrocarbon group is a hydrocarbon group having 1 to 10 carbon atoms having an isocyanate group or an isothiocyanate group. The present invention also provides an adhesive composition comprising the boron-containing polyorganosilsesquioxane as an adhesive component.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The boron-containing polyorganosilsesquioxane of the present invention is a novel compound having a structure in which a part of a silicon atom in a molecule is bonded to a boron atom via an oxygen atom. The boron atom may be introduced into the molecular chain, may be introduced at the molecular end, or may be introduced into both of them. One organic group is bonded to the silicon atom in the molecule, and the organic group is preferably a hydrocarbon group having 1 to 12 carbon atoms and a hydrocarbon group having 1 to 12 carbon atoms having a functional group. . Here, the hydrocarbon group having 1 to 12 carbon atoms includes 1 to 12 carbon atoms.
12 alkyl groups, alkenyl groups having 2 to 12 carbon atoms, and 6 to 1 carbon atoms having or not having a substituent on an aromatic ring.
2 aryl groups and aralkyl groups having 7 to 12 carbon atoms with or without a substituent on an aromatic ring. The alkyl group having 1 to 12 carbon atoms may be linear, branched, or cyclic. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, and n. -Butyl group, isobutyl group, sec-
Examples thereof include a butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, and a cyclohexyl group. An alkenyl group having 2 to 12 carbon atoms is
It may be linear, branched or cyclic, and examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a hexenyl group and an octenyl group.
Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, a phenethyl group, and a phenylpropyl group. And a naphthylmethyl group.

On the other hand, examples of the functional group in the hydrocarbon group having a functional group having 1 to 12 carbon atoms include a hydroxyl group, a thiol group, an amino group, a cyano group, an isocyanate group, an isothiocyanate group, an epoxy group and (meth) acryloyl. At least one selected from oxy groups and the like can be mentioned. 1 carbon atom into which these functional groups are introduced
Examples of the hydrocarbon group having 1 to 12 include the same as those exemplified in the description of the hydrocarbon group having 1 to 12 carbon atoms. 1 to 12 carbon atoms having this functional group
Examples of the hydrocarbon group include 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-mercaptoethyl, 3-mercaptopropyl, 2-mercaptopropyl, 2-aminoethyl, 3-aminopropyl group, 2-aminopropyl group, 2
-Dimethylaminoethyl group, 4-dimethylaminobenzyl group, 2-cyanoethyl group, 3-cyanopropyl group, 2
-Cyanopropyl group, 3-isocyanatopropyl group, 3
-Isothiocyanatopropyl group, 3-glycidoxypropyl group, 3,4-epoxycyclohexyl group, 3-acryloyloxypropyl group, 3-methacryloyloxypropyl group, and the like.

In the present invention, the organic groups bonded to the silicon atom in the molecule may be of the same type or different types. In particular, if the organic group bonded to the silicon atom in the molecule is a hydrocarbon group having the above functional group, when the boron-containing polyorganosilsesquioxane of the present invention is used as an adhesive component, The adhesion is improved. On the other hand, in the boron-containing polyorganosilsesquioxane of the present invention, a boron atom to which a part of a silicon atom is bonded via an oxygen atom can be present in a molecular chain or at a molecular terminal or both. One organic group may be bonded to the boron atom present in the molecular chain, and one or two organic groups or chlorine atoms may be bonded to the boron atom present at the molecular end. You may. This organic group has 1 to 1 carbon atoms.
Twelve hydrocarbon groups are preferred. Examples of the hydrocarbon group having 1 to 12 carbon atoms include the same as those exemplified in the description of the hydrocarbon group having 1 to 12 carbon atoms in the organic group bonded to the silicon atom. The organic group may be a bulky hydrocarbon group. Examples of such a bulky hydrocarbon group include a tert-butyl group and a tert-butyl group.
-Amyl group, tert-octyl group, phenyl group, cyclohexyl group and the like. When two C1-C12 hydrocarbon groups are bonded to the terminal boron atom, these may be bonded to each other to form a bulky mono- or polycyclo ring group together with the boron atom. Examples of such bulky groups include boracyclooctane-1-
Yl group, 8-borabicyclo [3.2.1] octane-8
-Yl group and the like. In such a boron-containing polyorganosilsesquioxane into which such a boron atom has been introduced, the bond between the boron atom and the oxygen atom is cut by moisture to form a hydroxyl group at the terminal, and polymerization (polycondensation) proceeds. When used as an adhesive component, a moisture-curable adhesive can be obtained.

The ratio of silicon atoms to boron atoms in the boron-containing polyorganosilsesquioxane of the present invention is as follows:
The molar ratio is usually selected in the range of 5: 1 to 500: 1. If the content of boron atoms is less than the above range, the effect of introducing boron atoms may not be sufficiently exerted, while if it is more than the above range, performance as polyorganosilsesquioxane may be lost, which is not preferable. . For these reasons, the preferred ratio of silicon atoms to boron atoms is in the range of 5: 1 to 100: 1, especially 5:
A range of 1 to 20: 1 is preferred. The boron-containing polyorganosilsesquioxane of the present invention can be produced by the following two methods. First, the first method, (a) the general formula _{^{R 1 -B-R 2 2 ······}} (I) ( wherein, R ¹ is a hydroxyl group, an alkoxyl group or a chlorine atom 1 to 4 carbon atoms , R ² is a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydrocarbon group or a chlorine atom having 1 to 12 carbon atoms, the two R ² may be the same or different from each other,
Further, they may combine with each other to form a mono- or polycyclo ring. A boron compound represented by), (b) the general formula ^{(II) R 3 -Si-R} 4 3 ······ (II) ( wherein, R ³ is an organic group, R ⁴ is a hydrolyzable Is a halogen atom or an alkoxyl group having 1 to 4 carbon atoms, and three R ^{4 's} may be the same or different from each other.)

In the compound represented by the general formula (I) of the component (a), examples of the alkoxyl group having 1 to 4 carbon atoms in R ¹ and R ² include methoxy, ethoxy, n- Propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert
-Butoxy group. And the number of carbon atoms in R ² is 1
Examples of the hydrocarbon group having 12 to 12 include the same as those exemplified in the description of the hydrocarbon group having 1 to 12 carbon atoms in the organic group bonded to the silicon atom. As the boron compound represented by the general formula (I), as a monofunctional boron compound, for example, a compound represented by the general formula (I-
^{a) R 1 -B-R 7} 2 ······ (I-a) ( wherein, R ¹ is the same as defined above, R ⁷ is a carbon number 1 to 1
R 2 represents two hydrocarbon groups or chlorine atoms, and two R ^{7 s} may be the same or different, and may combine with each other to form a mono- or polycyclo ring. )).

Examples of the compound represented by the general formula (Ia) include dimethylhydroxyborane, diethylhydroxyborane, di-tert-butylhydroxyborane, diphenylhydroxyborane, dibenzylhydroxyborane, tert-butylethyl. Hydroxyborane,
1-hydroxyboracyclooctane, 8-hydroxy-
8-borabicyclo [3.2.1] octane, dimethylmethoxyborane, diethylmethoxyborane, di-ter
t-butylmethoxyborane, diphenylmethoxyborane, dibenzylmethoxyborane, tert-butylethylmethoxyborane, 1-methoxyboracyclooctane,
8-methoxy-8-borabicyclo [3.2.1] octane, dicyclohexylchloroborane and the like.
As bifunctional boron compounds, for example the general formula _{^{(I-b) R 1 2}} -B-R 7 ······ (I-b) ( wherein, R ¹ and R ⁷ are as defined above, 2 Two R ¹
They may be the same or different. )).

Examples of the compound represented by the general formula (Ib) include dihydroxymethylborane, dihydroxyethylborane, tert-butyldihydroxyborane,
Dihydroxyphenylborane, benzyldihydroxyborane, dimethoxymethylborane, dimethoxyethylborane, tert-butyldimethoxyborane, dimethoxyphenylborane, benzyldimethoxyborane, hydroxymethoxymethylborane, ethylhydroxymethoxyborane, t-butylhydroxymethoxyborane, hydroxymethoxyphenyl Borane, benzylhydroxymethoxyborane and the like. As a trifunctional boron compound,
For example in the general formula _{^{(I-c) R 1 3}} -B ······ (I-c) ( wherein, R ¹ is the same as defined above, three of R ¹ are also the same with or different from each other Good)). Examples of the compound represented by the general formula (Ic) include boric acid, dihydroxymethoxyborane, dimethoxyhydroxyborane, trimethoxyborane and the like.

In the present invention, as the boron compound as the component (a), the above-mentioned general formulas (Ia), (Ib),
One of the boron compounds represented by (Ic) may be selected and used, or two or more may be selected and used. On the other hand, in the compound represented by the general formula (II) of the component (b), the organic group represented by R ³ includes a hydrocarbon group having 1 to 12 carbon atoms and a carbon group having 1 to 12 carbon atoms having a functional group. Can be mentioned. Here, examples of the hydrocarbon group having 1 to 12 carbon atoms include the same as those exemplified in the description of the hydrocarbon group having 1 to 12 carbon atoms in the organic group bonded to the silicon atom. Also,
Examples of the functional group in the hydrocarbon group having a functional group having 1 to 12 carbon atoms include a hydroxyl group, a thiol group, an amino group,
Examples include at least one selected from a cyano group, an epoxy group, a (meth) acryloyloxy group, and the like.

Examples of the C1-C12 hydrocarbon group having a functional group include a 2-hydroxyethyl group and a 3-hydroxyethyl group.
Hydroxypropyl group, 2-hydroxypropyl group, 2
-Mercaptoethyl group, 3-mercaptopropyl group, 2
-Mercaptopropyl group, 2-aminoethyl group, 3-aminopropyl group, 2-aminopropyl group, 2-dimethylaminoethyl group, 4-dimethylaminobenzyl group, 2-
Examples include a cyanoethyl group, a 3-cyanopropyl group, a 2-cyanopropyl group, a 3-glycidoxypropyl group, a 3,4-epoxycyclohexyl group, a 3-acryloyloxypropyl group, and a 3-methacryloyloxypropyl group. Further, as the halogen atom in R ^4, a chlorine atom is preferably mentioned, and as the alkoxyl group having 1 to 4 carbon atoms, the alkoxyl group having 1 to 4 carbon atoms in the general formula (I) can be used.
And the same as those exemplified in the description of the alkoxyl group.

The silicon compound represented by the general formula (II) includes, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Propyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, 2
-Hydroxyethyltrimethoxysilane, 3-hydroxypropyltrimethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 2-mercaptopropyltrimethoxysilane, 2-
Aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane, 2-dimethylaminoethyltrimethoxysilane, 4-dimethylaminobenzyltrimethoxysilane,
2-cyanoethyltrimethoxysilane, 3-cyanopropyltrimethoxysilane, 2-cyanopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3,4-epoxycyclohexyltrimethoxysilane, 3-acryloyloxypropyltrimethoxy Examples include trialkoxysilanes such as silane and 3-methacryloyloxypropyltrimethoxysilane, and trichlorosilanes corresponding thereto. One of these silicon compounds may be used alone, or two or more thereof may be used in combination.

In the present invention, a predetermined ratio of the component (a), ie, the boron compound represented by the general formula (I),
The silicon compound represented by the general formula (II), which is the component (b), is preferably used in a solvent containing at least water in the presence of an acid or base catalyst, preferably hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid. In the presence of an acid catalyst such as
The boron-containing polyorganosilsesquioxane of the present invention can be obtained by condensing while partially hydrolyzing at a temperature of about 50 ° C, preferably 10 to 40 ° C. In this reaction, when a monofunctional boron compound is used as the boron compound represented by the general formula (I) as the component (a), the silicon atom at the terminal of the polyorganosilsesquioxane is bonded via oxygen. Bonds to boron atoms.

The boron compound may be bifunctional or trifunctional.
When a functional boron compound is used, a boron atom can be introduced into the molecular chain of the polyorganosilsesquioxane, and can be bonded to a silicon atom via oxygen. As the boron compound represented by the general formula (I), the boron compound represented by the general formula (I)
When a monofunctional boron compound represented by -a) is condensed with a silicon compound represented by the general formula (II),
For example, the general formula (V)

[0018]

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(Wherein, R ³ and R ⁷ are the same as described above, and n represents the degree of polymerization.) A boron-containing polyorganosilsesquioxane represented by the following formula: Next, the second method comprises (a) a boron compound represented by the general formula (I), (b) a silicon compound represented by the general formula (II), and (c) a silicon compound represented by the general formula (III). ) in _{^{H-Si-R 5 3 ······}} (III) ( wherein, R ⁵ represents an alkoxyl group or a chlorine atom 1 to 4 carbon atoms, even three R ⁵ are identical or different from each other Good). (D) CH ₂シ ラ ン CH—R ⁶ ... (IV) wherein R ⁶ is a carbon atom having a functional group. By adding a vinyl compound represented by the formula (1), a —CH ₂ CH ₂ —R ⁶ group (R ⁶ is the same as described above) is introduced into a part of the silicon atom. This is a method for producing a boron-containing polyorganosilsesquioxane.

This method introduces a functional group which cannot be easily hydrolyzed into the boron-containing polyorganosilsesquioxane, for example, an isocyanate group or an isothiocyanate group, in the first method. Is the way. In the general formula (III) of the component (c), R ⁵
Examples of the alkoxyl group having 1 to 4 carbon atoms represented by are the same as those exemplified in the description of the alkoxyl group having 1 to 4 carbon atoms in the general formula (I). Examples of the silane compound represented by the general formula (III) include trimethoxysilane, triethoxysilane, and trichlorosilane. Further, in the general formula (IV) of the component (d), as the functional group in the hydrocarbon group having 1 to 10 carbon atoms having a functional group represented by R ⁶ , an isocyanate group or an isothiocyanate group is particularly preferable. Can be. Preferred examples of the vinyl compound represented by the general formula (IV) include allyl isocyanate and allyl isothiocyanate.

In the present invention, a predetermined ratio of the component (a), a boron compound represented by the general formula (I),
(B) a silicon compound represented by the general formula (II), which is a component, and a trialkoxysilane represented by the general formula (III):
In a solvent containing at least water, in the presence of an acid or base catalyst, preferably in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, and methanesulfonic acid,
At a temperature of about 100 ° C., preferably at a temperature of 20 to 90 ° C., boron-containing polyorganosilsesquioxane is produced by condensation while partially hydrolyzing. The produced boron-containing polyorganosilsesquioxane can be recovered by precipitation by adding an organic solvent such as hexane. In this reaction, the boron compound represented by the general formula (I) is used as the boron compound represented by the general formula (I).
When the monofunctional boron compound represented by -a) is used, for example, the compound represented by the general formula (VI)

[0022]

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(Wherein R ³ , R ⁷ and n are the same as described above). Next, a vinyl compound represented by the general formula (IV) is added to the boron-containing polyorganosilsesquioxane thus obtained by using, for example, a chloroplatinic acid catalyst, usually at 50 to 200 ° C., preferably at 80 ° C. By adding at a temperature of １５０150 ° C., a part of the silicon atom —CH ₂ CH ₂ —R ⁶ group (R ⁶
Is the same as above. ) To obtain a boron-containing polyorganosilsesquioxane. in this case,
When the vinyl compound is added to the compound represented by the general formula (VI), the compound represented by the general formula (VII)

[0024]

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(Wherein R ³ , R ⁶ , R ⁷ and n are the same as those described above), thereby obtaining a boron-containing polyorganosilsesquioxane represented by the formula: Such a boron-containing polyorganosilsesquioxane of the present invention has such a property that the space between the boron atom and the oxygen atom is cut off by water to further promote polymerization and gelation. Therefore, it is useful as an adhesive component of a moisture-curable adhesive. It is also possible to introduce various functional groups into the silicon atom,
Thereby, when used as an adhesive component, good adhesion to an adherend can be achieved. The adhesive composition of the present invention contains the above-mentioned boron-containing polyorganosilsesquioxane of the present invention as an adhesive component, and is a moisture-curable type which is cured by moisture in the air. In this adhesive composition, as long as the object of the present invention is not impaired,
If desired, an inorganic filler, a curing catalyst, a colorant, and the like can be contained. Examples of the inorganic filler include silica, alumina, aluminum hydroxide, magnesium oxide, calcium carbonate, talc, mica, and clay.

Further, when the boron-containing polyorganosilsesquioxane as the adhesive component has a photopolymerizable functional group such as an acryloyloxy group or a methacryloyloxy group introduced into a silicon atom, a photopolymerization initiator may be used. The adhesive layer may be irradiated with an actinic ray such as ultraviolet rays at the time of bonding to improve the adhesion to the adherend. When the boron-containing polyorganosilsesquioxane has an epoxy functional group such as a glycidyl group introduced into a silicon atom, the adhesive layer is treated with an alkaline solution or the like at the time of bonding to open the epoxy group. Let it ring
Adhesion with an adherend can be improved. The curing time of the adhesive composition of the present invention in the atmosphere is generally about 6 to 48 hours at room temperature.

[0027]

Next, the present invention will be described in more detail with reference to Examples.
As will be explained, the present invention is not limited by these examples.
It is not something to be done. Example 1 10 g of phenyltrimethoxysilane as a silicon compound
And 1.3 g of diethylmethoxyborane as a boron compound
Mixed solution having a toluene-water weight ratio of 22: 2.5.
5 g and methanesulfonic acid 0.2 as a catalyst.
4 g at 3 ° C. while distilling off low boiling components.
The reaction was continued at 90 ° C. for 6 hours. The completion of the reaction
Thereafter, hexane was added to the reaction solution to precipitate a reaction product.
2 g were recovered. The following method is used for this reaction product.
In addition to measuring the number average molecular weight, elemental analysis, infrared
Absorption spectrum (IR), nuclear magnetic resonance spectrum (NM
R) was measured. (1) Number average molecular weight For gel permeation chromatography (GPC)
The number average molecular weight in terms of polystyrene was measured from (T
SK gel, G2500, G2000, G1000, TH
F solvent). For measurement, use HLC-8020 chromatograph
(Tosoh Corporation) was used. (2) Elemental analysis By ICP spectroscopy, the ratio of silicon atoms to boron atoms was determined.
It was measured. The measurement was performed by adding 0.01 g of the reaction product to 100 ml.
After dispersing in water and adding a small amount of hydrogen fluoride to decompose,
Further, water was added to about 100 ppm. For measurement
Is ICP. S-1000IV (manufactured by Shimadzu Corporation)
It was used. (3) Infrared absorption spectrum (IR) Using FT / IR1600 (manufactured by PerkinElmer)
Was. (4) Nuclear magnetic resonance spectrum¹ H NMR and¹³FX 270 (day
Honden Co., Ltd.) ²⁹Si CP / MAS NMR
JNM A-500 (manufactured by JEOL Ltd.) was used for measurement.
Used. The results are shown below. Number average molecular weight Mn = 1400 Elemental analysis Si: B ≒ 5: 1 Infrared absorption spectrum 3490 cm^-1(OH), 2950cm^-1(-CH) 1600, 1440, 720, 700 cm^-1(Ph) 1110cm^-1(C-Si), 1040cm^-1(Si-
O-Si) Nuclear magnetic resonance spectrum¹1 H NMR: 1.2 ppm (BCH_Two CH ₃ ) 3.6 ppm (BCH ₂ CH_Three), 7.4 ppm (Ph)¹³C NMR: 8.2 ppm (CH_Three), 20.8 ppm (CH_Two) 129,133,155 ppm (Ph)²⁹Si CP / MAS NMR: -78 ppm From these results, the reaction product was bonded to boron at the terminal.
Having an ethyl group and a mole of silicon and boron atoms
Polyorganosilses having a ratio of 5: 1 and having phenyl groups
It was identified as squioxane.

Example 2 The reaction was carried out in the same manner as in Example 1, except that 10 g of 3-methacryloyloxypropyltrimethoxysilane was used as a silicon compound, and 0.8 g of dicyclohexylchloroborane and 0.24 g of methanesulfonic acid were used as a boron compound. 6.8 g of the product were obtained. The number average molecular weight of this reaction product was measured in the same manner as in Example 1, and the elemental analysis was performed.
IR and NMR measurements were performed. The results are shown below. Number average molecular weight Mn = 1200 Elemental analysis Si: B ≒ 10: 1 Infrared absorption spectrum 2954 cm ^-1 (CH), 1716 cm ^-1 (C = O) 1,637 cm ^-1 (C = C), 1124 cm ^-1 (CO-
C) 1039 cm ^-1 (Si-O-Si) nuclear magnetic resonance spectrum ¹ H NMR: 0.5 to 2.0 ppm (C ₆ H ₁₁ -CH ₂ ) 4.0 ppm (OCH ₂ ) 5.5, 6.0 ppm ^{(CH = C) 13 C NMR} : 10ppm (CH 2), 18ppm (CH 3) 22~30ppm (C 6 H 11 -B) 67ppm (OCH 2), 125,135ppm (CH = C) 168ppm (C = O ) ²⁹ Si CP / MAS NMR: -78 ppm From these results, the reaction product has a cyclohexyl group bonded to boron, a molar ratio of silicon atom to boron atom of 10: 1, and a 3-methacryloyloxypropyl group. Has been identified to be a polyorganosilsesquioxane having

Example 3 The procedure of Example 1 was repeated, using 10 g of 3-glycidoxypropyltrimethoxysilane as the silicon compound, 1.3 g of diethylmethoxyborane as the boron compound and 0.35 g of concentrated hydrochloric acid as the catalyst. 5.0 g of reaction product was obtained. The number average molecular weight of this reaction product was measured in the same manner as in Example 1, and elemental analysis, IR and NMR were performed.
Was measured. The results are shown below. Number average molecular weight Mn = 2000 Elemental analysis Si: B ≒ 10: 1 Infrared absorption spectrum 2950 cm ^-1 (CH), 1110 cm ^-1 (CO-
C) 1040 cm ^-1 (Si-O-Si) Nuclear magnetic resonance spectrum ¹ H NMR: 1.2 ppm (BCH ₂ CH ₃ ) 3.6 ppm (B CH _{2 CH 3) 1.5~2.0ppm (CH 2)} 2.5~3.5ppm (CH 2) 13 C NMR: 7.1ppm (SiCH 2), 8.2ppm (CH 3) 15.5ppm (SiCH 2 CH ₂ ) 20.8 ppm (CH ₂ ) 43.0, 50.5 ppm (CH—O—CH ₂ ) 73.1 ppm (CH ₂ ) ²⁹ Si CP / MAS NMR: −78 ppm From these results, the reaction product was located at the terminal. Having an ethyl group bonded to boron, and having a molar ratio of silicon atom to boron atom of 10: 1, wherein 3-glycidoxypropyl group and 3-
It was identified as a polyorganosilsesquioxane having a methacryloyloxypropyl group.

Example 4 The reaction was carried out in the same manner as in Example 1, except that 10 g of 3-methacryloyloxypropyltrimethoxysilane was used as the silicon compound, 0.8 g of dihydroxyphenylborane was used as the boron compound, and 0.35 g of concentrated hydrochloric acid was used as the catalyst. 7.2 g of the product were obtained. This reaction product was prepared in Example 1
The number average molecular weight was measured in the same manner as in
R and NMR measurements were made. The results are shown below. The number average molecular weight Mn = 4000 Elemental analysis Si: B ≒ 10: 1 infrared absorption spectrum ^{3490cm -1 (OH), 2950cm -1} (CH) 1720cm -1 (C = O), 1637cm -1 (C = C) 1120cm - ¹ (C—O—C) 1040 to 1080 cm ⁻¹ (Si—O—Si) Nuclear magnetic resonance spectrum ¹ H NMR: 1.9 ppm (CH ₃ ), 4.0 ppm (OCH ₂ ) 5.5, 6.0 ppm (CH = C) 7.2-7.8 ppm (Ph-B) ¹³ C NMR: 8 ppm (CH ₂ ), 18 ppm (CH ₃ ) 67,68 ppm (OCH ₂ ), 22 ppm (CH ₂ ) 125,135 ppm (C = C) 128,129.132ppm (Ph-B ) 29 Si CP / MAS NMR: -78ppm these results, the reaction product off bonded to the boron in the end Having a group, and the molar ratio of silicon atoms and boron atoms are 10: 1, it is polyorganosilsesquioxane having a 3-methacryloyloxypropyl group is identified.

Example 5 10 g of 3-glycidoxypropyltrimethoxysilane as a silicon compound, 2.6 g of trimethoxysilane as a silane compound and 0.9 g of diphenylhydroxyborane as a boron compound were mixed in a toluene-water weight ratio of 22: 2.5.
Was added thereto, and 0.24 g of methanesulfonic acid was further added as a catalyst. The mixture was reacted at 23 ° C. for 3 hours and continuously at 90 ° C. for 6 hours while distilling off low boiling components. Then, hexane was added to the reaction solution, and 6.5 g of a precipitated reaction product was recovered. Next, as a solvent, toluene 1
After 6.5 g of the above reaction product was added to 8 g, 2 g of allyl isocyanate as a vinyl compound and 1 mg of chloroplatinic acid as a catalyst were added, and the mixture was reacted at 80 ° C. for 3 hours. The thing was collected. Yield 7.0 g. The number average molecular weight of this reaction product was measured in the same manner as in Example 1, and at the same time, elemental analysis, IR and NMR were measured. The results are shown below. The number average molecular weight Mn = 2000 Elemental analysis Si: B ≒ 8: 1 Infrared absorption spectrum ^{2950cm -1 (CH), 2240cm -1} (NCO) 1110cm -1 (C-O-C), 1040cm -1 (Si
—O—Si) Nuclear magnetic resonance spectrum ¹ H NMR: 1.5 to 2.0 ppm (CH ₂ ) 2.5 to 3.5 ppm (CH ₂ ) 7.25 to 7.5 ppm (Ph-B) ¹³ C NMR _{: 7.1ppm (SiCH 2) 15.5ppm (} SiCH 2 CH 2) 17.9ppm (SiCH 2) 43.0,50.5ppm (CH-O-CH 2) 73.1ppm (CH 2), 38.3ppm ( CH ₂ -N) 122 ppm (C = O) 128-135 ppm (Ph-B) ²⁹ Si CP / MAS NMR: -78 ppm From these results, the reaction product has a phenyl group bonded to boron at the terminal and silicon It was identified as a polyorganosilsesquioxane having a 3-glycidoxypropyl group and an allyl group with a molar ratio of atoms to boron atoms of 8: 1.

Comparative Example 1 10 g of phenyltrimethoxysilane was added to 24.5 g of a mixed solution of toluene / water at a weight ratio of 22: 2.5, and 0.24 g of methanesulfonic acid was further added as a catalyst. Performed to obtain 7.0 g of polyorganosilsesquioxane.

Examples 6 to 10 Each of the boron-containing polyorganosilsesquioxanes obtained in Examples 1 to 5 was coated on a 2 mm-thick glass plate (manufactured by Paltec Co., Ltd.), a polyethylene terephthalate film [manufactured by Toray Industries, Inc. Product name: Lumirror, thickness 188μ
m) and a polycarbonate film (trade name: Lexan 8101, manufactured by Sansho Bussan Co., Ltd., thickness: 100 μm) to give an adhesive layer having a thickness of 20 μm. In Examples 2 and 4, α-hydroxycyclohexyl phenyl ketone 0.14 was used in advance as a photoinitiator.
g was added, and the adhesive layer was irradiated with ultraviolet rays at 300 mJ. In Examples 3 and 5, the adhesive layer was immersed in a 10% by weight aqueous sodium hydroxide solution for 10 minutes to react an epoxy group. After curing under the conditions shown in Table 1 at 23 ° C. and a relative humidity of 50%, a weathering acceleration test was conducted for 200 hours with a sunshine weatherometer WEL-SUN-HCH (manufactured by Suga Test Instruments Co., Ltd.). Thereafter, the adhesion to three adherends and the hardness were evaluated according to the following methods.
Table 1 shows the results. (5) Adhesion Adhesion was evaluated by a cellophane adhesive tape peeling test (cross-cut method) according to JIS K5400. ○ Evaluation score 8-10 △ Evaluation score 4-6 × Evaluation score 0-2 (6) Hardness The surface of the adhesive layer was rubbed five times with # 0000 steel wool, and the surface was visually observed and evaluated according to the following criteria. did. ○ No scratches on the surface △ Some scratches on the surface. × Scratches are observed on the entire surface.

Comparative Examples 2 to 4 Water Glass No. 3 (Comparative Example 2), 3-Methacryloyloxypropyltrimethoxysilane (Comparative Example 3) and Comparative Example 1
Using the polyorganosilsesquioxane obtained in the above (Comparative Example 4), in the same manner as in Examples 6 to 10, a glass plate,
It was applied to each of a polyethylene terephthalate film and a polycarbonate film so as to have a thickness of 20 μm, and an adhesive layer was provided. Time shown in Table 1, 23 ° C,
After curing under the condition of a relative humidity of 50%, a weathering acceleration test was performed for 200 hours with a sunshine weatherometer in the same manner as in Examples 6 to 10, and then the adhesion and hardness to three types of adherends were determined. evaluated. The results are shown in Table 1.

[0035]

[Table 1]

[0036]

Industrial Applicability The boron-containing polyorganosilsesquioxane of the present invention is a novel compound, which is excellent in heat resistance, weather resistance, etc. and has good moisture-curing adhesion to an adherend. It is useful as an adhesive component in the agent composition. The adhesive composition of the present invention is a moisture-curable type containing the above-mentioned boron-containing polyorganosilsesquioxane as an adhesive component, and has an organic-inorganic material, an organic-organic material, and an inorganic-inorganic material having an adhesive property. Good adhesion and excellent heat resistance and weather resistance.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J027 AF03 AF05 AF06 CB10 CD09 4J034 DA10 DB01 DM01 DM04 HA01 HA04 HA18 HC03 KA01 KC37 KD25 RA08 4J035 BA12 CA021 CA131 CA14N CA141 HA04 HB02 LA03 LB02 4J040 EK071

Claims (7)

[Claims] 1. A boron-containing polyorganosilsesquioxane having a structure in which a part of a silicon atom in a molecule is bonded to a boron atom via an oxygen atom. 2. The boron-containing polyorganosilsesquioxane according to claim 1, wherein the ratio of silicon atoms to boron atoms is 5: 1 to 500: 1 in molar ratio. Wherein (a) the general formula ^{(I) R 1 -B-R} 2 2 ······ (I) ( wherein, R ¹ is a hydroxyl group, an alkoxyl group or a chlorine atom 1 to 4 carbon atoms , R ² is a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydrocarbon group or a chlorine atom having 1 to 12 carbon atoms, the two R ² may be the same or different from each other,
Further, they may combine with each other to form a mono- or polycyclo ring. A boron compound represented by), (b) the general formula ^{(II) R 3 -Si-R} 4 3 ······ (II) ( wherein, R ³ is an organic group, R ⁴ is a hydrolyzable A halogen atom or an alkoxyl group having 1 to 4 carbon atoms, and three R ^{4 s} may be the same or different from each other.) 3. The boron-containing polyorganosilsesquioxane according to 1 or 2. Wherein (a) the general formula ^{(I) R 1 -B-R} 2 2 ······ (I) ( wherein, R ¹ is a hydroxyl group, an alkoxyl group or a chlorine atom 1 to 4 carbon atoms , R ² is a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms, a hydrocarbon group or a chlorine atom having 1 to 12 carbon atoms, the two R ² may be the same or different from each other,
Further, they may combine with each other to form a mono- or polycyclo ring. A boron compound represented by), (b) the general formula ^{(II) R 3 -Si-R} 4 3 ······ (II) ( wherein, R ³ is an organic group, R ⁴ is a hydrolyzable A halogen atom or an alkoxyl group having 1 to 4 carbon atoms, wherein three R ^{4 's} may be the same or different from each other); and (c) a compound represented by the general formula (III) H- _{^{Si-R 5 3 ······ (III}} ) ( wherein, R ⁵ represents an alkoxyl group or a chlorine atom 1 to 4 carbon atoms, the three R ⁵ may be the same or different.) (D) CH ₂シ ラ ン CH—R ⁶ ... (IV) wherein R ⁶ is a carbon atom having a functional group. . showing the 10 hydrocarbon group) represented by be comprised by an addition of vinyl compounds, -CH ₂ CH ₂ in a part of the silicon atoms -
3. The boron-containing polyorganosilsesquioxane according to claim 1, wherein an R ⁶ group (R ⁶ is as defined above) is introduced. 5. In the general formula (II) of the component (b), R
^The organic group represented by ³ is a hydrocarbon group having 1 to 12 carbon atoms or a hydrocarbon group having 1 to 12 carbon atoms having a functional group,
5. The boron-containing polyorganosilsesquioxane according to claim 3, wherein R ⁴ is an alkoxyl group having 1 to ⁴ carbon atoms. 6. In the general formula (IV) of the component (d),
The C1 to C10 hydrocarbon group having a functional group represented by ⁶ is a C1 to C10 hydrocarbon group having an isocyanate group or an isothiocyanate group.
The boron-containing polyorganosilsesquioxane as described. 7. An adhesive composition comprising the boron-containing polyorganosilsesquioxane according to any one of claims 1 to 6 as an adhesive component.