JP4187941B2 - Boron-containing polyorganosilsesquioxane and adhesive composition - Google Patents

Boron-containing polyorganosilsesquioxane and adhesive composition Download PDF

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JP4187941B2
JP4187941B2 JP2001071730A JP2001071730A JP4187941B2 JP 4187941 B2 JP4187941 B2 JP 4187941B2 JP 2001071730 A JP2001071730 A JP 2001071730A JP 2001071730 A JP2001071730 A JP 2001071730A JP 4187941 B2 JP4187941 B2 JP 4187941B2
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boron
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JP2002265609A (en
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治 守谷
壮 宮田
俊夫 杉崎
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リンテック株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a boron-containing polyorganosilsesquioxane and an adhesive composition. More specifically, the present invention is a boron-containing polyorganosilsesquioxide useful as an adhesive component in a moisture-curing adhesive composition having excellent heat resistance and weather resistance and good adhesion to an adherend. Sun and the adhesive composition which has the said characteristic containing this as an adhesive component.
[0002]
[Prior art]
Conventionally, water glass is known as a representative inorganic adhesive, but since this water glass is strongly basic, it is generally used for bonding an inorganic material and an inorganic material. Moreover, as an organic-inorganic composite-based adhesive, a silicone resin-based adhesive is known, but this adhesive is generally irradiated with ultraviolet rays at the time of curing or requires heating. In order to improve the adhesion, the wettability to the adherend needs to be considered. Among these silicone resin adhesives, a moisture curing type using alkoxysilane is known as a special type. However, since this has a slow reaction with moisture and poor reactivity (low curing rate), 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 excellent in 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. This polyorganosilsesquioxane is used as an inorganic substrate or a binder in the inorganic material layer when an inorganic material layer is formed on the organic substrate. And by using groups containing functional groups such as epoxy groups, hydroxyl groups, and thiol groups as non-hydrolyzable organic groups in polyorganosilsesquioxane, the adhesion between the substrate and the inorganic material layer can be improved. It is illustrated.
By the way, in recent years, the application development of adhesives has further diversified, and adhesives are used in various fields such as industrial fields such as packaging / binding, civil engineering / architecture, electronic / electric equipment, automobiles, optical parts, and general consumer fields. Is being used.
As the adhesive, generally epoxy, urethane, acrylic, silicone, rubber, vinyl acetate, inorganic, etc. are used, and among these adhesives, it is a moisture curable type, Those that harden at room temperature with moisture in the atmosphere and are excellent in heat resistance and weather resistance, and that adhere organic materials-inorganic materials, organic materials-organic materials and inorganic materials-inorganic materials with good adhesion, are industrially applied. The field is extremely wide.
[0003]
[Problems to be solved by the invention]
Under such circumstances, the present invention is a moisture curable adhesive that is excellent in heat resistance and weather resistance and can adhere an organic material-inorganic material, organic material-organic material, and inorganic material-inorganic material with good adhesion. It is an object of the present invention to provide a novel polyorganosilsesquioxane useful as an adhesive component in a composition, and an adhesive composition having the above-mentioned properties containing this as an adhesive component.
[0004]
[Means for Solving the Problems]
  As a result of intensive studies to achieve the above object, the present inventors have found that polyorganosilsesquioxane has a structure in which some silicon atoms in the molecule are bonded to boron atoms through oxygen atoms. It has been found that a compound having a is novel and can be adapted to its purpose. The present invention has been completed based on such findings.
  That is, the present invention
(1)(A) General formula (I)
R1-BR2 2・ ・ ・ ・ ・ ・ (I)
(Wherein R1Is a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms or a chlorine atom, R2Represents a hydrocarbon group having 1 to 12 carbon atoms, and two R2May be the same or different from each other, and may be bonded to each other to form a mono- or polycyclo ring), and (b) the general formula (II)
RThree-Si-RFour Three・ ・ ・ ・ ・ ・ (II)
(Wherein RThreeHas at least one functional group selected from a hydrocarbon group having 1 to 12 carbon atoms, a hydroxyl group, a thiol group, an amino group, a cyano group, an isocyanate group, an isothiocyanate group, an epoxy group, and a (meth) acryloyloxy group. A hydrocarbon group having 1 to 12 carbon atoms, RFourIs a hydrolyzable group and represents a halogen atom or an alkoxyl group having 1 to 4 carbon atoms, and 3 RFourWherein the silicon atoms at the terminal of the polyorganosilsesquioxane obtained by condensing the silicon compounds represented by (1) may be the same or different from each other) are bonded to the boron atom via an oxygen atom. A boron-containing polyorganosilsesquioxane, characterized in that
(2) The boron-containing polyorganosilsesquioxane according to the above (1), wherein the molar ratio of silicon atom and boron atom is 5: 1 to 500: 1,
as well as
[0005]
(3) (a) General formula (I)
R1-BR2 2・ ・ ・ ・ ・ ・ (I)
(Wherein R1Is a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms or a chlorine atom, R2Represents a hydrocarbon group having 1 to 12 carbon atoms, and two R2May be the same as or different from each other, and may combine with each other to form a mono- or polycyclo ring)
A boron compound represented by formula (b): general formula (II)
RThree-Si-RFour Three・ ・ ・ ・ ・ ・ (II)
(Wherein RThreeHas at least one functional group selected from a hydrocarbon group having 1 to 12 carbon atoms, a hydroxyl group, a thiol group, an amino group, a cyano group, an isocyanate group, an isothiocyanate group, an epoxy group, and a (meth) acryloyloxy group. A hydrocarbon group having 1 to 12 carbon atoms, RFourIs a hydrolyzable group and represents a halogen atom or an alkoxyl group having 1 to 4 carbon atoms, and 3 RFourMay be the same or different from each other), and (c) the general formula (III)
H-Si-RFive Three・ ・ ・ ・ ・ ・ (III)
(Wherein RFiveRepresents an alkoxyl group having 1 to 4 carbon atoms or a chlorine atom, and three RFiveMay be the same or different from each other)
A silane compound represented by
(D) General formula (IV)
CH2= CH-R6・ ・ ・ ・ ・ ・ (IV)
(Wherein R6Is a C1-C10 hydrocarbon group having an isocyanate group or an isothiocyanate group)
Vinyl compounds represented byWithIn which a part of the silicon atom is —CH2CH2-R6Group (R6Represents a C1-C10 hydrocarbon group having an isocyanate group or an isothiocyanate group), and the boron-containing polyorganosilsesquioxane described in (1) or (2) above,
(4) The boron compound represented by the general formula (I) is dimethylhydroxyborane, diethylhydroxyborane, di-tert-butylhydroxyborane, diphenylhydroxyborane, dibenzylhydroxyborane, tert-butylethylhydroxyborane, 1- Hydroxyboracyclooctane, 8-hydroxy-8-borabicyclo [3.2.1] octane, dimethylmethoxyborane, diethylmethoxyborane, di-tert-butylmethoxyborane, diphenylmethoxyborane, dibenzylmethoxyborane, tert-butylethyl Boron-containing as described in (1) or (2) above, which is any one of methoxyborane, 1-methoxyboracyclooctane, 8-methoxy-8-borabicyclo [3.2.1] octane and dicyclohexylchloroborane Li organosilsesquioxane, and
(5) An adhesive composition comprising the boron-containing polyorganosilsesquioxane according to any one of (1) to (4) as an adhesive component is provided.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
  The boron-containing polyorganosilsesquioxane of the present invention is a novel compound having a structure in which a part of silicon atoms in a molecule is bonded to a boron atom through an oxygen atom.Is minutesIntroduced at the child endThe
  One organic group is bonded to the silicon atom in the molecule. Preferred examples of the organic group include a hydrocarbon group having 1 to 12 carbon atoms and a hydrocarbon group having 1 to 12 carbon atoms having a functional group. . Here, as a C1-C12 hydrocarbon group, a C1-C12 alkyl group, a C2-C12 alkenyl group, a C6-C12 carbon atom which has or does not have a substituent on an aromatic ring. Examples thereof include an aryl group and an aralkyl group having 7 to 12 carbon atoms which may or may not have a substituent on the aromatic ring. The alkyl group having 1 to 12 carbon atoms may be linear, branched or cyclic, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group and the like. The alkenyl group having 2 to 12 carbon atoms may be linear, branched or cyclic, and examples of the alkenyl group include vinyl group, allyl group, butenyl group, hexenyl group and octenyl group. Can be mentioned. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, tolyl group, xylyl group, and naphthyl group. Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group, phenethyl group, phenylpropyl group, And a naphthylmethyl group.
[0007]
On the other hand, examples of the functional group in the hydrocarbon group having 1 to 12 carbon atoms having a functional group include a hydroxyl group, a thiol group, an amino group, a cyano group, an isocyanate group, an isothiocyanate group, an epoxy group, and a (meth) acryloyloxy group. At least one selected from among the above. Examples of the hydrocarbon group having 1 to 12 carbon atoms into which these functional groups are introduced are the same as those exemplified in the description of the hydrocarbon group having 1 to 12 carbon atoms.
Examples of the hydrocarbon group having 1 to 12 carbon atoms having this functional group include 2-hydroxyethyl group, 3-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-cyanoethyl group, 3-cyanopropyl group, 2-cyano Propyl group, 3-isocyanatopropyl group, 3-isothiocyanatopropyl group, 3-glycidoxypropyl group, 3,4-epoxycyclohexyl group, 3-acryloyloxypropyl group, 3-methacryloyloxypropyl group, etc. It is done.
[0008]
  In the present invention, the organic group bonded to the silicon atom in the molecule may be the same or different. 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, Adhesion is improved.
  On the other hand, in the boron-containing polyorganosilsesquioxane of the present invention, a boron atom in which a part of silicon atoms are bonded through an oxygen atom is, MinutesChildOn the edgeExistsTheAlso, MinutesThe boron atom present at the child end contains organicTwo groupsOneTheThis organic group is a hydrocarbon group having 1 to 12 carbon atoms.It is.As this C1-C12 hydrocarbon group, the same thing as what was illustrated in description of the C1-C12 hydrocarbon group in the above-mentioned organic group couple | bonded with a silicon atom can be mentioned. The organic group may be a bulky hydrocarbon group, and examples of such a bulky hydrocarbon group include a tert-butyl group, a tert-amyl group, a tert-octyl group, a phenyl group, and a cyclohexyl group. In addition, the boron atom present at the terminal is a hydrocarbon group having 1 to 12 carbon atoms.flagIt may be bonded to an insulator to form a mono- or polycyclo ring bulky group with a boron atom. Examples of such bulky groups include a boracyclooctane-1-yl group and an 8-borabicyclo [3.2.1] octane-8-yl group.
  In such a boron-containing polyorganosilsesquioxane into which boron atoms are introduced, the bond between the boron atom and the oxygen atom is broken by moisture to generate a hydroxyl group at the terminal, and polymerization (polycondensation) proceeds. When used as an adhesive component, a moisture curable adhesive can be obtained.
[0009]
  The ratio of silicon atom and boron atom in the boron-containing polyorganosilsesquioxane of the present invention is selected in a molar ratio, usually in the range of 5: 1 to 500: 1. If the boron atom content is less than the above range, the effect of introducing boron atoms may not be sufficiently exhibited, while if it exceeds the above range, the performance as polyorganosilsesquioxane may be lost, which is not preferable. . For these reasons, the preferred ratio of silicon atoms and boron atoms is in the range of 5: 1 to 100: 1, with 5: 1 to 20: 1 being particularly preferred.
  The boron-containing polyorganosilsesquioxane of the present invention can be produced by the following two methods.
  First, the first method is (a) a general formula.
      R1-BR2 2・ ・ ・ ・ ・ ・ (I)
(Wherein R1Is a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms or a chlorine atom, R2 Is charcoal1 to 12 hydrocarbonsGroup2 R2May be the same or different from each other and may be bonded to each other to form a mono- or polycyclo ring.I)
A boron compound represented by formula (b): general formula (II)
      RThree-Si-RFour Three・ ・ ・ ・ ・ ・ (II)
(Wherein RThreeIsCarbon having at least one functional group selected from a hydrocarbon group having 1 to 12 carbon atoms or a hydroxyl group, a thiol group, an amino group, a cyano group, an isocyanate group, an isothiocyanate group, an epoxy group, and a (meth) acryloyloxy group Hydrocarbon group of 1 to 12, RFourIs a hydrolyzable group and represents a halogen atom or an alkoxyl group having 1 to 4 carbon atoms, and 3 RFourMay be the same or different from each otherI)Is a method of condensing a silicon compound represented by the formula:
[0010]
  In the compound represented by the general formula (I) of the component (a), R 1 ofExamples of the alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, and tert-butoxy group. Also R2 CharcoalExamples of the hydrocarbon group having 1 to 12 primes include the same ones as exemplified in the description of the hydrocarbon group having 1 to 12 carbon atoms in the organic group bonded to the silicon atom.
  Examples of the boron compound represented by the general formula (I) include a monofunctional boron compound such as the general formula (Ia).
      R1-BR7 2・ ・ ・ ・ ・ ・ (Ia)
(Wherein R1Is the same as above and R7Is a hydrocarbon having 1 to 12 carbon atomsGroup2 R7May be the same or different, and may be bonded to each other to form a mono- or polycyclo ring.I)
The compound represented by these can be mentioned.
[0011]
  Examples of the compound represented by the general formula (Ia) include dimethylhydroxyborane, diethylhydroxyborane, di-tert-butylhydroxyborane, diphenylhydroxyborane, dibenzylhydroxyborane, tert-butylethylhydroxyborane, 1-hydroxyboracyclooctane, 8-hydroxy-8-borabicyclo [3.2.1] octane, dimethylmethoxyborane, diethylmethoxyborane, di-tert-butylmethoxyborane, diphenylmethoxyborane, dibenzylmethoxyborane, tert- Examples include butylethylmethoxyborane, 1-methoxyboracyclooctane, 8-methoxy-8-borabicyclo [3.2.1] octane, dicyclohexylchloroborane and the like..
[0012]
  In the present invention, as the boron compound of component (a), one type may be selected from the boron compounds represented by the general formula (Ia), or two or more types may be selected and used.
[0013]
oneOn the other hand, in the compound represented by the general formula (II) of the component (b), RThreeExamples of the organic group represented by the formula include a hydrocarbon group having 1 to 12 carbon atoms and a hydrocarbon group having 1 to 12 carbon atoms having a functional group.
  Here, as a C1-C12 hydrocarbon group, the same thing as what was illustrated in description of a C1-C12 hydrocarbon group in the above-mentioned organic group couple | bonded with a silicon atom can be mentioned. Moreover, as a functional group in a C1-C12 hydrocarbon group which has a functional group, for example, a hydroxyl group, a thiol group, an amino group, a cyano group,Isocyanate groups, isothiocyanate groups,Examples thereof include at least one selected from an epoxy group and a (meth) acryloyloxy group.
[0014]
Examples of the hydrocarbon group having 1 to 12 carbon atoms having this functional group include 2-hydroxyethyl group, 3-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-cyanoethyl group, 3-cyanopropyl group, 2-cyano A propyl group, 3-glycidoxypropyl group, 3,4-epoxycyclohexyl group, 3-acryloyloxypropyl group, 3-methacryloyloxypropyl group and the like can be mentioned.
RFourAmong them, a chlorine atom is preferably exemplified, and the alkoxy group having 1 to 4 carbon atoms is the same as that exemplified in the description of the alkoxy group having 1 to 4 carbon atoms in the general formula (I). Can be mentioned.
[0015]
Examples of the silicon compound represented by the general formula (II) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and propyltriethoxy. Silane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 3-hydroxypropyltri Methoxysilane, 2-hydroxypropyltrimethoxysilane, 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 2-mercaptopropyltri Methoxysilane, 2-aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane, 2-dimethylaminoethyltrimethoxysilane, 4-dimethylaminobenzyltrimethoxysilane, 2-cyanoethyltrimethoxy Silane, 3-cyanopropyltrimethoxysilane, 2-cyanopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3,4-epoxycyclohexyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyl Examples include trialkoxysilanes such as oxypropyltrimethoxysilane and the corresponding trichlorosilanes. These silicon compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
[0016]
In the present invention, the boron compound represented by the general formula (I) as the component (a) in a predetermined ratio and the silicon compound represented by the general formula (II) as the component (b) are 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, methanesulfonic acid, etc., at a temperature of about 0-50 ° C., preferably 10-40. The boron-containing polyorganosilsesquioxane of the present invention can be obtained by condensation while partially hydrolyzing at a temperature of ° C.
In this reaction, when a monofunctional boron compound is used as the boron compound represented by the general formula (I) of the component (a), the terminal silicon atom of the polyorganosilsesquioxane is bonded via oxygen. Bonds to a boron atom.
[0017]
oneWhen the monofunctional boron compound represented by the general formula (Ia) is used as the boron compound represented by the general formula (I), and this is condensed with the silicon compound represented by the general formula (II) For example, the general formula (V)
[0018]
[Chemical 1]
[0019]
(Wherein RThreeAnd R7Is the same as described above, and n represents the degree of polymerization. )
The boron-containing polyorganosilsesquioxane represented by this can be manufactured.
Next, the second method includes (a) a boron compound represented by the general formula (I), (b) a silicon compound represented by the general formula (II), and (c) a general formula (III). )
H-Si-RFive Three・ ・ ・ ・ ・ ・ (III)
(Wherein RFiveRepresents an alkoxyl group having 1 to 4 carbon atoms or a chlorine atom, and three RFiveMay be the same or different.
A silane compound represented by formula (IV):
CH2= CH-R6  ・ ・ ・ ・ ・ ・ (IV)
(Wherein R6Represents a C1-C10 hydrocarbon group having a functional group. )
By adding a vinyl compound represented by the formula: —CH2CH2-R6Group (R6Is the same as above. ) Is introduced into the boron-containing polyorganosilsesquioxane.
[0020]
This method is a method of introducing a functional group that cannot be easily hydrolyzed and introduced into the boron-containing polyorganosilsesquioxane, such as an isocyanate group or an isothiocyanate group, in the first method described above. .
In the general formula (III) of the component (c), RFiveAs a C1-C4 alkoxyl group represented by these, the same thing as what was illustrated by description of a C1-C4 alkoxyl group in the said general formula (I) can be mentioned. Examples of the silane compound represented by the general formula (III) include trimethoxysilane, triethoxysilane, and trichlorosilane.
In the general formula (IV) of the component (d), R6As a functional group in a C1-C10 hydrocarbon group which has a functional group represented by this, an isocyanate group and an isothiocyanate group can be mentioned preferably especially. Preferred examples of the vinyl compound represented by the general formula (IV) include allyl isocyanate and allyl isothiocyanate.
[0021]
In the present invention, the boron compound represented by the general formula (I) as the component (a) in a predetermined ratio, the silicon compound represented by the general formula (II) as the component (b), and the general formula The trialkoxysilane represented by (III) is present in a solvent containing at least water, preferably 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, methanesulfonic acid, etc. The boron-containing polyorganosilsesquioxane is produced by condensation while partially hydrolyzing at a temperature of about 10 to 100 ° C., preferably 20 to 90 ° C. The resulting boron-containing polyorganosilsesquioxane can be recovered by adding an organic solvent such as hexane to precipitate.
In this reaction, when the monofunctional boron compound represented by the general formula (Ia) is used as the boron compound represented by the general formula (I), for example, the general formula (VI)
[0022]
[Chemical 2]
[0023]
(Wherein RThree, R7And n are the same as described above. )
Is obtained.
Next, to the boron-containing polyorganosilsesquioxane thus obtained, a vinyl compound represented by the general formula (IV) is used, for example, with a chloroplatinic acid catalyst, usually 50 to 200 ° C., preferably 80 By adding at a temperature of ˜150 ° C., —CH2CH2-R6Group (R6Is the same as above. Boron-containing polyorganosilsesquioxane is obtained.
In this case, when the vinyl compound is added to the compound represented by the general formula (VI), the general formula (VII)
[0024]
[Chemical 3]
[0025]
(Wherein RThree, R6, R7And n are the same as described above. )
A boron-containing polyorganosilsesquioxane represented by the following formula is obtained.
Such a boron-containing polyorganosilsesquioxane of the present invention has the property that the boron atom and the oxygen atom are cut by moisture, polymerization further proceeds, and gelation occurs. Therefore, it is useful as an adhesive component of a moisture curable adhesive. In addition, various functional groups can be introduced into the silicon atom, and thereby, when used as an adhesive component, the adhesion to the adherend can be improved.
The adhesive composition of the present invention contains the above-described boron-containing polyorganosilsesquioxane of the present invention as an adhesive component, and is a moisture curable type that is cured by moisture in the air.
This adhesive composition can contain an inorganic filler, a curing catalyst, a colorant, and the like as desired, as long as the object of the present invention is not impaired. Examples of the inorganic filler include silica, alumina, aluminum hydroxide, magnesium oxide, calcium carbonate, talc, mica, and clay.
[0026]
Furthermore, when the boron-containing polyorganosilsesquioxane, which is an adhesive component, is a compound in which a photopolymerizable functional group such as acryloyloxy group or methacryloyloxy group is introduced into a silicon atom, a photopolymerization initiator is added. During the bonding, the adhesive layer can be irradiated with an actinic ray such as ultraviolet rays to improve the adhesion to the adherend.
Further, 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. It can be made to ring, and adhesiveness with an adherend can be improved.
The curing time in the atmosphere of the adhesive composition of the present invention is normal temperature and is generally about 6 to 48 hours.
[0027]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Example 1
10 g of phenyltrimethoxysilane as a silicon compound and 1.3 g of diethylmethoxyborane as a boron compound are added to 24.5 g of a mixed solution having a toluene-water weight ratio of 22: 2.5, and 0.24 g of methanesulfonic acid is added as a catalyst. Then, the reaction was carried out at 23 ° C. for 3 hours and then at 90 ° C. for 6 hours while distilling off the low boiling point components.
After completion of the reaction, hexane was added to the reaction solution, and 6.2 g of the precipitated reaction product was recovered.
For this reaction product, the number average molecular weight was measured by the following method, and elemental analysis, infrared absorption spectrum (IR), and nuclear magnetic resonance spectrum (NMR) were measured.
(1) Number average molecular weight
The number average molecular weight in terms of polystyrene was measured by gel permeation chromatography (GPC) (TSK gel, G2500, G2000, G1000, THF solvent). For the measurement, HLC-8020 chromatography (manufactured by Tosoh Corporation) was used.
(2) Elemental analysis
The ratio of silicon atoms to boron atoms was measured by ICP spectroscopic analysis. The measurement was carried out by dispersing 0.01 g of the reaction product in 100 ml of water, adding a small amount of hydrogen fluoride for decomposition, and then adding water to about 100 ppm. For the measurement, ICP. S-1000IV (manufactured by Shimadzu Corporation) was used.
(3) Infrared absorption spectrum (IR)
FT • IR1600 (manufactured by PerkinElmer) was used.
(4) Nuclear magnetic resonance spectrum
  1H NMR and13For the measurement of C NMR, FX270 (manufactured by JEOL Ltd.) was used.29For the measurement of Si CP / MAS NMR, JNM A-500 (manufactured by JEOL Ltd.) was used.
The results are shown below.
Number average molecular weight
Mn = 1400
Elemental analysis
Si: B≈5: 1
Infrared absorption spectrum
3490cm-1(OH), 2950cm-1(-CH)
1600, 1440, 720, 700cm-1(Ph)
1110cm-1(C-Si), 1040cm-1(Si-O-Si)
Nuclear magnetic resonance spectrum
29Si CP / MAS NMR: -78 ppm From these results, the reaction product has an ethyl group bonded to boron at the terminal, a molar ratio of silicon atom to boron atom of 5: 1, and a polyorgano having a phenyl group. Silsesquioxane was identified.
[0028]
Example 2
The same procedure as in Example 1 was carried out using 10 g of 3-methacryloyloxypropyltrimethoxysilane as the silicon compound, 0.8 g of dicyclohexylchloroborane and 0.24 g of methanesulfonic acid as the boron compound, and 6.8 g of a reaction product was obtained. It was.
About this reaction product, while measuring the number average molecular weight similarly to Example 1, the elemental analysis, IR, and the measurement of NMR were performed. The results are shown below.
Number average molecular weight
Mn = 1200
Elemental analysis
Si: B≈10: 1
Infrared absorption spectrum
2954cm-1(CH), 1716cm-1(C = O)
1637cm-1(C = C), 1124cm-1(C-O-C)
1039cm-1(Si-O-Si)
Nuclear magnetic resonance spectrum
From these results, the reaction product is a polyorganosilsesquioxane having a cyclohexyl group bonded to boron and a molar ratio of silicon atom to boron atom of 10: 1 and having a 3-methacryloyloxypropyl group. It was identified.
[0029]
  Example 3
  The same procedure as in Example 1 was carried out 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. Got.
  About this reaction product, while measuring the number average molecular weight similarly to Example 1, the elemental analysis, IR, and the measurement of NMR were performed. The results are shown below.
Number average molecular weight
  Mn = 2000
Elemental analysis
  Si: B≈10: 1
Infrared absorption spectrum
  2950cm-1(CH), 1110cm-1(C-O-C)
  1040cm-1(Si-O-Si)
Nuclear magnetic resonance spectrum
   11 H NMR: 1.2 ppm (BCH2 CH Three )
                3.6 ppm (BCH 2 CHThree)
                1.5-2.0 ppm (CH2)
                2.5-3.5 ppm (CH2)
  13C NMR: 7.1 ppm (SiCH2), 8.2 ppm (CHThree)
                15.5 ppm (SiCH2 CH 2 )
                20.8ppm (CH2)
                43.0, 50.5 ppm (CH—O—CH2)
                73.1 ppm (CH2)
  29Si CP / MAS NMR: -78 ppm
  From these results, the reaction product has a polyorganosilsesquioxy having an ethyl group bonded to boron at the terminal, a molar ratio of silicon atom to boron atom of 10: 1, and a 3-glycidoxypropyl group. Identified as Sun.
[0030]
  Reference example 1
  The same reaction as in Example 1 was carried out using 7.2 g of 3-methacryloyloxypropyltrimethoxysilane as a silicon compound, 0.8 g of dihydroxyphenylborane as a boron compound and 0.35 g of concentrated hydrochloric acid as a catalyst, to obtain 7.2 g of a reaction product. It was.
  About this reaction product, while measuring the number average molecular weight similarly to Example 1, the elemental analysis, IR, and the measurement of NMR were performed. The results are shown below.
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)
  1040-1080cm-1(Si-O-Si)
Nuclear magnetic resonance spectrum
  1HNMR: 1.9 ppm (CH3), 4.0 ppm (OCH2)
                5.5, 6.0 ppm (CH = C)
                7.2 to 7.8 ppm (Ph-B)
  13C NMR: 8 ppm (CH2), 18 ppm (CH3)
                67,68 ppm (OCH2), 22 ppm (CH2)
                125,135 ppm (C = C)
                128,129.132 ppm (Ph-B)
  29Si CP / MAS NMR: -78 ppm
  From these results, the reaction product is a polyorganosilsesquioxy having a phenyl group bonded to boron at the end, a molar ratio of silicon atom to boron atom of 10: 1, and a 3-methacryloyloxypropyl group. Identified as Sun.
[0031]
  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 are mixed in 24.5 g of a toluene-water weight ratio of 22: 2.5. In addition, 0.24 g of methanesulfonic acid was added as a catalyst, and the mixture was reacted at 23 ° C. for 3 hours and then at 90 ° C. for 6 hours while distilling off low-boiling components. Next, hexane was added to the reaction solution, and 6.5 g of precipitated reaction product was recovered.
  Next, 6.5 g of the above reaction product was added as a solvent to 18 g of toluene, 2 g of allyl isocyanate as a vinyl compound and 1 mg of chloroplatinic acid as a catalyst were added and reacted at 80 ° C. for 3 hours, and then hexane. And precipitated to collect the reaction product. Yield 7.0g.
  About this reaction product, while measuring the number average molecular weight similarly to Example 1, the elemental analysis, IR, and the measurement of NMR were performed. The results are shown below.
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), 1040 cm-1(Si-O-Si)
Nuclear magnetic resonance spectrum
   11 H NMR: 1.5-2.0 ppm (CH2)
                2.5-3.5 ppm (CH2)
                7.25 to 7.5 ppm (Ph-B)
  13C NMR: 7.1 ppm (SiCH2)
                15.5 ppm (SiCH2CH2)
                17.9 ppm (SiCH2)
                43.0,50.5 ppm (CH—O—CH2)
                73.1 ppm (CH2), 38.3 ppm (CH 2 -N)
                122ppm (C = O)
                128-135 ppm (Ph-B)
  29Si CP / MAS NMR: -78 ppm
  From these results, the reaction product has a phenyl group bonded to boron at the terminal, a molar ratio of silicon atom to boron atom of 8: 1, and a polyglyceride having 3-glycidoxypropyl group and isocyanate group. It was identified as an organosilsesquioxane.
[0032]
Comparative Example 1
10 g of phenyltrimethoxysilane was added to 24.5 g of a mixed solution having a weight ratio of toluene: water of 22: 2.5, and 0.24 g of methanesulfonic acid was further added as a catalyst. 7.0 g of silsesquioxane was obtained.
[0033]
  Example 6-8,10
  Example 13,5And Reference Example 1Each of the boron-containing polyorganosilsesquioxanes obtained in 1 above was obtained by using a 2 mm thick glass plate (manufactured by Partec Co., Ltd.), a polyethylene terephthalate film [manufactured by Toray Industries, Inc., trade name: Lumirror, thickness 188 μm] and a polycarbonate film [ Three types of adherends manufactured by Sansho Bussan Co., Ltd., trade name: Lexan 8101, thickness 100 μm] were applied so as to have a thickness of 20 μm, and an adhesive layer was provided.
  Example 2And Reference Example 1In advance, 0.14 g of α-hydroxycyclohexyl phenyl ketone was previously added as a photoinitiator, and the adhesive layer was irradiated with ultraviolet rays of 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 epoxy groups.
  After curing under the conditions shown in Table 1 under conditions of 23 ° C. and 50% relative humidity, a 200-hour weathering acceleration test was conducted with a sunshine weatherometer WEL-SUN-HCH (manufactured by Suga Test Instruments Co., Ltd.). Thereafter, the adhesion and hardness to the three types of adherends were evaluated according to the following methods. The results are shown in Table 1.
(5) Adhesiveness
  The cellophane adhesive tape peeling test (cross cut method) was evaluated 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 5 times with # 0000 steel wool, and the surface was visually observed and evaluated according to the following criteria.
            ○ No scratches on the surface
            △ A part of the surface is scratched.
            × Scratches are observed on the entire surface.
[0034]
Comparative Examples 2-4
Examples 6-10 using water glass No. 3 (Comparative Example 2), 3-methacryloyloxypropyltrimethoxysilane (Comparative Example 3) and polyorganosilsesquioxane obtained in Comparative Example 1 (Comparative Example 4) In the same manner as described above, each of the glass plate, the polyethylene terephthalate film and the polycarbonate film was applied to a thickness of 20 μm, and an adhesive layer was provided.
After curing under the conditions shown in Table 1 under conditions of 23 ° C. and 50% relative humidity, a 200-hour weather resistance acceleration test was conducted with a sunshine weatherometer in the same manner as in Examples 6 to 10, The adhesion to the adherend and the hardness were evaluated. The results are shown in Table 1.
[0035]
[Table 1]
[0036]
【The invention's effect】
The boron-containing polyorganosilsesquioxane of the present invention is a novel compound that has excellent heat resistance and weather resistance, and adhesion in a moisture-curable adhesive composition having good adhesion to an adherend. Useful as an ingredient.
The adhesive composition of the present invention is a moisture curable type containing the above boron-containing polyorganosilsesquioxane as an adhesive component, and adheres an organic-inorganic material, an organic-organic material, and an inorganic-inorganic material. Adhesive well and excellent in heat resistance and weather resistance.

Claims (5)

  1. (A) General formula (I)
    R 1 -B-R 2 2 (I)
    (Wherein R 1 represents a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms or a chlorine atom, R 2 represents a hydrocarbon group having 1 to 12 carbon atoms, and two R 2 s may be the same as or different from each other; And may combine with each other to form a mono- or polycyclo ring) and (b) a general formula (II)
    R 3 -Si-R 4 3 (II)
    (In the formula, R 3 is at least selected from a hydrocarbon group having 1 to 12 carbon atoms or a hydroxyl group, a thiol group, an amino group, a cyano group, an isocyanate group, an isothiocyanate group, an epoxy group, and a (meth) acryloyloxy group). A hydrocarbon group having 1 to 12 carbon atoms having one kind of functional group, R 4 is a hydrolyzable group, and 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. It is characterized in that a part of the silicon atom at the end of the polyorganosilsesquioxane obtained by condensing the silicon compound represented by the formula (1) may be bonded to a boron atom through an oxygen atom. Boron-containing polyorganosilsesquioxane.
  2.   The boron-containing polyorganosilsesquioxane according to claim 1, wherein the ratio of silicon atom to boron atom is 5: 1 to 500: 1 in molar ratio.
  3. (A) General formula (I)
    R 1 -B-R 2 2 (I)
    (Wherein R 1 represents a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms or a chlorine atom, R 2 represents a hydrocarbon group having 1 to 12 carbon atoms, and two R 2 s may be the same as or different from each other; And may be bonded to each other to form a mono or polycyclo ring)
    A boron compound represented by formula (b): general formula (II)
    R 3 -Si-R 4 3 (II)
    (In the formula, R 3 is at least selected from a hydrocarbon group having 1 to 12 carbon atoms or a hydroxyl group, a thiol group, an amino group, a cyano group, an isocyanate group, an isothiocyanate group, an epoxy group, and a (meth) acryloyloxy group). A hydrocarbon group having 1 to 12 carbon atoms having one kind of functional group, R 4 is a hydrolyzable group, and 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. And (c) the general formula (III)
    H-Si-R 5 3・ ・ ・ ・ ・ ・ (III)
    (Wherein R 5 represents an alkoxyl group having 1 to 4 carbon atoms or a chlorine atom, and three R 5 may be the same or different from each other)
    A silane compound represented by formula (IV):
    CH 2 = CH-R 6 (IV)
    (In the formula, R 6 represents a C 1-10 hydrocarbon group having an isocyanate group or an isothiocyanate group)
    A is a in represented by vinyl compounds made by vulcanizing with a part of the silicon atoms -CH 2 CH 2 -R 6 group (R 6 is from 1 to 10 carbon atoms having an isocyanate group or isothiocyanate group The boron-containing polyorganosilsesquioxane according to claim 1 or 2, wherein a hydrocarbon group is introduced).
  4.   The boron compound represented by the general formula (I) is dimethylhydroxyborane, diethylhydroxyborane, di-tert-butylhydroxyborane, diphenylhydroxyborane, dibenzylhydroxyborane, tert-butylethylhydroxyborane, 1-hydroxyboracyclo. Octane, 8-hydroxy-8-borabicyclo [3.2.1] octane, dimethylmethoxyborane, diethylmethoxyborane, di-tert-butylmethoxyborane, diphenylmethoxyborane, dibenzylmethoxyborane, tert-butylethylmethoxyborane, The boron-containing polyorganosyl according to claim 1 or 2, which is any one of 1-methoxyboracyclooctane, 8-methoxy-8-borabicyclo [3.2.1] octane, and dicyclohexylchloroborane. Sukiokisan.
  5.   An adhesive composition comprising the boron-containing polyorganosilsesquioxane according to any one of claims 1 to 4 as an adhesive component.
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US8080604B2 (en) * 2007-03-02 2011-12-20 Lintec Corporation Adhesive containing ladder-type polysilsesquioxane and adhesive sheet
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US8349985B2 (en) 2009-07-28 2013-01-08 Cheil Industries, Inc. Boron-containing hydrogen silsesquioxane polymer, integrated circuit device formed using the same, and associated methods
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