JPH0995608A - Improvement of stretch characteristic of hardened propylene oxide polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the improvement (the enlargement) of a stretch strength and the improvement (the reduction of stickiness) of a residual tack by adjusting a content of silicone functional groups in a polymer by blending or reacting a specific silicone compound. SOLUTION: A propylene oxide polymer having at least one reactive silicone functional group in a molecule is cured after mixed with a compound capable of forming a trimethylsilanol (CH3 )3 SiOH by reacting with water in an amount of >=0.3 times the reactive silicone functional group in the polymer in terms of a silanol equivalent, and a silanol condensation catalyst. Further, it is preferable that at least one kind of vinyl monomer selected from compounds of formula I [R<1> is H, a halogen or a 1-10C (substituted) aliphatic hydrocarbon; R<2> is same as R<1> or a (substituted) monovalent aromatic hydrocarbon, etc.] and formula II [R<3> is a monovalent hydrocarbon, etc.; R<4> is an organic residue having a polymerizable double bond; X is OH, etc. ; (a)=0, 1-3; (b) 0, 1, 2; (m)=0-13] be polymerized in the presence of the propylene oxide polymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for improving the tensile properties of a cured product of a propylene oxide polymer having a reactive silicon functional group. More specifically, a propylene oxide polymer having at least one reactive silicon functional group in the molecule is reacted with water to add a compound having one silanol group in the molecule and a silanol condensation catalyst, and then cured. And a method for improving the tensile properties of a cured product of a propylene oxide-based polymer having a reactive silicon functional group.

[0002]

2. Description of the Related Art As will be described later, many methods for producing a propylene oxide polymer having at least one reactive silicon functional group in the molecule have been proposed and already produced industrially. For example, there is an organic polymer (trade name: MS polymer) manufactured and sold by Kanegafuchi Chemical Industry Co., Ltd. in which the main chain is polyoxypropylene and a methoxysilyl functional group is bonded to the end. However, the elongation of the cured product and the residual tack (stickiness) of the surface are not sufficient for some applications due to the influence of the compounding composition and use conditions, and improvement thereof has been desired.

[0003]

The inventors of the present invention have conducted extensive studies on improvement of tensile properties (high elongation) and improvement of residual tack (reduction of stickiness) of the polymer, and as a result, a specific silicone has been obtained. The inventors have found that the object can be achieved by blending or reacting compounds and adjusting the silicon functional group content of the polymer, and thus arrived at the present invention.

That is, the present invention adds a compound having one silanol group in the molecule and a silanol condensation catalyst to a propylene oxide polymer having at least one reactive silicon functional group in the molecule by reacting with water. The present invention relates to a method for improving the tensile properties of a cured product of a propylene oxide-based polymer having a reactive silicon functional group, which is characterized by curing after curing.

Propylene oxide-based polymers having at least one reactive silicon functional group in the molecule are, for example, Japanese Patent Publications Nos. 45-36819, 46-12154, and 4-4.
9-32678, JP-A-50-156599, and 51-
78561, 54-6096, 55-13767,
55-13768, 55-32123, 55-1
23620, 55-125121, 55-1310
21, the same 55-131022, the same 55-135135,
It can be obtained by the method proposed in JP-A-55-137129, but preferably has a molecular weight of 300 to 30,000. More preferably, the molecular weight is 500-15
000 of a propylene oxide-based polymer and having a reactive silicon functional group attached to the end of the molecule.

The reactive silicon functional group as used herein means condensation such as a hydrolyzable group or silanol group bonded to a silicon atom in the presence of moisture or a cross-linking agent, if necessary, by using a catalyst or the like. It can be defined as a group that causes a reaction, and is typically represented by the general formula (3)

[0007]

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(In the formula, R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms selected from an alkyl group, an aryl group and an aralkyl group, or (R ′) ₃ SiO— (R ′ is 1 to carbon atoms.
20 representing the same or different monovalent hydrocarbon groups), X is a hydroxyl group or a different or the same type of hydrolyzable group, and a is selected from 0, 1, 2 or 3 An integer, b is an integer selected from 0, 1 or 2, and m is an integer selected from 0 to 13).

The propylene oxide polymer having such a reactive silicon functional group is represented by, for example, the general formula (4).

[0010]

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A silicon hydride compound represented by the formula (wherein R ³ , X, a, b and m are the same as above) is represented by the general formula (5)

[0012]

[Chemical 6]

[In the formula, Z is -R ^6- , -R ⁶ OR ^6- ,

[0014]

[Chemical 7]

(R ⁶ is the same or different carbon number 1 to 20
Divalent hydrocarbon group), R ⁵ is a hydrogen atom or has 1 carbon atom.
To 20 substituted or unsubstituted monovalent organic groups, c is an integer of 0 or 1)], a so-called propylene oxide polymer having an olefin group is used as a catalyst with a platinum compound such as chloroplatinic acid. It can be produced by addition by a hydrosilylation reaction.

Other than the above, as a method for producing a propylene oxide polymer having a reactive silicon functional group, (i) a hydroxyl group-terminated propylene oxide polymer is reacted with a polyisocyanate compound such as toluene diisocyanate to obtain an isocyanate group. A terminal propylene oxide polymer is prepared, and then the isocyanate group is added to the compound represented by the general formula (6)

[0017]

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(In the formula, W is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group and an amino group (primary or secondary), b, R ³ , R ⁶ and X are the same as above).
A method of reacting a W group of a silicon compound represented by: (Ii) a method of adding the mercapto group of the silicon compound represented by the general formula (6), in which W is a mercapto group, to the olefin group of the propylene oxide polymer having the olefin group represented by the general formula (5), And (iii) the general formula (7) is added to the hydroxyl group of the hydroxyl group-terminated propylene oxide polymer.

[0019]

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(Wherein R ³ , R ⁶ , X and b are the same as above)
And the like, but the present invention is not limited to these methods described above.

R ³ in the general formula (4) has 1 to 2 carbon atoms.
The same or different monovalent hydrocarbon groups of 0, and specific examples thereof include alkyl groups such as methyl and ethyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl group; aralkyl groups such as benzyl group. And so on.

Further, R ³ is represented by the general formula (R ') ₃ SiO-
(R 'represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, which is the same or different and may be different) and may be a triorganosiloxy group. X in the general formula (4) is a silanol group or a different or the same type of hydrolyzable group, and specific examples thereof include, for example, a halogen group, a hydride group, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, Examples thereof include an amide group, an aminooxy group, a mercapto group and an alkenyloxy group. Specific examples of the hydrogenated silicon compound represented by the general formula (4) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and trimethylsiloxydichlorosilane; trimethoxysilane, triethoxysilane and methylmethoxy. Silane, Phenyldimethoxysilane, 1,3,3,5,5,7,7-
Alkoxysilanes such as heptamethyl-1,1-dimethoxytetrasiloxane; methyldiacetoxysilane,
Acyloxysilanes such as trimethylsiloxymethylacetoxysilane; bis (dimethylketoximate) methylsilane, bis (cyclohexylketoximate) methylsilane, bis (diethylketoximate) ketoximatesilanes such as trimethylsiloxysilane; dimethylsilane , Trimethylsiloxymethylsilane, 1,1-
Examples thereof include, but are not limited to, hydrosilanes such as dimethyl-2,2-dimethyldisiloxane; alkenyloxysilanes such as methyltri (isopropenyloxy) silane.

In the method of reacting the silicon hydride compound represented by the general formula (4) with the propylene oxide polymer having an olefin group represented by the general formula (5), after reacting them, Part or all of the X groups can be converted to further hydrolyzable or hydroxyl groups. For example, when the X group is a halogen group or a hydride group, a method of converting it into an alkoxy group, an acyloxy group, an aminooxy group, an alkenyloxy group, a hydroxyl group or the like for use is preferable.

In the general formula (5), R ⁵ is a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group,
It is particularly preferably a hydrogen atom. Z has 1 to 1 carbon atoms
40, preferably 1 to 20 divalent organic groups,

[0025]

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It is preferable that it is, and a methylene group is particularly preferable.

As a specific method for producing the propylene oxide polymer having an olefin group represented by the general formula (5), the method disclosed in JP-A-54-6097, ethylene oxide, propylene oxide or the like can be used. When polymerizing an epoxy compound, a method of introducing an olefin group into a side chain by adding an olefin group-containing epoxy compound such as allyl glycidyl ether and copolymerizing can be exemplified.

Generally, the main chain of the alkylene oxide polymer is essentially of the general formula --RO-- (wherein R is a divalent organic group, most of which is a hydrocarbon having 1 to 4 carbon atoms). Most preferred when it is a group). Specific examples of R include —CH ₂ —,
-CH ₂ CH ₂ -,

[0029]

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And the like. In the present invention

[0031]

[Chemical 12]

However, other repeating units may be included. The main chain of the alkylene oxide polymer is 1
The repeating unit may be composed of only one kind of repeating unit, or may be composed of two or more kinds of repeating units.

[0033]

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Is preferred. The propylene oxide polymer preferably has a molecular weight of 500 to 30,000, more preferably 3,000 to 15,000.

The above propylene oxide polymer having a reactive silicon functional group may be used alone or
It is also possible to use two or more species in combination. Also, a mixture containing 50% by weight or more of the polymer can be used. Further, a propylene oxide polymer obtained by polymerizing various vinyl monomers in the presence of the propylene oxide polymer can also be used. Regarding the method for producing the propylene oxide polymer, see JP-A-59-78223 and JP-A-59-848.
48, Japanese Patent Application No. 59-84849, specifically, in the presence of a propylene oxide polymer having at least one reactive silicon functional group in the molecule, the following general Obtained by polymerizing one or more vinyl-based monomers selected from the group consisting of vinyl-based monomers represented by the formula (1) and vinyl-based monomers represented by the general formula (2). You can

[0036]

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(In the formula, R ¹ is a hydrogen atom, a halogen atom,
Alternatively, a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, R ² is the same group as R ¹ , a substituted or unsubstituted monovalent aromatic hydrocarbon group, an alkenyl group, or a carboxyl group. Group, acyloxy group, alkoxycarbonyl group, nitrile group, pyridyl group, amide group, glycidoxy group)

[0038]

[Chemical 15]

(In the formula, R ³ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 20 carbon atoms, an aryl group and an aralkyl group, or (R ′) ₃ SiO— (R ′ is 1 to carbon atoms.
20 represents the same or different kinds of monovalent hydrocarbon groups), R ⁴ is an organic residue having a polymerizable double bond, X is a hydroxyl group or a different or same kind of hydrolyzable group. , A is an integer selected from 0, 1, 2 or 3, b is an integer selected from 0, 1 or 2, m is 0
Indicates an integer selected from ~ 13)

Specific examples of the vinyl monomer represented by the general formula (1) include ethylene, propylene, isobutylene, butadiene, chloroprene, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid, vinyl acetate, acrylonitrile, Pyridine, styrene, chlorostyrene,
2-methylstyrene, divinylbenzene, methyl acrylate, ethyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, benzyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid Isobutyl, 2-ethylhexyl methacrylate,
2-hydroxyethyl methacrylate, methacrylic acid-2
-Hydroxyethyl, benzyl methacrylate, glycidyl methacrylate, acrylamide, methacrylamide, n-methylol acrylamide and the like can be exemplified.

In the case of applying to the sealing material composition and the adhesive material composition, especially the general formula (8)

[0042]

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(In the formula, R ⁷ is a substituted or unsubstituted monovalent aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms,
R ¹ is preferably a so-called acrylic acid or methacrylic acid ester-based monomer represented by the above). That is,
R ¹ is preferably a hydrogen atom or a methyl group, and the substituted or unsubstituted monovalent hydrocarbon group represented by R ⁷ is a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, 1- Ethylpropyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, isooctyl group, 3,5,5-trimethylhexyl group, 2
-Ethylhexyl group, decyl group, dodecyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, diaminoethyl group, diethylaminoethyl group, glycidyl group, tetrahydrofurfuryl group, benzyl group, and the like, n-butyl And a 2-ethylhexyl group are preferred.

Specific examples of the vinyl monomer represented by the general formula (2) include

[0045]

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[0046]

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Examples include

[0048]

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Is preferred.

Polymerization can be carried out by a usual method, and specifically, a method using a radical initiator, a method using irradiation with ultraviolet rays, X-rays or γ-rays can be adopted. As the radical initiator, specifically, a radical polymerization initiator having a reactive silicon functional group, benzoyl peroxide, benzoyl hydroperoxide, di-t-butyl peroxide, di-t-butyl hydroperoxide, Peroxides such as acetyl peroxide, lauroyl peroxide, hydrogen peroxide, etc .; Azo compounds such as azobisisobutyronitrile; Persulfates, peroxide compounds such as di-isopropylperoxy-dicarbonate, etc. Can be mentioned.

The solvent can be used if necessary. When used, a solvent inert to both the propylene oxide polymer having a reactive silicon functional group and the vinyl monomer is preferable, and specifically, ethers, hydrocarbons, acetic acid esters, etc. Is mentioned.

The polymerization temperature is not particularly limited, and in the case of the polymerization method and the method using a radical initiator, the optimum temperature can be set depending on the type of the initiator used, but it is usually 50 to 150 ° C. preferable. If necessary, the polymerization degree of the vinyl-based monomer can be adjusted by using a chain transfer agent such as a mercaptan or a halogen-containing compound and a chain transfer agent having a reactive silicon functional group. The vinyl monomer may be charged all at once, or may be charged in a divided manner or continuously for the purpose of adjusting the amount of heat generated.

The compound having one silanol group in the molecule used in the present invention is not particularly limited as long as it is a compound having one ≡SiOH group in the molecule. In particular,

[0054]

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General formula (R) ₃ SiOH (wherein
R is the same or different and may be represented by a substituted or unsubstituted alkyl group or aryl group),

[0056]

[Chemical 21]

Cyclic polysiloxane compounds containing silanol groups such as:

[0058]

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Examples thereof include chain polysiloxane compounds containing silanol groups. The higher the ≡SiOH group content, the greater the effect with the same amount of addition, (CH ₃ ).
₃ SiOH, (CH ₃ CH ₂ ) ₃ SiOH, etc. are preferable, and are easy to handle and stable in air.

[0060]

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Is preferred.

A compound capable of reacting with water to form a compound having one silanol group in the molecule is known as a so-called silica agent.

[0063]

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Etc. can be preferably used, but from the content of ≡SiOH contained in the hydrolysis product,

[0065]

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Is particularly preferred.

These compounds are effective for improving the tensile properties of the cured product, that is, for lowering the modulus and increasing the elongation, and for improving the residual tack. The resulting silanol compound reacts with the reactive silicon functional group in the propylene oxide-based polymer, and by capping, the number of cross-linking points of the cured propylene oxide-based polymer is decreased, and the molecular weight between cross-linking points is increased. As a result, low modulus and high elongation are expected to be achieved. Although the reason why the residual tack is improved is not clear, in the present invention, since the molecular weight between the cross-linking points becomes large and the modulus decreases, there are few free molecular chains / branches not involved in the cross-linking, and therefore the residual tack is It is thought that it is decreasing.

The amount of these compounds added may vary depending on the expected physical properties of the cured product. With respect to the number of moles of the reactive silicon functional group contained in the propylene oxide-based polymer,
Silanol equivalent (≡SiOH) may be used to determine the amount to be added. In order to achieve low modulus and high elongation, the silanol group equivalent is usually 0 with respect to the number of moles of the reactive silicon functional group. The addition amount of the compound is determined so as to be 0.1 to 0.9 times. However, it must be considered that the number of reactive silicon functional groups that remain uncapped by the compound remains at least one in the molecule. It is possible to use the silanol group equivalent in excess of 0.9 times, but it is not advantageous from the economical point of view. In particular, a composition used in an amount of 0.3 times or more, preferably 0.5 times or more, the silanol group equivalent may not be sufficiently cured, and may be in an unhardened state.

However, surprisingly, the thin layer portion on the surface of the post-cured product is sufficiently cured to be completely tack-free. That is, a semi-cured product is obtained in which the surface portion is completely cured, but the interior is in a final cured state. The composition can be suitably used as a so-called mastic type sealant for applications such as a sealing material.

There are roughly three addition methods. One is to simply add the compound to the propylene oxide-based polymer. The properties of the compound and the like may be uniformly dispersed and dissolved by devising heating and stirring conditions and the like as necessary. In this case, it is not necessary to have a completely uniform and transparent state, and even in the opaque state, the purpose can be achieved if the particles are sufficiently dispersed. If necessary, a dispersibility improving agent such as a surfactant may be used in combination.

The second method is a method in which a predetermined amount of the compound is added and mixed when the final product is used. For example, when it is used as a two-component type sealing material, the base and the curing agent are mixed. Besides, the compound can be mixed and used as a third component.

The third method is to react the compound with a propylene oxide polymer in advance. If necessary, a tin catalyst, a titanate ester catalyst, an acid or a basic catalyst may be used in combination, and a water content may be added. Thus, in the case of a compound which produces a compound containing a silanol group, the object can be achieved by adding a necessary amount of water and heating and devolatilizing under reduced pressure.

As the catalyst which can be used here, titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; organic tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate. Lead octylate; butylamine, octylamine, dibutylamine,
Monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-
Amine compounds such as tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,3-diazabicyclo (5,4,6) undecene-7 (DBU) or salts thereof such as carboxylic acid; excess polyamine And a low molecular weight polyamide resin obtained from a polybasic acid; a reaction product of an excess polyamine and an epoxy compound; a silane coupling agent having an amino group, for example, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) amino. Specific examples thereof include silanol condensation catalysts such as propylmethyldimethoxysilane. These may be used alone or in combination of two or more.

The composition of the present invention thus obtained is filled with a reinforcing or non-reinforcing agent such as white carbon, carbon black, calcium carbonate, titanium oxide, talc, asbestos, glass fiber, etc., if necessary. By mixing various additives such as adhesives, plasticizers and antioxidants, ultraviolet absorbers, pigments, flame retardants, etc., adhesives, adhesives, paints, sealant compositions, waterproof materials, spraying materials, and molds It can be usefully used as a material and a cast rubber material.
Among them, the application to the sealing material composition and the pressure-sensitive adhesive composition is particularly useful.

When the curable composition of the present invention is used as a sealing material, if necessary, a plasticizer, a filler, a reinforcing agent, an anti-sagging agent, a coloring agent, an antiaging agent, an adhesion promoter, a curing catalyst. , A physical property adjusting agent and the like may be added.

As the plasticizer, phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylexyl) phthalate, butyl benzyl phthalate and butyl phthalyl butyl glycolate are used for the purpose of controlling physical properties and properties. Non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate; Polyalkylene glycol esters such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Chloride Paraffins; hydrocarbon-based oils such as alkyldiphenyl and partially hydrogenated terphenyl may be used alone or in admixture of two or more, but they are not always necessary. It should be noted that these plasticizers can be added at the time of polymer production.

As fillers and reinforcing agents, heavy and light calcium carbonates; calcium carbonate surface-treated with fatty acids, resin acids, cationic surfactants, anionic surfactants, etc .; magnesium carbonate; talc; oxidation Titanium; barium sulphate; alumina; metal powder such as aluminum, zinc, iron; bentonite; kaolin clay; fumed silica; quartz powder; carbon black etc.
One kind or two or more kinds are used. In particular, it is possible to make a sealing material having excellent transparency by using a filler and a reinforcing material that give transparency such as fumed silica.

Hydrogenated castor oil derivative as an anti-sagging agent;
Calcium stearate, aluminum stearate,
Examples thereof include metal soaps such as barium stearate, but they may not be necessary depending on the purpose of use or the blending of fillers and reinforcing materials.

As the colorant, a usual inorganic material, if necessary,
Organic pigments, dyes, etc. can be used.

As the physical property adjusting agent, various silane coupling agents, for example, alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltrisilane. Alkylisopropenoxysilanes such as isopropenoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane; γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane , Vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercap Alkoxysilanes having a functional group such as propyl methyl dimethoxy silane; silicone varnishes; polysiloxanes and the like are added as needed. By using the physical property adjusting agent, the hardness of the composition of the present invention when cured can be increased, or the hardness can be lowered to provide elongation.

As the adhesion promoter, the polymer itself according to the present invention has adhesiveness to glass, ceramics other than glass, metals and the like, and it is possible to adhere to a wide range of materials by using various kinds of primers. However, it is not always necessary to use various kinds of epoxy resins, phenol resins, various silane coupling agents, alkyl titanates, aromatic polyisocyanates, etc., for more kinds of adherends. Can also improve adhesion.

As a curing catalyst, titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin maleate,
Organotin compounds such as dibutyltin diacetate, tin octylate, tin naphthenate; lead octylate; butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine. , Cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,3-diazabicyclo ( 5, 4, 6) amine compounds such as undecene-7 (DBU) or salts thereof such as carboxylic acids; low molecular weight obtained from excess polyamine and polybasic acid Liamide resin; reaction product of excess polyamine and epoxy compound; silane coupling agent having amino group, for example, known silanol such as γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane One kind or two or more kinds of condensation catalysts may be used as necessary.

A solvent may be blended for the purpose of improving workability and decreasing the viscosity. For example, an aromatic hydrocarbon solvent such as toluene or xylene, ethyl acetate, butyl acetate, amyl acetate, cellosolve acetate, etc. And ester type solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone. You may use those solvents at the time of polymer manufacturing. Although it is not necessary to add an antioxidant, a usual antioxidant or ultraviolet absorber may be used.

Such a sealing material composition may be prepared as a one-component type in which all compounding ingredients are previously compounded and sealed and stored, and then cured by moisture in the air after construction, or as a curing agent, a separate curing catalyst and filler. It is also possible to prepare a two-component type in which components such as a plasticizer and water are mixed in advance and the compounding material (material) and the polymer composition are mixed before use. When the sealant composition is a one-component type, all the compounding ingredients are pre-compounded, so that the compounding ingredients containing water are dehydrated and dried before use, or dehydrated by reducing pressure during compounding and kneading. Is preferred. When the sealing material composition is a two-component type, it is not necessary to add a curing catalyst to the main agent containing a polymer, so there is little concern about gelation even if the compounding agent contains some water, When long-term storage stability is required, dehydration drying is preferred.

As a dehydration and drying method, a heat drying method is suitable for a solid substance such as powder, and a reduced pressure dehydration method for a liquid substance or a dehydration method using synthetic zeolite, activated alumina, silica gel or the like. Alternatively, a small amount of an isocyanate compound may be blended to react the isocyanate group with water for dehydration. In addition to such dehydration drying method, methanol,
Lower alcohols such as ethanol; Add alkoxysilane compounds such as n-propyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane By doing so, the storage stability is further improved.

When the composition of the present invention is used as a pressure-sensitive adhesive, a curing catalyst used in the above-mentioned sealing material, if necessary,
Antiaging agents, plasticizers, reinforcing materials, physical property modifiers, solvents and the like may be used. Depending on the purpose, petroleum resin such as rosin ester resin, phenol resin, xylene resin, xylene phenol resin, coumarone resin, aromatic system, aliphatic / aromatic copolymer system and alicyclic system, terpene resin, terpene phenol resin Well-known additives that are added to ordinary pressure-sensitive adhesive compositions, such as low molecular weight polystyrene resin, may be added.

The pressure sensitive adhesive composition can be widely applied to tapes, sheets, labels, foils and the like. That is, for example, a solvent-free liquid type, a solvent type, an emulsion type or a substrate material such as synthetic resin film or modified natural product film, paper, all kinds of cloth, metal foil, metallized plastic foil, asbestos or glass fiber cloth. The pressure-sensitive adhesive composition may be applied in the form of a hot-melt type or the like, exposed to moisture or water, and cured at room temperature or heat.

(Examples and Effects) Hereinafter, examples will be specifically described.

Example 1 80% of all Suizei

[0090]

[Chemical formula 26]

To 100 g of a reactive silicon-terminated propylene oxide polymer having an average molecular weight of 8200, which is a group, 1.5 g of triphenylsilanol was added, and 90 ° C.
After stirring for 2 hours, it became completely transparent and uniform. To this, 150 g of fatty acid-treated colloidal charcoal (manufactured by Shiraishi Industry Co., Ltd., trade name: CCR), 65 g of dioctyl phthalate,
6 g of water-added castor oil, 1 g of styrenated phenol (manufactured by Ouchi Shinko Co., Ltd., trade name: Nocrac-SP), 3 g of tin octylate, and 1 g of lauryl amine were added, and three paint rolls were passed three times to thoroughly knead .

In accordance with the method defined in JIS-A5758, type 2 H type was prepared (adherend: anodized aluminum, primer: APZ-730, manufactured by Nippon Unicar Co., Ltd.), and subjected to predetermined curing. After that, it was subjected to a tensile test.

The results are shown in Table 1 together with the comparative example in which triphenylsilanol was not added. It can be seen from Table 1 that the addition of triphenylsilanol significantly improved the tensile properties and achieved low modulus and high elongation.

[0094]

[Table 1]

Examples 2 to 4 The same experiment as in Example 1 was carried out except that various silanol compounds shown in Table 2 were used instead of using 1.5 g of triphenylsilanol. The results are shown in Table 2.

[0096]

[Table 2]

When any of the silanol compounds is added, a remarkable effect is obtained in lowering the modulus and increasing the elongation.

Examples 5 to 7 Similar to Example 1 except that, instead of using 1.5 g of triphenylsilanol, various compounds shown in Table 3 which react with water to produce a silanol group-containing compound are used. We conducted an experiment. The results are shown in Table 3.

[0099]

[Table 3]

Reference Example 1 80% of all ends

[0101]

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100 g of a reactive silicon-terminated propylene oxide polymer having an average molecular weight of 8200 is placed in a reaction vessel, devolatilized under reduced pressure, replaced with nitrogen, and then heated to 90 ° C. and stirred. N- that was prepared separately there
Butyl acrylate 96.9 g, γ-methacryloxypropyldimethoxysilane 0.8 g, γ-mercaptopropyldimethoxysilane 1.6 g, AIBN 0.5 g
The solution consisting of is added dropwise over 2 hours under a nitrogen atmosphere.
AIBN 0.0 and 15 minutes and 30 minutes after the dropping, respectively.
Dissolve 25 g each in 4 times by weight acetone and add.
After the addition is completed, stirring is continued for 30 minutes to complete the polymerization reaction.
The obtained polymer was a pale yellow, transparent viscous liquid and had a residual monomer amount of 0.7% by GC analysis and a viscosity of 490 poise (23 ° C.).

Examples 8 and 9 To 100 g of the organic polymer obtained in Reference Example 1 and having on average at least one reactive silicon functional group in the molecule, 100 g of fatty acid-treated colloidal calcium carbonate (Shiraishi Kogyo ( stock)
Manufactured, trade name: CCR) 120 g, titanium oxide 30 g, butylbenzyl phthalate 60 g, hydrogenated castor oil 6 g,
After adding 1 g of styrenated phenol and thoroughly kneading through 3 paint rolls 3 times, a separately prepared curing catalyst consisting of 3 g of tin octylate and 1 g of lauryl amine and the silicon compound shown in Table 4 were added sufficiently. Knead. J
Based on IS-A5758, a type 2 H-type test piece (adherent: glass, primer: APZ-730, manufactured by Nippon Unicar) was prepared, and after predetermined curing, a tensile test was performed. The results are shown in Table 4 together with a comparative example in which no silicon compound is added.
It was shown to.

[0104]

[Table 4]

Example 10 80% of all ends

[0106]

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With respect to 100 g of a reactive silicon-terminated propylene oxide polymer having an average molecular weight of 8200 as a group,
Fatty acid-treated colloidal calcium carbonate (manufactured by Shiraishi Industry Co., Ltd., trade name: CCR) 120 g, titanium oxide 30 g, dioctyl phthalate 60 g, hydrogenated castor oil 6 g, styrenated phenol 1 g are added, and three paint rolls are passed three times. After fully kneading, separately prepared tin octylate 3
and 3 g of bis (trimethylsilyl) acetamide and a curing catalyst composed of 1 g of laurylamine and kneaded thoroughly.

According to JIS-A5758, Type 2 H-shaped test piece (adherent: glass, primer: APZ-73)
0, made by Nippon Unicar) and subjected to prescribed curing.
After curing for 1 week at 23 ° C./50% RH, the surface was completely tack-free, but the interior was post-cured and the spacer could not be removed. It was cured at 50 ° C for 1 week without removing the spacer, but the interior was not cured, and then it was left still at 90 ° C or in a gear oven for 1 month.
After all, the interior was hardened and the spacer could not be removed.

A similar experiment was conducted using 5 g of hexamethylsilazane instead of using 3 g of bis (trimethylsilyl) acetamide. As a result, in the same manner, the surface was hardened and became tack-free, but the inner part was hardened. Met. Thus, it can be seen that a mastic type sealant can be produced by increasing the amount of the silicon compound used in the present invention.

Example 11 80% of all ends

[0111]

[Chemical 29]

With respect to 100 g of a reactive silicon-terminated propylene oxide polymer having an average molecular weight of 8200 as a group,
Add 1.5 g of triphenylsilanol and stir at 90 ° C. for 1 hour under nitrogen atmosphere.

After confirming that triphenylsilanol was completely dissolved and uniformly dispersed, 0.1 g of dibutyltin dilaurate was added, and the mixture was devolatilized at 90 ° C. under reduced pressure for about 5 hours. After cooling, a separately prepared curing catalyst composed of 3 g of tin octylate and 1 g of laurylamine is added and mixed sufficiently. After defoaming, pour into a 3mm thick frame,
After left at room temperature for 1 day, it is cured at 50 ° C. for 2 days to obtain a cured product. A No. 3 dumbbell according to JIS-K6301 was punched out from the same cured product sheet and subjected to a tensile test (pulling speed: 500 mm / min). The strength at break was 4.7 kg / cm ³ and the elongation was 760%. When a similar test was conducted on a polymer not treated with triphenylsilanol,
The strength at break is 5.6 kg / cm ³ and the elongation is 260%, so that the effect of the present invention can be clearly confirmed.

[Procedure amendment]

[Submission date] May 2, 1996

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction contents]

That is, according to the present invention, a propylene oxide polymer having at least one reactive silicon functional group in the molecule is reacted with water to form trimethylsilanol (CH ₃ ) ₃
A compound capable of forming SiOH (this compound is propylene
For reactive silicon functional groups in oxide polymers,
It is used at least 0.3 times as much as the equivalent amount of the lanol group) and a silanol condensation catalyst are added and then cured, and the tensile properties of a cured product of a propylene oxide polymer having a reactive silicon functional group are characterized. Regarding how to improve.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

Further, R ³ is represented by the general formula (R ') ₃ SiO-
(R 'represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, which is the same or different and may be different) and may be a triorganosiloxy group. X in the general formula (4) is a silanol group or a different or the same type of hydrolyzable group, and specific examples thereof include, for example, a halogen group, a hydride group, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, Examples thereof include an amide group, an aminooxy group, a mercapto group and an alkenyloxy group. Specific examples of the hydrogenated silicon compound represented by the general formula (4) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and trimethylsiloxydichlorosilane; trimethoxysilane, triethoxysilane and methylmethoxy. Silane, Phenyldimethoxysilane, 1,3,3,5,5,7,7-
Alkoxysilanes such as heptamethyl-1,1-dimethoxytetrasiloxane; methyldiacetoxysilane,
Acyloxysilanes such as trimethylsiloxymethylacetoxysilane; bis (dimethylketoximate) methylsilane, bis (cyclohexylketoximate) methylsilane, bis (diethylketoximate) trimethyloxysilane such as trimethylsiloxysilane; dimethylsilane , Trimethylsiloxymethylsilane, 1,1-
Hydrosilane such as dimethyl-2,2-dimethyldisiloxane; the like Application Benefits alkenyloxy silanes such as (isopropenyloxy) silane and the like, but is not limited thereto.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction item name] 0053

[Correction method] Change

[Correction contents]

[0053] Generally, the compound having one silanol group in the molecule, Ru compound der having one ≡SiOH groups in the molecule. In concrete terms,

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

[Correction contents]

Examples thereof include chain polysiloxane compounds containing silanol groups. The higher the ≡SiOH group content, the more the silanol group is used at the same amount.
_{High, (CH 3) 3 SiOH,} (CH 3 CH 2) 3 Si
OH is preferable, and it is easy to handle and stable in air.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction contents]

Are useful .

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0066

[Correction method] Change

[Correction contents]

Is particularly preferred. In the present invention, water
Reacted with trimethylsilanol (CH ₃ ) ₃ SiOH
(CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ which can be formed
Such compounds are used.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0069

[Correction method] Change

[Correction contents]

However, surprisingly, the thin layer portion on the surface of the post-cured product is sufficiently cured to be completely tack-free. That is, a semi-cured product is obtained in which the surface portion is completely cured, but the interior is in a final cured state. The compositions, for example in applications such as sealants, a so-called, and can be suitably used <br/> as Masuchitsuku type sealant. In the present invention, trimethylsila reacts with water.
The compound capable of forming a nor (CH ₃ ) ₃ SiOH is described above.
Reactive Silicon Functional Groups in Propylene Oxide Polymers
The silanol group equivalent is 0.3 times or more.

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0089

[Correction method] Change

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Reference Example 1 80% of all ends

[Procedure amendment 10]

[Document name to be amended] Statement

[Correction target item name]

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[0094]

[Table 1]

[Procedure amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0095

[Correction method] Change

[Correction contents]

[0095] Instead of using a reference example 2-4 triphenylsilanol 1.5g, but using various silanol compounds shown in Table 2, ginseng
KoTsuta The same experiment as considered Example 1. The results are shown in Table 2.

[Procedure amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0096

[Correction method] Change

[Correction contents]

[0096]

[Table 2]

[Procedure amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0098

[Correction method] Change

[Correction contents]

[0098] Example 1-3 triphenylsilanol instead of 1.5g use, shown in Table 3, similar but using various compounds capable of reacting with water to generate a silanol group-containing compounds Example 1 We conducted an experiment. The results are shown in Table 3.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

[0099]

[Table 3]

[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0100

[Correction method] Change

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Reference Example 5

[Procedure Amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0103

[Correction method] Change

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Reference Example 6 and Example 4 100 g of the organic polymer obtained in Reference Example 5 having an average of at least one reactive silicon functional group in the molecule was added to fatty acid-treated colloidal calcium carbonate (Shiraishi). Industry Co., Ltd.
Made, product name: CCR) 120 g, titanium oxide 30 g, butylbenzyl phthalate 60 g, hydrogenated castor oil 6 g,
After adding 1 g of styrenated phenol and thoroughly kneading it through three paint rolls three times, a separately prepared curing catalyst consisting of tin octylate 30 and 1 g of laurylamine and the silicon compound shown in Table 4 were added sufficiently. Knead. J
Based on IS-A5758, a type 2 H-type test piece (adherent: glass, primer: APZ-730, manufactured by Nippon Unicar) was prepared, and after predetermined curing, a tensile test was performed. The results are shown in Table 4 together with a comparative example in which no silicon compound is added.
It was shown to.

[Procedure amendment 17]

[Document name to be amended] Statement

[Correction target item name] 0104

[Correction method] Change

[Correction contents]

[0104]

[Table 4]

[Procedure amendment 18]

[Document name to be amended] Statement

[Correction target item name] 0105

[Correction method] Change

[Correction contents]

Example 5 80% of all ends

[Procedure amendment 19]

[Document name to be amended] Statement

[Correction target item name] 0110

[Correction method] Change

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Reference Example 7 80% of all ends

[Procedure amendment 20]

[Document name to be amended] Statement

[Name of item to be corrected] 0113

[Correction method] Change

[Correction contents]

After confirming that triphenylsilanol was completely dissolved and uniformly dispersed, 0.1 g of dibutyltin dilaurate was added, and the mixture was devolatilized at 90 ° C. under reduced pressure for about 5 hours. After cooling, a separately prepared curing catalyst composed of 3 g of tin octylate and 1 g of laurylamine is added and mixed sufficiently. After defoaming, pour into a 3mm thick frame,
After left at room temperature for 1 day, it is cured at 50 ° C. for 2 days to obtain a cured product. A No. 3 dumbbell according to JIS-K6301 was punched out from the same cured product sheet and subjected to a tensile test (pulling speed: 500 mm / min). The strength at break was 4.7 kg / cm ³ and the elongation was 760%. When a similar test was conducted on a polymer not treated with triphenylsilanol,
The strength at break is 5.6 kg / cm ³ and the elongation is 260%, which is low.
It can be seen that the modulus and high elongation have been achieved.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsuhiko Isayama 4-8-7 Chikushigaoka, Kita-ku, Kobe-shi, Hyogo (72) Inventor Takahisa Iwahara 712-1 Nagata, Higashi-tarumizu-cho, Tarumi-ku, Kobe-shi, Hyogo

Claims (4)

[Claims] 1. A compound and a silanol condensation catalyst capable of reacting moisture with a propylene oxide polymer having at least one reactive silicon functional group in the molecule to produce a compound having one silanol group in the molecule. A method for improving the tensile properties of a cured product of a propylene oxide-based polymer having a reactive silicon functional group, characterized in that the cured product is added. 2. A compound represented by the general formula (1): embedded image in the presence of a propylene oxide-based polymer. (In the formula, R ¹ is a hydrogen atom, a halogen atom, or a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, R ² is the same group as R ¹ , a substituted or unsubstituted 1 A vinyl monomer represented by a valent aromatic hydrocarbon group, an alkenyl group, a carboxyl group, an acyloxy group, an alkoxycarbonyl group, a nitrile group, a pyridyl group, an amide group or a glycidoxy group), and a general formula (2) [Chemical 2] (In the formula, R ³ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 20 carbon atoms, an aryl group and an aralkyl group, or (R ′) ₃ SiO— (R ′ is the same type having 1 to 20 carbon atoms). Or represents a different monovalent hydrocarbon group), R ⁴ is an organic residue having a polymerizable double bond, X is a hydroxyl group or a different or similar hydrolyzable group, and a is An integer selected from 0, 1, 2 or 3, b
Is an integer selected from 0, 1 or 2 and m is an integer selected from 0 to 13), and 1 or 2 or more vinyl-based monomers selected from the group consisting of vinyl-based monomers The method according to claim 1, which is a propylene oxide-based polymer obtained by polymerization. 3. A compound capable of reacting with water to form a compound having one silanol group in the molecule is: The method of claim 1 wherein: 4. A methoxysilyl group (≡SiOCH ₃ ) is used as the reactive silicon functional group in the propylene oxide polymer.
The method of claim 1 wherein: