JP2000063661A - Composition for organic/inorganic hybrid polyurethane and organic/inorganic hybrid polyurethane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which can give an organic/inorganic hybrid polyurethane improved in adhesion to an inorganic substrate without detriment to flexibility by mixing a polyurethane having an alkoxysilyl at each terminal with a hydrolyzable alkoxysilane. SOLUTION: The polyurethane used is desirably the reaction product of a polyurethane having an isocyanate group at each terminal with an amino- containing alkoxysilane. In the polyurethane, the polyol component is desirably a polyester polyol. The organic polyisocyanate compound used is exemplified by methylene diisocyanate. The hydrolyzable alkoxysilane desirably comprises a tetraalkoxysilane and/or a condensate thereof and is used in an amount of, desirably, about 1-50 pts.wt. in terms of the formed silica based on 100 pts.wt. polyurethane. The curing catalyst used is desirably an organic acid catalyst and is exemplified by formic acid or acetic acid. The organic/inorganic hybrid polyurethane composition is useful as an adhesive used to bond a plastic, glass, a metal or concrete.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composition for organic-inorganic hybrid polyurethane and an organic-inorganic hybrid polyurethane. The composition for organic-inorganic hybrid polyurethane of the present invention can be used in various fields such as paints, inks, coating agents and adhesives. In particular, it is useful as an adhesive, and means for adhering various base materials such as plastic, glass, metal, mortar, concrete, leather material, wood, paper, rubber, woven fabric, and non-woven fabric, specifically, the various base materials described above. It can be used as an adhesive, a sealing agent, etc. In particular,
INDUSTRIAL APPLICABILITY The composition for organic-inorganic hybrid polyurethane of the present invention is useful as an adhesive, a sealant or the like for an inorganic substance such as glass, metal, mortar, metal vapor-deposited polymer film, concrete or the like, or an inorganic base material containing an inorganic substance as a main component.

[0002]

2. Description of the Related Art Conventionally, various organic polymers have been used as means for adhering various base materials in various fields. For example, polyurethane has been widely used as an adhesive, a sealing agent, etc. because it has rubber elasticity and excellent mechanical strength. The rubber elasticity of such polyurethane is exhibited because the hard segment having toughness is insolubilized from the matrix of the soft segment having flexibility to form a domain. However, polyurethane generally does not have sufficient adhesiveness to an inorganic base material.

Polyurethane is generally a material having low heat resistance, and there is a problem in that rubber elasticity disappears due to melting of the hard segment at 100 to 160 ° C., resulting in liquefaction. Therefore, polyurethane could not be applied to the bonding field under high temperature environment.

As a method for improving the adhesiveness of such a polyurethane to an inorganic base material, there has been proposed a method of using a polyurethane having a silane coupling agent reacted at its end (JP-A-2-145660). . However, although the silane coupling agent improves the adhesion to an inorganic base material to some extent, it cannot sufficiently improve the heat resistance.

On the other hand, as a method for improving the heat resistance of polyurethane, the proportion of the hard segment is increased,
There is a method of introducing many urea bonds into the hard segment. However, such a method is not preferable since it causes insolubilization of the solvent in the polyurethane and increases the viscosity.

In addition to the above method, as a method of imparting heat resistance to polyurethane, there is a method of applying a sol-gel method to synthesize a hybrid with an inorganic glass. According to such a sol-gel method, the number of grown glass particles is several n.
Since the glass particles are very small, the transparency of the organic polymer is not lost even when the glass particles are dispersed in polyurethane. That is, by utilizing hydrolysis and polycondensation of hydrolyzable alkoxysilane such as tetraethoxysilane, a hybrid body in which inorganic glass is dispersed in polyurethane by a so-called filler effect is manufactured. However, when the organic-inorganic hybrid body of polyurethane is manufactured by the sol-gel method, the performance such as heat resistance is improved by the filler effect, but the flexibility of the soft segment peculiar to polyurethane is lost because the glass particles are dispersed throughout the polyurethane. In some cases, it becomes brittle and does not function sufficiently as an adhesive or the like. For example, JP-A-6
JP-A-136321 describes a method for producing an organic / inorganic hybrid body using an alcohol sol solution obtained by dissolving a hydrophilic soft segment polyurethane, a hydrolyzable alkoxysilane, and optionally a catalyst in a lower alcohol. However, the obtained organic / inorganic hybrid is inflexible and brittle.

Further, in Japanese Patent Application Laid-Open No. 9-291131, an organic / inorganic hybrid is prepared by reacting a polyol having hydroxyl groups at both ends with a metal alkoxysilane containing an isocyanate group and alkoxytitanium by a sol-gel method. It is also proposed that However, in such a method, the organic / inorganic hybrid body contains titanium oxide generated from alkoxytitanium, and therefore has poor light resistance.

[0008]

DISCLOSURE OF THE INVENTION The present invention aims at improving the adhesiveness to various base materials including an inorganic base material while maintaining the flexibility of polyurethane, and at the same time, it is excellent in heat resistance and light resistance. It is an object to provide an inorganic hybrid polyurethane and a composition capable of providing an organic / inorganic hybrid polyurethane.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, have previously modified polyurethane with an alkoxysilane and prepared a sol with a hydrolyzable alkoxysilane. It was found that an organic-inorganic hybrid polyurethane meeting the above purpose can be obtained by curing by the gel method. It is considered that a part of the hydrolyzable alkoxysilane in the composition becomes a silanol group and contributes to the adhesiveness with the inorganic compound. Most of the silica produced by the reaction of hydrolyzable alkoxysilane is introduced into the hard segment domain of polyurethane to form a composite domain, and the composite domain and the soft segment form a two-layer separated (sea-island) structure and a hybrid body. Become. Due to the two-layer separation (sea-island) structure, the soft segment of the polyurethane that constitutes the matrix of the hybrid does not contain silica and thus retains its flexibility, while the hard segment of the polyurethane retains only that domain due to the composite domain with silica. Can be made tougher and the heat resistance can be improved. The present invention is based on such new findings,
It has been completed.

That is, the present invention comprises (1) a composition having an alkoxysilyl group at both ends thereof, and (2) a composition for an organic-inorganic hybrid polyurethane containing a hydrolyzable alkoxysilane; and further containing a curing catalyst. An organic-inorganic hybrid polyurethane obtained by curing the composition; an adhesive composition comprising the composition; a substrate and a substrate, and the composition containing the curing catalyst. After contacting via the composition, the composition is cured and the substrates are bonded to each other.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION (1) The polyurethane having alkoxysilyl groups at both ends of the present invention is not particularly limited as long as it has a structure having alkoxysilyl groups at both ends of the polyurethane. Such (1) polyurethane is
For example, (a) a polyurethane having a functional group selected from an isocyanate group, a hydroxyl group and an amino group at both ends is reacted with (b) an alkoxysilane having a functional group capable of reacting with the terminal functional group of the polyurethane. It is obtained by

The polyurethane (a) can be produced by reacting a polyol component, an organic polyisocyanate compound, and further with a chain extender, and the polyol component, the organic polyisocyanate compound, and the chain extender are appropriately added. By adjusting, a desired functional group can be introduced at the terminal.

The polyol component forms a soft segment of polyurethane, and various compounds having two or more hydroxyl groups can be used, but it is preferable to use a high molecular polyol. Examples of the high-molecular polyols include polyether polyols such as polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran, etc .; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,
3-propanediol, 1,3-butanediol, 1,
4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol,
1,6-hexanediol, octanediol, 1,4
-Saturated or unsaturated known low-molecular-weight glycols such as butynediol and dipropylene glycol, or n
-Alkyl glycidyl ethers such as butyl glycidyl ether and 2-ethylhexyl glycidyl ether, monocarboxylic acid glycidyl esters such as versatic acid glycidyl ester, adipic acid, maleic acid, fumaric acid, phthalic anhydride, isophthalic acid, and terephthalic acid ,
Polyester polyols obtained by dehydration condensation with dibasic acids such as succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid and suberic acid, or their corresponding acid anhydrides and dimer acids. Polyester polyols obtained by ring-opening polymerization of cyclic ester compounds; Others Polycarbonate polyols, polybutadiene diols, polyisoprene diols, polychloroprene diols, polybutadiene glycol hydrides, polyisoprene glycol hydrides, and other polyolefin diols , A glycol obtained by adding ethylene oxide or propylene oxide to bisphenol A, an alkyl (meth) acrylate in the presence of a chain transfer agent having two or more hydroxyl groups and one chain transfer group such as a mercapto group. Various radical-polymerizable unsaturated monomer to macromonomer such as acrylic polymer obtained by polymerizing, polyalkoxy silanes such as polydimethylsiloxane, castor oil polyols, chlorinated polypropylene polyols and the like. Among such polymer polyols, polyester polyols are preferably used in the present invention because of their excellent adhesiveness. The number average molecular weight of these polymer polyols is usually 1
It is preferably 500 or more, and more preferably 2000 or more. The number average molecular weight is preferably 6000 or less.

The organic polyisocyanate compound forms a hard segment of polyurethane. Examples of the organic polyisocyanate compound include various compounds such as a chain aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, an aromatic polyisocyanate, an araliphatic polyisocyanate, and a polyisocyanate obtained from an amino acid derivative.

Specific examples of the chain aliphatic diisocyanate include methylene diisocyanate, isopropylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-. Examples include trimethylhexamethylene diisocyanate and dimerisocyanate in which the carboxyl group of dimer acid is replaced with an isocyanate group. Specific examples of the cycloaliphatic diisocyanate include cyclohexane-
1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-di (isocyanatomethyl) cyclohexane, methylcyclohexanediisocyanate and the like can be mentioned. Specific examples of the aromatic diisocyanate include:
Dialkyldiphenylmethane diisocyanates such as 4,4′-diphenyldimethylmethane diisocyanate,
Tetraalkyldiphenylmethane diisocyanate such as 4,4′-diphenyltetramethylmethane diisocyanate, 1,5-naphthylene diisocyanate, 4,4 ′
-Diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4
Examples include-tolylene diisocyanate and 2,6-tolylene diisocyanate. Specific examples of the araliphatic diisocyanate include xylylene diisocyanate, m
-Tetramethylxylylene diisocyanate and the like. Specific examples of the diisocyanate obtained from the amino acid derivative include lysine diisocyanate.

The chain extender usually has 2 carbon atoms.
It is preferred to use low molecular weight polyols and / or low molecular weight polyamines of the order of -6. As the low molecular weight polyol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,
3-propanediol, 1,3-butanediol, 1,
4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol,
Low molecular weight glycols such as 1,6-hexanediol, trihydric alcohols such as glycerin, butanetriol, pentanetriol, hexanetriol, trimethylolethane, and trimethylolpropane; tetrahydric or higher alcohols such as pentaerythritol and sorbitol. To be As the low molecular weight polyamine, amine compounds such as ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine; 2-hydroxyethylethylenediamine, 2-hydroxyethyl Propylenediamine, di-2-hydroxyethylethylenediamine, di-
Examples thereof include diamine compounds having a hydroxyl group such as 2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine and di-2-hydroxypropylethylenediamine. The amount of these chain extenders is preferably 20% by weight or less, and more preferably 15% by weight or less, based on the total amount of the hydrophobic polymer diol and the organic polyisocyanate compound.

The polyurethane (a) of the present invention can be obtained by reacting a polymer polyol, an organic polyisocyanate compound and, if necessary, a chain extender. The reaction can adopt a general polyurethane manufacturing method,
In addition to batch charging, when a chain extender is used, a urethane prepolymer method in which a polymer polyol and an organic polyisocyanate compound are reacted in advance can also be adopted. In addition, by appropriately adjusting the amount of each component used, an isocyanate group is added to the terminal of the (a) polyurethane of the present invention,
Either a hydroxyl group or an amino group is introduced. In the (a) polyurethane of the present invention, if necessary, a dialkylamine such as di-n-butylamine; a chain length terminating agent such as monohydric alcohol such as ethanol or isopropanol may be used. To the extent that the purpose can be achieved, (1)
A part of the polyurethane may be a polyurethane unmodified with alkoxysilyl at one end or both ends. The number average molecular weight of the thus obtained (a) polyurethane is 1
It is preferably about 800 to 100,000.

The above-mentioned (a) an alkoxysilane having a functional group capable of reacting with the terminal functional groups of the polyurethane, which is reacted with a polyurethane having a functional group at both ends,
(A) A polyurethane having a functional group corresponding to the functional group is appropriately selected and used. That is, when the terminal functional group of (a) polyurethane is an isocyanate group,
The alkoxysilane having a hydroxyl group and / or an amino group (b) is used, and when the terminal functional group of the polyurethane (a) is a hydroxyl group or an amino group, an alkoxysilane having an isocyanate group (b) is used.

Examples of the alkoxysilane having an amino group include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropidimethylethoxysilane, 3-aminopropylmethyldiethoxysilane and 4-amino. Butyltriethoxysilane, 3-aminopropyltris (trimethylsiloxy) silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane , N
Examples thereof include-(6-aminohexyl) -aminopropyltrimethoxysilane, 3- (m-aminophenoxy) propyltrimethoxysilane and aminophenyltrimethoxysilane. Examples of the alkoxysilane having an isocyanate group include 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmonomethyldiethoxysilane, and 3-isocyanatopropyldimethylethoxysilane.

In the present invention, (1) a polyurethane having an alkoxysilyl group at both ends is used as a polyurethane having an isocyanate group at both ends for the sake of simplicity of synthesis.
It is preferable to use a product obtained by reacting an alkoxysilane having an amino group.

(2) As the hydrolyzable alkoxysilane, those generally used in the sol-gel method can be used. For example, the general formula: R ¹ _n Si (OR ² )
_4-n (In the formula, n represents an integer of 0 to 2, R ¹ is a lower alkyl group which may have a functional group directly bonded to a carbon atom,
Aryl group, unsaturated aliphatic residue. It may be the same or different. R ² represents a hydrogen atom or a lower alkyl group. Examples thereof include compounds represented by the formula (1) or partial condensates thereof. The lower alkyl group means a linear or branched alkyl group having 6 or less carbon atoms.

Specific examples of such (2) hydrolyzable alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane and other tetraalkoxysilanes, and methyltrimethoxy. Silane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane,
Ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4 Trialkoxysilanes such as epoxycyclohexylethyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane,
Examples thereof include diethyldiethoxysilane and partial condensates thereof. Among these, tetraalkoxysilanes, partial condensates thereof, and the like are preferable because they have good affinity with the domain formed by the hard segment of polyurethane. In particular, tetramethoxysilane, tetraethoxysilane or their partial condensates are preferred.

(2) The amount of the hydrolyzable alkoxysilane used is such that when the silica produced by condensation of the hydrolyzable alkoxysilane exceeds (a) the total amount of domains formed by the hard segment of polyurethane, the silica adheres. Since the particles are aggregated and precipitated in the layers and phase-separated, and a good adhesive state cannot be obtained, the amount is 1 to 50 parts by weight in terms of silica to be produced based on 100 parts by weight of (a) polyurethane. Is preferred. It is more preferably 3 parts by weight or more, and further preferably 30 parts by weight or less.

The composition for organic-inorganic hybrid polyurethane of the present invention containing (1) polyurethane and (2) hydrolyzable alkoxysilane can be used as it is as a solventless composition, and Can be used as a solution composition in which is dissolved in a soluble organic solvent. Whether the adhesive composition of the present invention is used in the form of a solvent-free composition or a solution composition may be appropriately determined according to various uses to which the composition of the present invention is applied. When used for an adhesive composition or the like, it is preferably used as a solution composition in view of handleability.

The organic solvent used in the solution composition is such that (1) polyurethane and (2) hydrolyzable alkoxysilane can be dissolved and (2) hydrolysis of hydrolyzable alkoxysilane can proceed. The one that can contain water is used. For example, aromatic solvents such as benzene, toluene, xylene; ester solvents such as ethyl acetate, butyl acetate; alcohol solvents such as methanol, ethanol, isopropanol, n-butanol; acetone, methyl ethyl ketone, diethyl ketone,
Examples thereof include ketone solvents such as methyl isobutyl ketone; amide solvents such as dimethylformamide; sulfoxide solvents such as dimethyl sulfoxide; ether solvents such as dimethyl ether and diethyl ether. Usually, the solid content concentration of a solution composition is about 10 to 40% by weight.

When the composition for organic-inorganic hybrid polyurethane of the present invention is used for various purposes, in general, in order to accelerate curing, (2) curing capable of hydrolyzing and condensing a hydrolyzable alkoxysilane. A catalyst is used. Examples of the curing catalyst include organic acid catalysts such as formic acid, acetic acid, propionic acid, paratoluenesulfonic acid, and methanesulfonic acid, inorganic acid catalysts such as boric acid and phosphoric acid, and alkaline catalysts. In particular, when (1) is used, silica tends to be induced in the domain formed by the hard segment of (1) polyurethane, which is preferable. By hydrolyzing a hydrolyzable alkoxysilane with an organic acid catalyst, silanol residues are increased, and (1) the hydrogen-bonding interaction with the hard segment of polyurethane is strengthened. Among these organic acid catalysts, formic acid, acetic acid, and paratoluenesulfonic acid are preferable.

The curing catalyst may be used in so-called catalytic amounts. That is, the amount of the catalyst used can be appropriately determined depending on the activity of the catalyst used. Usually, the molar ratio to the hydrolyzable alkoxysilane used is about 0.001 to 5 mol% of paratoluenesulfonic acid having a high catalytic ability,
0.01 to 50 mol% with formic acid and acetic acid, which have low catalytic ability
Used to a degree. The timing of addition of the curing catalyst is not particularly limited, and (1) polyurethane and (2) when preparing a solventless composition from a hydrolyzable alkoxysilane,
(1) Polyurethane and (2) Hydrolyzable alkoxysilane and the like may be added when dissolved in an organic solvent to prepare a solution composition, or may be added immediately before the composition is used for various purposes. .

The composition for organic-inorganic hybrid polyurethane of the present invention contains a viscosity modifier, a plasticizer, an antibacterial agent, an antifungal agent, a leveling agent, an antifoaming agent, and a coloring agent as long as the effects of the present invention are not impaired. If necessary, various organic and inorganic additives such as agents, stabilizers, solvents for adjusting the solubility, etc. can also be added. In addition, it goes without saying that the components that are usually used can be mixed and used in various applications.

The composition for organic-inorganic hybrid polyurethane of the present invention thus prepared can be used for various purposes, but it is preferably used as an adhesive composition, an adhesive, a sealing agent and the like. In particular, it has excellent adhesiveness to substrates such as metal, mortar, and metal evaporated polymer film.

The composition for organic-inorganic hybrid polyurethane of the present invention is cured (hydrolyzed and condensed) to obtain an organic-inorganic hybrid polyurethane. The water required for curing is
It can be added as appropriate, or one existing in the air can be used. Although the curing temperature may be room temperature, it may be adequately adjusted to 3 when paying attention to the evaporation of the silica precursor.
It is also possible to heat at a temperature of 00 ° C. or lower. In addition, when the substrate and the substrate are brought into contact with the composition for organic-inorganic hybrid polyurethane of the present invention, the substrate is brought into contact with the substrate through the composition and then cured to form the substrate. Let it adhere. The base material can be appropriately selected and used according to various uses.

[0031]

Industrial Applicability According to the present invention, it is possible to provide an organic / inorganic hybrid polyurethane having excellent adhesiveness to various base materials including an inorganic base material. In addition, the organic / inorganic hybrid polyurethane has the flexibility of polyurethane, and is also excellent in heat resistance and light resistance.

[0032]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. In the examples, parts and% are based on weight unless otherwise specified.

Production Example 1 A 3L 4-necked Kolben equipped with a thermometer and a cooling tube was placed under the trade name CLAPOL P2010 (number average molecular weight 200).
0, polyester polyol consisting of adipic acid and 3-methyl-1,5-pentanediol, manufactured by Kuraray Co., Ltd.)
148 parts, trade name Praxel 220 (number average molecular weight 20
00, adipic acid, a polyester polyol consisting of ε-caprolactone and neopentyl glycol, manufactured by Daicel Chemical Industries Ltd.) 222 parts and isophorone diisocyanate 102.7 parts are reacted at 80 ° C. for 5 hours under a nitrogen stream to produce an isocyanate end. A urethane prepolymer was obtained. Next, 383 parts of toluene and 383 g of methyl ethyl ketone were added to the system, and after cooling to 50 ° C. with good stirring, 38.8 parts of isophoronediamine and 27.2 parts of 3-aminopropyltriethoxysilane were added to 383 parts of 2-propanol. Add the dissolved solution dropwise over 10 minutes,
Then, the mixture was reacted at the same temperature for 1 hour. Thus, a polyurethane (alkoxysilyl group-containing) solution having a number average molecular weight of about 17,000 and a solid content of 30% was obtained.

Production Example 2 Reaction was performed in the same manner as in Production Example 1 except that 19.8 parts of 3-aminopropyldimethylethoxysilane was used in place of 3-aminopropyltriethoxysilane in Production Example 1. A polyurethane (alkoxysilyl group-containing) solution having an average molecular weight of about 17,000 and a solid content of 30% was obtained.

Comparative Production Example 1 The reaction was performed in the same manner as in Production Example 1 except that 6.71 parts of dibutylamine was used in place of 3-aminopropyltriethoxysilane in Production Example 1, and the number average molecular weight was about 170000. A polyurethane solution having a solid content of 30% was obtained.

Example 1 100 parts of the polyurethane solution obtained in Production Example 1, 2.94 parts of tetramethoxysilane partial condensate (manufactured by Tama Chemical Co., Ltd., trade name MS51), 10% aqueous paratoluenesulfonic acid solution. 1 g was mixed to prepare an adhesive solution.

Examples 2 to 4 Adhesive solutions were prepared in the same manner as in Example 1 except that the kind or amount of metal alkoxide used in Example 1 was changed as shown in Table 1.

Comparative Example 1 The polyurethane solution obtained in Production Example 1 was used as it was as an adhesive solution.

Comparative Example 2 The polyurethane solution obtained in Production Example 2 was directly used as an adhesive solution.

Comparative Example 3 The polyurethane solution obtained in Comparative Production Example 1 was used as it was as an adhesive solution.

Comparative Example 4 An adhesive solution was prepared in the same manner as in Example 1 except that the kind or amount of metal alkoxide used in Example 1 was changed as shown in Table 1.

[0042]

[Table 1]

In Table 1, MS-51: tetramethoxysilane partial condensate (Tama Chemical Co., Ltd., trade name MS-5)
1), TEOS: tetraethoxysilane (manufactured by Hüls, brand name Dynasil A), TPT: tetraisopropoxytitanium (manufactured by Nippon Soda Co., Ltd., A-1), PT
S aqueous solution: Indicates a 10% paratoluenesulfonic acid aqueous solution.

The following tests were conducted on the adhesive solutions obtained in Examples or Comparative Examples to evaluate the performance.

(Adhesiveness) A bar coater No. 16 was used to coat two silica vapor-deposited PET films, and then the solvent was dried with a normal air dryer at 80 ° C. for 3 minutes. Then, the two films were pressure-bonded at 3 kg / cm ² . After curing at room temperature for 1 day, the pressure-bonded film was cut into a width of 15 mm, and a 180 ° peel strength (kg / cm, pulling speed 50 mm / min) test was conducted. The results are shown in Table 1.

[0046]

[Table 2]

(Light resistance) A container coated with the above adhesive solution was coated with a fluororesin (length × width × depth = 10 cm).
(× 10 cm × 1.5 cm), the mixture was left for 3 days to be completely cured, and then dried at 100 ° C. for 1 hour to remove the residual solvent to form a resin film (film thickness: about 0.6).
mm). Peel off the resin film from the container and use the super accelerated weather resistance tester (Iwasaki Electric Co., Ltd., trade name I Super)
UV tester F-11, wavelength 295-450 nm, illuminance 100 mW / cm ² , temperature 75 ° C.) was used for ultraviolet irradiation for 24 hours. The film before and after UV irradiation was punched out with dumbbell No. 1, and Tensilon tester (Orientec Co., Ltd.)
The film was stretched at 50 cm / min using a product name, UCT-500 manufactured by K.K., and the elongation of the film until it was broken was measured. The measurement was performed 3 times at 25 ° C., and the average value is shown in Table 3.

[0048]

[Table 3]

It can be seen from Table 2 that the hybrid body of the present invention has improved adhesiveness as compared with the polyurethane containing a terminal alkoxysilyl group. Further, from Table 3, the hybrid of the present invention has the same flexibility as the terminal alkoxysilyl group-containing polyurethane in the state of being unirradiated with ultraviolet light, and is more flexible after irradiation with ultraviolet light as compared with the terminal alkoxysilyl group-containing polyurethane. It can be seen that the deterioration of the property is small and the light resistance is excellent.

(Heat Resistance) Examples 1 and 2 or Comparative Example 1,
Regarding No. 3, the dynamic storage elastic modulus of the resin film prepared in the section of light resistance was measured with a viscoelasticity measuring instrument (Rheology, trade name D
VE-V4, measurement conditions: amplitude 10 μm, frequency 10 Hz,
The slope was measured at 3 ° C./min) to evaluate the heat resistance. The measurement results are shown in FIG.

From FIG. 1, the polyurethane containing terminal alkoxysilyl group of Comparative Example 1 has a dynamic storage elastic modulus of 100 ° C.
Although it drastically decreases by the above, in the hybrid bodies of the present invention of Examples 1 and 2, no drastic decrease is observed even when the temperature exceeds 200 ° C. From these, it is recognized that the hybrid body formed according to the present invention has excellent heat resistance.

[Brief description of drawings]

FIG. 1 is a graph of dynamic storage elastic modulus of Examples 1 and 2 and Comparative Examples 1 and 3.

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Claims (13)

[Claims] 1. A composition for organic-inorganic hybrid polyurethane comprising (1) a polyurethane having alkoxysilyl groups at both ends and (2) a hydrolyzable alkoxysilane. 2. A polyurethane having (1) an alkoxysilyl group at both ends, (a) a polyurethane having at least one functional group selected from an isocyanate group, a hydroxyl group and an amino group at both ends, and (b) the polyurethane. The composition according to claim 1, which is a reaction product of an alkoxysilane having a functional group capable of reacting with the terminal functional group of. 3. The method according to claim 1, wherein (1) the polyurethane having an alkoxysilyl group at both ends is a reaction product of (a) a polyurethane having an isocyanate group at both ends and (b) an alkoxysilane having an amino group. The composition according to 2. 4. The composition according to any one of claims 1 to 3, wherein the polyurethane (a) comprises a polymer polyol and an organic polyisocyanate compound as main components. 5. The composition according to claim 1, wherein the polyurethane (a) comprises a polymer polyol, an organic polyisocyanate compound and a chain extender as main components. 6. The composition according to claim 4, wherein the polymer polyol is a polyester polyol. 7. (2) The hydrolyzable alkoxysilane is
The adhesive composition according to any one of claims 1 to 6, which is tetraalkoxysilane and / or a condensate thereof. 8. The composition according to claim 1, which contains a curing catalyst. 9. The curing catalyst is an organic acid catalyst.
The composition as described. 10. The organic acid catalyst is at least one selected from formic acid, acetic acid and paratoluenesulfonic acid.
The composition of claim 9 which is a seed. 11. An organic-inorganic hybrid polyurethane obtained by curing the composition according to claim 8. 12. An adhesive composition comprising the composition according to any one of claims 1 to 10. 13. A method of contacting a base material and a base material via the composition according to any one of claims 8 to 10 and then curing the composition to bond the base material to the base material.