JP2002069084A - New compound, method for producing the same, silane coupling agent, and curing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silane coupling agent capable of being cured by active energy rays, excellent in compatibility with resins, and capable of giving chemical resistance and stain resistance to a resin film, and to provide a curing composition containing the silane coupling agent, and to provide a method for producing a new compound used as a raw material for the silane coupling agent, capable of producing the compound under a mild condition. SOLUTION: This new compound having a maleimide group and an alkoxysilyl group together bonded through a urethane bond is obtained by reacting an alcohol having the maleimide group with a silane compound having an isocyanate group to synthesize the compound. The silane coupling agent contains the compound as an active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel compound and a silane coupling agent comprising the compound, and more particularly, to a novel compound, a method for producing the same, a silane coupling agent comprising the compound, and a silane coupling agent comprising the compound. The present invention relates to a curable composition containing a ring agent, and belongs to various technical fields such as a chemical product production technology and an adhesion technology using a silane coupling agent.

[0002]

2. Description of the Related Art A silane coupling agent is used for the purpose of improving the adhesiveness between different materials, and its importance has been increased with the development of composite materials. It is also used for improving the surface state of a substrate by imparting a crosslinked structure to a polymer, imparting water repellency or oil repellency, preventing static charge, and the like, and further improving the dispersibility of a filler.

This silane coupling agent is a compound in which a hydrolyzable group such as a methoxy group or an ethoxy group and an organic functional group such as an amino group or an epoxy group are bonded to a silicon atom. It is hydrolyzed by the moisture in the air and further by the adsorbed moisture on the surface of the base material, changes into active silanol groups, and reacts with the surface of the base material to form a strong bond or is adsorbed on the surface of the base material. The organic functional group is a group capable of reacting with the organic material, and has an effect of firmly bonding to the organic material by the reaction.

[0004] As such a silane coupling agent, a compound in which a hydrolyzable group such as a methoxy group or an ethoxy group and an organic functional group such as an amino group or an epoxy group are bonded to a silicon atom includes, for example, , Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane,
3-glycidoxypropyltrimethoxysilane, 2-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-
Examples thereof include aminopropylmethyldimethoxysilane, 2-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-chloropropyltrimethoxysilane.

Among these compounds, a silane coupling agent comprising a compound having a polymerizable unsaturated group such as a vinyl group or a methacryloxy group is copolymerized with a polymerizable compound such as vinyl, acrylic or styrene. Or by graft-polymerizing a polymer in the presence of a radical generator to form a graft-polymerized copolymer, which is used as a sealing agent or as a crosslinked polyethylene.

In view of the usefulness of these polymerizable silane coupling agents, the present inventors have studied various silane compounds and found that they have an imide group having an imide group proposed in JP-A-63-1486891. It has been found that silanes (hereinafter, referred to as silane-based compounds) exhibit excellent photopolymerizability by utilizing the imide group, and easily give a cured product by energy rays such as light.

[0007]

However, the silane compound disclosed in the above publication requires severe conditions such as the use of a halogen compound in the production thereof, and is compounded in a resin as a silane coupling agent. When used, especially at both ends of polyalkylene glycol such as polyethylene glycol and polypropylene glycol,
When compounded with a compound having an isocyanate group, there is a problem that compatibility is not satisfactory, and the resulting coating film is not satisfactory in terms of chemical resistance and stain resistance.

The inventors of the present invention have examined various problems in using the silane compound as a silane coupling agent from various angles, and have reacted an alcohol having a maleimide group with a silane compound having an isocyanate group. The reaction smoothly proceeds without any particular problem to give a novel compound having a maleimide group and an alkoxysilyl group, and the compound having the maleimide group and the alkoxysilyl group has good compatibility with the resin, They have found that they have excellent photocurability, and have completed the present invention.

The present invention provides a novel compound which can be easily produced, a method for producing the same, and a good compatibility with a resin at the time of use, and the resulting coating film has excellent chemical resistance and stain resistance.
An object of the present invention is to provide a novel silane coupling agent having photocurability and a curable composition containing the silane coupling agent.

[0010]

In order to achieve the above object, the invention according to claim 1 of the present invention comprises a novel compound having a maleimide group and an alkoxysilyl group via a urethane bond. It is.

The invention according to claim 2 is a method for producing a novel compound according to claim 1, characterized in that the compound is synthesized by reacting an alcohol having a maleimide group with a silane compound having an isocyanate group. .

Further, the invention according to claim 3 is a silane coupling agent comprising a compound having a maleimide group and an alkoxysilyl group via a urethane bond.

The invention described in claim 4 is directed to a compound having a maleimide group and an alkoxysilyl group via a urethane bond, which is produced by reacting a maleimide group-containing alcohol with an isocyanate group-containing silane compound. And a silane coupling agent.

The invention described in claim 5 is a curable composition containing a silane coupling agent comprising a compound having a maleimide group and an alkoxysilyl group via a urethane bond. .

Further, the invention described in the sixth aspect is characterized in that a curing agent comprising a silane coupling agent comprising a compound having a maleimide group and an alkoxysilyl group via a urethane bond, and a tetraalkoxysilane. The composition is an acidic composition.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The silane coupling agent of the present invention comprises a novel compound having a maleimide group and an alkoxysilyl group via a urethane bond. The novel compound comprises a maleimide group-containing alcohol, It can be easily obtained by reacting a silane compound having an isocyanate group.

Examples of the alcohol having a maleimide group include a reaction product of an acid anhydride and an alkanolamine. One of the acid anhydrides is maleic anhydride,
-Methyl maleic anhydride, 2-ethyl maleic anhydride,
2-propyl maleic anhydride, 2-isopropyl maleic anhydride, 2-butyl maleic anhydride, 2,3-dimethyl maleic anhydride, 2,3-diethyl maleic anhydride,
2,3-dipropyl maleic anhydride, 2,3-dibutyl maleic anhydride, 2-phenyl maleic anhydride, 2,3
-Diphenylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dichloromaleic anhydride, 3,4,5,6
-Tetrahydrophthalic anhydride and 3,6-endo-
Examples include methylene-3,4,5,6-tetrahydrophthalic anhydride.

Other alkanolamines include ethanolamine, 3-aminopropanol, 2-aminopropanol, 2-aminobutanol, 2-amino-2-methyl-1-propanol, diethanolamine and 2-ethanolamine.
Amino-2-methyl-1-propanediol and the like are exemplified.

The reaction between the acid anhydride and the alkanolamine is carried out at reflux temperature in a solvent such as toluene, and is a dehydration cyclization reaction in which water is eliminated to form a ring. An alcohol is formed.

Examples of the silane compound having an isocyanate group include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane,
And an alkylsilane having an isocyanate group such as γ-isocyanatopropyltripropoxysilane; a compound having a SiH bond such as trimethoxysilane, triethoxysilane and tripropoxysilane is added to an isocyanate compound having a carbon-carbon double bond. Compound: a reaction product of an aminosilane with a polyisocyanate compound such as an adduct or a burette obtained by reacting water or a polyhydric alcohol with a diisocyanate compound.

Examples of the diisocyanate compound include hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and xylylene diisocyanate, and dimer and trimer condensates thereof.

The reaction between an alcohol having a maleimide group and a silane compound having an isocyanate group is a well-known condensation reaction, which is carried out under conventionally known conditions, for example, a reaction at room temperature to 100 ° C. in a solvent such as toluene. At temperature,
By reacting for 1 to 24 hours, a compound having a maleimide group and an alkoxysilyl group via a target urethane bond can be easily obtained.

In the present invention, the compound having a maleimide group and an alkoxysilyl group via a urethane bond is
As described above, a compound obtained by reacting an alcohol having a maleimide group with a silane compound having an isocyanate group. The urethane bond is formed by a reaction between an alcohol and an isocyanate group. Is as shown in Chemical Formula 1.

[0024]

Embedded image In the formula, X represents a portion excluding the hydroxyl group of the alcohol having a maleimide group, and Y represents a portion excluding the isocyanate group of the silane compound having an isocyanate group.

The compound having a maleimide group and an alkoxysilyl group via a urethane bond of the present invention represented by the above structural formula is a silane compound having a photocurable maleimide group and a hydrolyzable alkoxy group. Therefore, it is useful as an excellent silane coupling agent having a specific function.

More specifically, a compound having a maleimide group and an alkoxysilyl group via a urethane bond of the present invention is represented by the following structural formula.

[0027]

Embedded image

In the above formula ( ²⁾ , R ¹ and R ² each represent an independent hydrogen atom or an alkyl group having 4 or less carbon atoms, a halogen atom, an aromatic group, or ^one of R ¹ and R ² or 5 or It represents a hydrocarbon group forming a 6-membered ring, and R ³ and R ⁴ each represent an organic group having a maleimide group bonded to a hydroxyl group and an organic group having an alkoxysilyl group bonded to an isocyanate group.

More specifically, R ⁵ and R ⁶ represent an alkylene group or a polyoxyalkylene group which may have a functional group such as a substituent, an alicyclic ring, a urethane bond, a urea bond, an amide bond, an ester bond, etc. Represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 or 1.

In the above R ¹ and R ² , a methyl group is preferable as the alkyl group, a chlorine atom is preferable as the halogen atom, and a phenyl group is preferable as the aromatic group. As the hydrocarbon group to be formed,
_{-CH 2 CH 2 CH 2 -,} - CH 2 CH 2 CH 2 CH 2
-And those represented by the following structural formulas are preferred.

[0031]

Embedded image

As R ³ , an alkylene group is preferable.
Examples of the alkylene group include an ethylene group, a methylethylene group, a propylene group, a methylpropylene group and a butylene group, and an ethylene group and a propylene group are preferred.

R ⁴ is preferably an alkylene group, an alkylene group having a urea bond, or a group having a urethane bond, an alkylene group and an oxyalkylene group.

The alkylene group includes an ethylene group and
And propylene groups are preferred and alkyl having a urea bond.
As the substituent group,-(CH_Two)₆NHCONH (CH_Two)
_ThreeIs preferred, and a urethane bond, an alkylene group and
Examples of the group having a silalkylene group include-(CH_Two)_m1N
HCO (CH_TwoCH_TwoO)_m2CONH (CH_Two)_m3NH
CONH (CH_Two)_m4− [M₁Is an integer of 1 to 10, m_Two
Is an integer of 1 to 25, m _ThreeIs an integer of 1 to 10 and m_FourIs 1
To an integer of to 6].

More specifically,-(CH_Two)₆NHCO
(CH_TwoCH_TwoO) CONH (CH _Two)₆NHCONH
(CH_Two)_Three-, And-(CH_Two)₆NHCO (CH_Two
CH _TwoO)_TwoCONH (CH_Two)₆NHCONH (CH
_Two)_Three-Is preferred.

The alkyl group for R ⁵ is preferably a methyl group, and the alkyl group for R ⁶ is preferably a methyl group, an ethyl group and a propyl group.

The compound represented by the above formula 2 includes R ¹
And R ² are each independently a hydrogen atom, an alkyl group having 4 or less carbon atoms, or a hydrocarbon group forming a 5- or 6-membered ring by combining R ¹ and R ² , and R ³ and R ⁴ are alkylene Compounds in which the groups R ³ and R ⁴ are alkyl groups having 1 to 4 carbon atoms are more preferred.

Specific compounds represented by the above formula 2 include compounds in which R ¹ and R ² are methyl groups, R ³ is an ethylene group, R ⁴ is a propylene group, R ⁶ is a methyl group and n is 0,
R ¹ and R ² combine to form a tetrahydrotal cyclic structure, and examples thereof include compounds in which R ³ is an ethylene group, R ⁴ is a propylene group, R ⁶ is an ethyl group, and n is 0.

The compound of the present invention is a compound having a maleimide group. Since the maleimide group causes a dimerization reaction when irradiated with light of 250 to 400 nm, it exhibits a function of photocuring by light irradiation. As U
V irradiation, sunlight irradiation, etc. are applied, and curing with other active energy rays is also possible.

The silane coupling agent of the present invention can be used in accordance with the method of use, application, and the like employed in conventional silane coupling agents.

For example, there is an example in which the silane coupling agent of the present invention is mixed with various resins and used for applications such as coating materials such as paints, sealing materials, adhesives, adhesives, sealing materials and molding materials. Can be

Examples of the resin include acrylic resin, polyester resin, epoxy resin, silicone resin, urethane resin, polyvinyl acetate, polyvinylpyrrolidone and polyacrylamide. In this case, an organic solvent or the like may be blended as necessary.

In particular, it is preferable that the silane coupling agent of the present invention is blended with tetraalkoxysilane such as tetramethoxysilane and tetramethoxysilane, or an oligomer thereof, and used as a coating material such as a paint. In this case, a resin, an organic solvent and a curing catalyst such as dibutyltin laurate as described above can be further blended.

The mixing ratio of the silane coupling agent of the present invention may be appropriately set according to the components to be used and the intended use, but is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin. .

[0045]

The compound of the present invention is a compound having a maleimide group and an alkoxysilyl group. It has been known that the maleimide group causes a dimerization reaction when irradiated with light of 250 to 400 nm. In addition, even if it has a bulky alkoxysilyl group at multiple ends, it has been discovered by the present inventors that the dimerization reaction by light irradiation proceeds without being inhibited, and that the alkoxysilyl group has In combination with the above, the compound of the present invention exhibits an action as a silane coupling agent having photocurability.

[0046]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments. In addition,% means mass% throughout all Examples.

Example 1 (Production of a silane coupling agent) In a flask in which 126 g of 2,3-dimethylmaleic anhydride and 126 g of toluene were mixed, a mixture of 61 g of ethanolamine and 61 g of toluene was mixed at a temperature of 80 ° C. Was added dropwise over 20 minutes with stirring. After completion of the dropwise addition, the temperature was raised to the reflux temperature of toluene, and a dehydration ring closure reaction was performed for 5 hours while removing generated water. 1 trapped water
At 7.1 g, a conversion of 95% was calculated. The obtained reaction solution was cooled to a temperature of 80 ° C., and 195 g of γ-isocyanatopropyltrimethoxysilane was added.
A condensation reaction was performed at 2 ° C. for 2 hours. Analysis by gas chromatography revealed that the consumption of γ-isocyanatopropyltrimethoxysilane was 92% and the silane coupling agent comprising a compound having a maleimide group and an alkoxysilyl group in a total yield of 87% was dissolved in a solution (hereinafter, referred to as “ S-1 "). The content of the active ingredient in S-1 is 66.
%Met.

It was confirmed from the results of elemental analysis, IR, Raman and NMR shown below that the obtained compound was a novel compound having a maleimide group and an alkoxysilyl group. Elemental analysis element HCN measured value 6.23 51.85 6.82 calculated value 7.05 50.98 6.99 IR: 1075 cm ^-1 (Si-OC), 1526 cm ^-1
(NH), 1697 cm ^-1 (C = O), 1768 cm ^-1
(Imide C = O), no NCO peak Raman: 1674 cm ^-1 (C = C in tetrahydrophthalimide), 1710 cm ^-1 (C = O), 1771 cm
^-1 (imide C = O) ¹ H-NMR: 0.6 ppm (t) [ CH ₂ Si (OC
H ₃ )], 1.6 ppm (quint) [CH ₂ CH ₂
CH _2], 1.7~1.8ppm (m) [CH ₂ CH ₂ in tetrahydrophthalimide], 3.1 ppm (t)
[NHCH _2], 3.5 ppm (S) [Si (O C
H _{3) 3],} 3.6~3.9ppm (m) [N CH ₂ C
H ₂ ], 4.2 ppm (t) [NCH ₂ CH ₂ O]

Example 2 (Production of silane coupling agent) 152 g of 2,3,4,5-tetrahydrotalic anhydride
And a mixture of 152 g of toluene and 0.3 g of a 1% toluene solution of catechol were added dropwise at 80 ° C. under stirring with a mixture of 61 g of ethanolamine and 61 g of toluene over 20 minutes. After completion of the dropwise addition, the temperature was raised to the reflux temperature of toluene, and a dehydration ring closure reaction was performed for 5 hours while removing generated water. The amount of water trapped was 16.8 g, which was calculated to be 93%. The obtained reaction liquid was cooled to a temperature of 80 ° C, 230 g of γ-isocyanatopropyltriethoxysilane was added, and a condensation reaction was performed at a temperature of 80 ° C for 2 hours. Analysis by gas chromatography revealed that the consumption of γ-isocyanatopropyltriethoxysilane was 95% and the total yield was 88%.
A solution of the silane coupling agent of the present invention in a solution
It is called "S-2." ). The active ingredient content in S-2 was 64%. As a result of analyzing the obtained compound in the same manner as in Example 1, it was confirmed that the target compound was obtained.

Examples 3 to 6, Comparative Examples 1 and 2 (Curable set
Preparation of Product and Performance Evaluation) The curable composition was prepared by mixing various components at the mixing ratios shown in Table 1. It is a result of comparison with a normal silane coupling agent. The unit in Table 1 is g,
In the table, "methyl silicate 51 (trademark)" is an oligomer of tetramethoxysilane manufactured by Tama Chemical Co., Ltd., and "DBTDL solution" is a 1% toluene solution of dibutyltin dilaurate.

[0051]

[Table 1]

Each of the prepared curable compositions was applied to glass with a bar coater so that the film thickness after drying was about 10 μm. The drying was performed under the following two conditions, and the characteristics of the dried sample were measured under the following conditions. The results are shown in Table 2 (drying condition 1) and Table 3 (drying condition 2), respectively. Drying condition 1: normal temperature × 7 days → temperature 200 ° C. × 10 minutes Drying condition 2: normal temperature × 7 days → UV irradiation (mercury lamp, 90
0 mJ / cm ² )

[0053]

[Table 2]

[0054]

[Table 3]

Characteristics Measurement Conditions 1) Xylene rubbing was applied with a load of 1 kg, and the appearance after 10 reciprocations was visually determined. ：: No abnormality Δ: Slight trace remains ×: Torn to the ground 2) Pencil hardness The maximum hardness without scratches was shown according to the method of JIS K5400. 3) Alkali resistance A 5% NaOH aqueous solution was spotted on the coating film, washed away after 24 hours, and the appearance was observed. ：: No abnormality △: Trace remains ×: Dissolution of coating film 4) Acid resistance 5% H ₂ SO ₄ aqueous solution is spotted on the coating film, and
After an hour, it was washed away and the appearance was observed. ○: No abnormality △: Trace remains ×: Dissolution of coating film 5) Magic Ink (registered trademark) Draw a line on the coating film with Mack ink (red), and after 24 hours, wipe with a paper impregnated with ethanol and remove It was evaluated visually. ：: Wipe off cleanly き れ い: Slight trace remains ×: Trace remains

As is clear from the above evaluation, that is, the comparison of the development of the characteristics under the drying conditions 1 and 2, the curing by heat (only the condensation of silicate) is different from the conventional silane coupling agent and the silane coupling agent of the present invention. Although there is no difference in properties with the ring agent, the one using the silane coupling agent of the present invention is remarkably improved in physical properties and shows excellent characteristics by being photocured.

[0057]

According to the present invention, a silane coupling agent can be produced under mild conditions, and unlike the conventional silane coupling agent, the obtained silane coupling agent is cured by an active energy ray. Therefore, it is excellent in hardness, chemical resistance, and stain resistance.Moreover, when compounded with a resin, particularly when compounded with a compound having an isocyanate group at both ends of a polyalkylene glycol such as polyethylene glycol or polypropylene glycol. Also have excellent compatibility.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Eiichi Okazaki 1-1, Funami-cho, Minato-ku, Nagoya City Toagosei Co., Ltd. Nagoya Research Laboratory F term (reference) 4H049 VN01 VP01 VQ59 VR22 VR23 VR42 VR43 VU22 VW02 4J002 BF021 BG021 BG131 BJ001 CD001 CF001 CK021 CP031 EX076 GH01 GJ01 GJ02

Claims (6)

[Claims] 1. A novel compound having a maleimide group and an alkoxysilyl group via a urethane bond. 2. The method for producing a novel compound according to claim 1, wherein the compound is synthesized by reacting an alcohol having a maleimide group with a silane compound having an isocyanate group. 3. A silane coupling agent comprising a compound having a maleimide group and an alkoxysilyl group via a urethane bond. 4. A silane cup comprising a compound having a maleimide group and an alkoxysilyl group via a urethane bond, produced by reacting an alcohol having a maleimide group with a silane compound having an isocyanate group. Ring agent. 5. A curable composition comprising a silane coupling agent comprising a compound having a maleimide group and an alkoxysilyl group via a urethane bond. 6. A curable composition comprising: a silane coupling agent comprising a compound having a maleimide group and an alkoxysilyl group via a urethane bond; and a tetraalkoxysilane.