JP2002003720A - Reactive additive for japan and japan analog compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a reactive additive for a japan and a japan analog compound, being chemically bonded to a coating film without inhibiting a curing reaction with an enzyme, enabling various chemical modifications on a japan film, chemically promoting a curing reaction. SOLUTION: This reactive additive is characterized in that the reactive additive contains an amino group at the end of a main chain or a branched chain of a hydrocarbon molecular chain and has a reactive group in which the number of straight-chain carbons adjacent to the amino group is two or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to lacquer and a lacquer-like compound which solidifies by a similar mechanism and can be used in a usual coating operation without inhibiting the enzymatic curing reaction of the compound. The present invention relates to a reactive additive capable of imparting a new function to a formed coating film by adding various chemical modifications or characteristic molecular structures to the polymer.

[0002]

Conventionally, lacquer and lacquer-like compounds have been widely used as natural paints, and have been used for a long time, from products excavated in the Kofun period to the manufacture of lacquerware and lacquer crafts, which are current traditional industries. Was. It is also widely used in buildings such as traditional shrines and temples.

However, it is known that lacquer is susceptible to ultraviolet rays, has poor weather resistance, and has a phenomenon that it does not cure depending on the additives mixed therein, and has limitations in terms of application and manufacturing process.

[0004] Lacquer liquor is made from sap collected from urchinoki, and its main component is urushiol or an urushiol analog having a partially different structure from that of urushiol, and the type of urushiol varies depending on the place of production. Other components include rubber, nitrogen-containing compounds, enzymes, and water.

[0005] Lacquer liquid is 20-35 ° C, high humidity (70% RH)
Oxidase (such as laccase) contained therein acts when it is exposed to the above, causing a curing reaction to be solidified to form a coating film. This curing mechanism is the same even if the type of lacquer is different.

Accordingly, lacquer ware and the like are generally dried by using a drying room called a lacquer bath, in which a product coated with a lacquer liquid is put in the drying room, and the product is exposed to the above-mentioned high humidity atmosphere.

[0007] Another important factor other than the curing conditions is that it is known that the lacquer liquid does not cure when an additive that interferes with the enzyme reaction system is added. Traditionally, widely used additives include linseed oil, sesame oil, paulownia oil, egg white, glue, and the like, and pigments such as red iron oxide, vermilion, and soot are added.

[0008] However, these additives are selected from long experience, and since the relationship between the reaction system and the chemical structure was not clearly understood, the addition of functions had to be limited. In addition, when used as a product, if it is not chemically bound, the additive may be eluted as it is.

[0009] In addition, in recent technology, an additive made of a protein hydrolyzate containing a natural protein and an amino acid has been proposed for the purpose of preventing rash. However, this additive binds to the site of urushiol that causes rash and inactivates it, and cannot add various functions.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a journal of the Chemical Society of Japan. 2 (1999); 3 (2
000), based on the newly elucidated curing reaction mechanism, chemically bonds with the coating film without inhibiting the enzymatic curing reaction, enabling various chemical modifications to the lacquer film or chemically curing It is to provide an additive for accelerating the reaction.

The mechanism of the elucidated curing reaction is as follows.
As shown in FIG. 6, the relationship between the field of the enzyme reaction at the time of curing the coating film and the behavior due to the characteristics of the molecular structure, as represented by the urushiol reverse micelle structure.

[0012]

The reactive additive for lacquer and lacquer-like compound according to claim 1 of the present invention has an amino group at a terminal of a main chain or a branched chain of a hydrocarbon molecular chain, and has an amino group. It has a reactive group having at least two straight-chain carbon atoms adjacent to the group.

The reactive additive for lacquer and lacquer-like compound according to claim 2 is characterized in that the hydrocarbon molecule has a linear carbon number of 10 to 2;
It has two aliphatic hydrocarbon chains.

The reactive additive for lacquer and lacquer-like compound according to claim 3 is characterized in that the hydrocarbon molecule is an aliphatic hydrocarbon,
It has an amino group at the terminal of a main chain or a branched chain of a hydrocarbon molecular chain, and has two or more reactive groups having two or more linear carbon atoms adjacent to the amino group.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The structure of the reactive additive for lacquer and lacquer-like compound according to claim 1 of the present invention has an amino group at a molecular chain terminal as shown in FIG. 1 and is adjacent to the amino group. It has a reactive group having two or more linear carbon atoms. Further, as shown in FIG. 2, the hydrocarbon chain has an amino group at the terminal of the branched chain, and has a reactive group having two or more straight-chain carbon atoms adjacent to the amino group.

The effect of this additive is that when a chemical bond is formed in a curing reaction atmosphere, an aliphatic hydrocarbon chain having an amino group at a terminal and a phenol or polyhydric phenol ring undergo a crosslinking reaction. This is achieved when the straight-chain hydrocarbon chain adjacent to the terminal amino group has two or more carbon atoms. This is due to the necessity that there is no steric hindrance in the vicinity for the amino group to chemically bond, and that the amino group is not electrically inactive.

In addition, as a method for producing the additive shown in FIG. 2, for example, a polymer such as polyethyleneimine or polyallylamine, which has an amino group at the terminal of a branched chain, is dissolved in water and diluted about twice. It is obtained by doing. Since the polymer forms the above-mentioned branched chain at a certain ratio irregularly apart from the repeating structure as the theory, it can be used if it can be assumed that it will be an amino group. For better dispersion in lacquer liquor, it is better to add it to unrefined lacquer and close it.

The reactive additive for lacquer and lacquer-like compound of the present invention is a single component, unlike natural compounds, and specifies a functional group that reacts with a phenol compound, so that the reaction efficiency and dispersibility are reduced. It is stable and resistant to deterioration.

Further, according to the present invention, in order to prevent the curing reaction from being hindered, it is necessary to first naturally and naturally take into the curing reaction system by the enzyme reaction. As one of the methods, an aliphatic hydrocarbon chain whose additive is the same as the alkenyl side chain of a phenol ring or a polyhydric phenol ring such as urushiol, lacquer, or thiol, which is a main component of lacquer and lacquer-like compounds, is used. Is achieved by having a molecular structure of

For this reason, the invention according to claim 2 is involved in the degree of steric hindrance to the urushiol reverse micelle structure shown in FIG.
Is preferably in the range of 10 to 22.

Compounds for various functions and modifications, such as compounds that act chemically and compounds that cause physical phenomena, are not incorporated into the core of the urushiol reverse micelle structure. The number of carbon atoms is selected from 10 to 22 and an additive is prepared by incorporating this chemical structure, thereby enabling chemical modification by adding to and using lacquer and lacquer-like compounds.

In this case, if the number of carbon atoms is less than 10, the additive is taken into the inside of the urushiol reverse micelle structure and the effect of the chemical modification is small, and if the number of carbon atoms exceeds 22, the additive becomes reverse micelle. It is located outside the structure and will inhibit the formation of a reverse micelle structure.

As a method for producing the additive according to the second aspect, a compound having a function to be added to lacquer or lacquer-like compound is selected, and a functional group having no relation to the expression of a function in the molecular structure of the compound and carbon is selected. It can be formed by chemically bonding to a functional group other than the amino group of the aliphatic compound having an amino group at the terminal in the number of 10 to 22. Since the length of the hydrocarbon chain to be added is important, the bond at this time may not be a carbon-carbon bond but may be, for example, a carbon-oxygen bond or a carbon-nitrogen bond.

The additive according to claim 3 of the present invention is characterized in that the hydrocarbon molecule is an aliphatic hydrocarbon and has an amino group at both ends of the main chain of the hydrocarbon molecular chain as shown in FIG. A phenol ring or a polyhydric phenol ring is connected by providing a reactive group having two or more straight-chain carbon atoms adjacent to the group, thereby making it possible to forcibly create a curing reaction field. Further FIG.
As shown in the above, two amino groups are provided at both ends of the main chain of the hydrocarbon molecular chain, and a reactive group having two or more straight-chain carbon atoms adjacent to the amino group is provided.

By connecting the hydrophilic sites of the molecule with a linear hydrocarbon chain in this manner, the phenol group involved in the reaction can be made closer while reducing the effect of steric hindrance on the enzymatic reaction. The coating film can be strengthened by the increase in cross-linking.

As a method for producing this additive, for example, each terminal functional group of a linear aliphatic hydrocarbon is substituted with an amino group, or an aliphatic compound having an amino group at a terminal is substituted with a functional group other than an amino group. It can be made by combining with The bond at this time is not limited to a carbon-carbon bond, and may be, for example, a carbon-oxygen bond or a carbon-nitrogen bond.

In the present invention, in the case of an additive imparting a function such as weather resistance, as a method for preventing the curing reaction from being hindered, it is possible to completely convert the additive into a high molecular compound and out of the curing reaction system. Can be The average molecular weight for out of the system is achieved above 1800.

As described above, by dispersing a high molecular compound having an average molecular weight of 1800 or more in which a reactive group is a branched chain in a lacquer solution, the branched chain is bonded to a phenol ring and a polyphenol ring. The curing reaction is accelerated, and the particle structure of the coating film is formed. As a result, the main chain of each coating particle is tied up, and the weather resistance of the coating film can be improved.

[0029]

Embodiments of the present invention will be described below. The lacquer used is all purified lacquer from China, commercially available sukuroiro lacquer and raw lacquer. No additives are used in the manufacturing process. The curing time was measured while placing a rotary drying time measuring device on a glass plate coated with lacquer and curing in a constant temperature and humidity chamber. The time when the circular locus drawn by the steel needle on the coating film disappeared was defined as the curing time. The reaction inhibition was evaluated by comparing the curing time between the case where the lacquer solution was used as it was and the case where the reagent was added. The case where it was short or there was almost no difference was regarded as no reaction inhibition.

Whether or not a chemical bond was favorably formed was evaluated based on the fact that the added additive or a compound resulting therefrom was not detected by mass spectrometry after thermal or solvent extraction. In the heat extraction, the temperature was kept at 100 ° C. for 3 minutes, and the temperature was raised to 300 ° C. at a rate of 30 ° C./min.
The sample was exposed under the condition of holding for 1 minute, and volatile components in the sample were extracted, concentrated, and measured. In the solvent extraction, the sample was immersed in a sealed bottle filled with alcohol for 2 months to obtain a measurement sample.
The gas chromatograph mass spectrometer used a metal capillary column and performed EI-positive measurement.

(Example 1) The effect of the present invention was confirmed in the case where an additive was added for the purpose of adding water repellency.
The additive was 1-aminobutyl-2 ', 2', 3 ', 3', 4 ', 4', 5 ',
5 ', 6', 6 ', 7', 7 ', 8', 8 ', 9',
7.45 mg (1 mol% based on urushiol contained in the lacquer solution) of 9 ', 9'-heptadecafluoroethyl ether (Chemical Formula 1) was added, mixed, and applied to a thickness of 20 μm with an applicator. , Humidity 75% RH, temperature 2
The curing reaction was carried out in a thermo-hygrostat at 0 ° C.

[0032]

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When the sample was observed, no reaction inhibition was observed, and no added reagent was detected by the mass spectrometer. Regarding the water repellency, the effect of improving the contact angle was confirmed as compared with the non-added coating film.

Example 2 The effect of the present invention was confirmed in the case where an additive for accelerating the curing reaction was added. As an additive, 3.79 mg (the same ratio as in Example 1) of 1,8-diaminooctane (chemical formula 2) was added to 1 g of the squeezed lacquer liquor and mixed.
Then, a curing reaction was carried out in a constant temperature and humidity chamber at a humidity of 75% RH and a temperature of 20 ° C.

[0035]

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When the sample was observed, no reaction inhibition was observed, and no added reagent was detected by the mass spectrometer. Further, for comparison, a coating film obtained by curing a lacquer solution without addition of an additive and a coating film to which the additive of the present invention was added were compared with each other in pencil hardness. The hardness of the coating film after a lapse of time showed a value about one step higher than that of the non-added film. This is the effect of accelerating the curing reaction and increasing the crosslinking at the molecular level.

[0037]

[Table 1]

Example 3 The effect of the present invention was confirmed when an additive for promoting the curing reaction was added. As an additive, 8.33 of propylenenyminetetraamine dendrimer (Chemical Formula 3) was added to 1 g of cascade color lacquer liquid.
mg (the same ratio as in Example 1) was added, mixed, and applied to a film thickness of 20 μm using an applicator.
The curing reaction was carried out in a constant temperature / humidity bath at 20% RH and a temperature of 20%. For comparison, a curing reaction was performed under the same curing conditions without adding an additive, and the curing times were compared.

[0039]

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When the sample was observed, no reaction inhibition was observed, and no added reagent was detected by the mass spectrometer. As shown in Table 2, it was confirmed that the curing time was shorter than that in the case where no additive was added, and that the curing was performed under the same conditions as the ordinary curing time even under the curing conditions of 55% RH and 20 ° C.

[0041]

[Table 2]

Example 4 32.88 mg of a 50% aqueous solution of polyethyleneimine (Chemical Formula 4) having an average molecular weight of 75,000 per 1.36 g of raw lacquer as an additive for the purpose of accelerating the curing reaction and forming a strong coating film. Added and tumbled on a 40 ° C. hot plate. After applying this to a film thickness of 20 μm with an applicator, the humidity is 75% RH and the temperature is 20 ° C.
The curing reaction was performed in a constant temperature / humidity bath. No reaction inhibition. No added reagent is detected by the mass spectrometer. The same effect as in Examples 2 and 3 was obtained for the curing reaction. Furthermore, in the accelerated exposure test (without rainfall) using a weathering tester, the reduction rate was reduced in comparison with the reduction rate of the film thickness with the lacquer coating film without the addition of the reagent, and improvement in light resistance was confirmed.

[0043]

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[0044]

The reactive additive for lacquer and lacquer-like compounds according to claim 1 of the present invention adds functions such as imparting functionality to lacquer and lacquer-like compounds and promoting the curing reaction. In this case, it can be added without inhibiting a conventional curing reaction involving an enzyme, and is characterized in that the additive is not detached from the formed coating film by a physical operation. For this reason, the method according to the invention does not require extensive equipment and can be used in normal application operations. In addition, since the additive is chemically bonded to lacquer and lacquer-like compound components, there is no elution during product use and no swelling on the surface, and the effect can be maintained for a long period of time. Is very useful.

The additive according to claim 2 has 1 carbon atom.
By selecting from 0 to 22, chemical modification becomes possible without inhibiting the formation of the urushiol reverse micelle structure.

Further, the additive according to claim 3 has two or more amino groups at the terminals of the main chain or the branched chain of the hydrocarbon molecular chain, respectively, and has two or more straight-chain carbon atoms adjacent to the amino group.
Having at least one reactive group reduces the effect of steric hindrance on the enzymatic reaction and makes it possible to bring the phenol group involved in the reaction closer to the coating. can do.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing a chemical structure of a reactive group having an amino group at a molecular chain terminal and having two or more straight-chain carbon atoms adjacent to the amino group.

FIG. 2 is an explanatory diagram showing a chemical structure of a reactive group having an amino group at a terminal of a branched chain and having two or more straight-chain carbon atoms adjacent to the amino group.

FIG. 3 shows a hydrocarbon molecule having an aliphatic hydrocarbon chain having 10 to 22 carbon atoms, an amino group at the molecular chain end, and a reactive group having two or more linear carbon atoms adjacent to the amino group. FIG. 3 is an explanatory view showing a chemical structure of an additive having the compound.

FIG. 4 shows an addition in which the hydrocarbon molecule is an aliphatic hydrocarbon, has an amino group at both ends of the main chain of the hydrocarbon molecular chain, and a reactive group having two or more straight-chain carbon atoms adjacent to the amino group. It is explanatory drawing which shows the chemical structure of an agent.

FIG. 5 is an explanatory diagram showing a chemical structure of an additive having an amino group at each end of a main chain of a hydrocarbon molecular chain and having a reactive group having two or more straight-chain carbon atoms adjacent to the amino group. is there.

FIG. 6 is an explanatory view showing a urushiol reverse micelle structure.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 193/00 C09D 193/00

Claims (3)

[Claims] 1. A lacquer having an amino group at the terminal of a main chain or a branched chain of a hydrocarbon molecular chain, and having a reactive group having at least two straight-chain carbon atoms adjacent to the amino group. Reactive additive for lacquer-like compounds. 2. The reactive additive for lacquer and lacquer-like compounds according to claim 1, wherein the hydrocarbon molecule has a linear aliphatic hydrocarbon chain having 10 to 22 carbon atoms. 3. A reaction in which the hydrocarbon molecule is an aliphatic hydrocarbon, has an amino group at the terminal of the main chain or branched chain of the hydrocarbon molecular chain, and has at least two straight-chain carbon atoms adjacent to the amino group. The reactive additive for lacquer and lacquer-like compound according to claim 1 or 2, wherein the reactive additive has two or more groups.