JP2002088049A - Polymerizable function group-containing alkylene amide derivative, gelling agent and coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gelling agent which can gel a wide range of organic media and can enlarge the molecule of the gel in a state holding a gel state by the irradiation of ultraviolet light on the gel thermally dissolved and formed in an organic solvent, because of containing a polymerizable functional group at the molecular terminal. SOLUTION: This gelling agent having an amino acid derivative segment and a polymerizable functional group, especially a new polymerizable functional group-containing alkylene amide derivative having a special structure represented by formula (1) [(n) is an integer of 2 to 30; A1 and A2 are each CH(CH3)2 or the like; B1 and B2 are each CONH(CH2)20COC(CH3)=CH2 or the like; (m1) and (m2) are each 1 or 2].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gelling agent having an amino acid derivative segment and a polymerizable functional group useful for thickening or gelling a wide range of liquid organic media, and a coated body using the same. Furthermore, the present invention relates to a polymerized functional group-containing alkyleneamide derivative of a novel compound having an amino acid derivative segment which is promising for use as a gelling agent and a polymerized functional group at a molecular end.

[0002]

2. Description of the Related Art In recent years, the development of low molecular weight compounds which can be added to an organic medium or form a gel by simple operations such as heating and cooling has been advanced. Gels are expected to be applied to techniques such as control of fluidity and processing of cosmetics, pharmaceuticals, adhesives, resins, paints, etc., which are liquid at room temperature. For example, if it is possible to gel or solidify waste oil or domestic waste oil due to a spill accident, it will be effective for easy and efficient collection and disposal of the waste oil and reuse of the waste solvent as fuel. In addition, the use of a gelling agent in the electrolyte solution of the dye-sensitized solar cell is being studied in order to prevent the solution from evaporating.
Further, also in a magnetic recording medium and the like, studies are being made on using a gelling agent as a viscosity modifier for various paints or as a coating material.

Examples of such a substance (gelling agent) having a function of gelling a liquid organic medium include alkali metal salts of long-chain fatty acids (JP-A-55-75493), 12
-Hydroxystearic acid (JP-B-60-44968), N-acylamino acid amide (JP-B-54-33)
798 publication) and the like. However, these require a large amount of addition in order to gel or solidify the liquid organic medium, there are restrictions on the use conditions such as pH, etc., the type of liquid organic medium that can be gelled is small, etc. There were drawbacks.

[0004] In order to solve the above-mentioned drawbacks, in recent years, low molecular compounds for gelling or solidifying a liquid organic medium have been actively developed. One example is cyclohexanetricarboxamide (JP-A-10-2732).
No. 77), a dialkyl urea derivative obtained by reacting diaminocyclohexane and an alkyl isocyanate (JP-A-8-231942), a cyclic dipeptide (JP-A-7-247474, JP-A-7-247473).
Publications). These low molecular weight compounds can be applied to a wide range of organic media as gelling agents, and the formed gel is thermoreversible, and therefore these compounds can be used as gelling agents in organic media. It has excellent characteristics such that a gel can be formed only by adding a small amount and heating and dissolving. However, since the gel state of the gel formed by the low molecular weight compound is a metastable state between the crystalline state and the solution state, it may be unstable when left for a long period of time, causing crystal transition. And there is a limit in maintaining the stability of the gel formed by the low molecular weight compound for a long period of time.

[0005] The stability of such a gel may be important in the above-mentioned applications.

The present inventors have previously proposed an alkyleneamide derivative having a styrene segment as a gelling agent. (The 78th Annual Meeting of the Chemical Society of Japan, Lecture No. 3B616, No. 49 At the Annual Meeting of the Molecular Society of Japan, lecture number II, Pd112), it was found that there were few types of liquid organic media that could be gelled.

[0007] Further, regarding the gelling agent according to the main application, in the dye-sensitized solar cell, the liquid organic medium (organic solvent) constituting the electrolyte can be gelled, and the performance of the battery can be improved. It is necessary to obtain a stable gel.

On the other hand, in recent years, in order to achieve high-density recording, various types of magnetic recording media having a thin magnetic layer have been proposed for the purpose of improving the self-demagnetization loss of the magnetic layer. JP-A-9-35264, etc.). When such a magnetic layer is applied, since a dilute solution containing a large amount of solvent is used as a coating solution, the rheological pseudoplastic flow characteristics of the coating solution, which is effective for improving the coating (coating) suitability, particularly the “yield value” , "Plastic viscosity" and the like are extremely reduced, it is difficult to apply, it is necessary to adjust the viscosity appropriately, and it is necessary to add a viscosity modifier. Therefore, when a gelling agent is used as a viscosity adjusting agent, characteristics suitable for it are required to obtain a uniform and flat magnetic layer highly filled with magnetic powder. In addition, it is indispensable for such a thin magnetic layer to have a structure in which an extremely smooth nonmagnetic layer is interposed between the support and the thin film magnetic layer. It is necessary to apply a smooth and uniform coating to the magnetic layer. Therefore, even in such a coating liquid, when a gelling agent is used as a viscosity modifier, a pseudoplastic flow characteristic is imparted to a coating liquid which has a low viscosity and approaches the Newton unflow characteristic due to a large amount of solvent dilution. Becomes effective.

In recent years, in optical information media such as a read-only optical disk and an optical recording disk, in order to record or store enormous information such as moving image information, it is required to increase the capacity of the medium by improving the recording density. In order to respond, research and development for higher recording density have been actively conducted.

As one of them, for example, DVD (Di
As shown in the “Gital Versatile Disk”, the recording / reproducing wavelength is shortened, and the numerical aperture (NA) of the objective lens of the recording / reproducing optical system is increased to reduce the laser beam spot diameter during recording / reproducing. It has been proposed to.
When comparing DVD with CD, the recording / reproducing wavelength is 780 nm.
From 650 nm to 650 nm and the NA from 0.45 to 0.6, the recording capacity of 6 to 8 times (4.7 GB /
Face).

Further, recently, in order to record a high-quality moving image for a long time, the recording / reproducing wavelength is shortened to about 400 nm, and the numerical aperture of the objective lens is increased to about 0.85. 4 times or more, that is, 20GB
Attempts have been made to achieve recording capacities of more than per side.

However, when the NA is increased as described above, the tilt margin is reduced. The tilt margin is
The tolerance of the tilt of the optical information medium with respect to the optical system.
Is determined by Assuming that the recording / reproducing wavelength is λ and the thickness of the transparent substrate on which the recording / reproducing light is incident is t, the tilt margin is proportional to λ / (t · NA ³ ). In addition, when the optical information medium is inclined with respect to the laser beam, that is, when tilt occurs, wavefront aberration (coma aberration) occurs. Assuming that the refractive index of the substrate is n and the inclination angle is θ, the wavefront aberration coefficient is (１ ／) · t · {n ² · sin θ · cos θ} · NA ³ / (n
² −sin ² θ) ^-5/2 . From these equations, it can be seen that the thickness t of the base may be reduced in order to increase the tilt margin and suppress the occurrence of coma. Actually, in the DVD, the tilt margin is secured by setting the thickness of the base to about half (about 0.6 mm) of the thickness of the CD base (about 1.2 mm).

By the way, in order to record a higher-quality moving image for a long period of time, there has been proposed a structure in which the substrate can be made thinner. In this structure, a substrate having a normal thickness is used as a support substrate for maintaining rigidity, an information recording surface including pits and a recording layer is formed on the surface thereof, and a light having a thickness of about 100 μm is formed thereon as a thin substrate. A transmission layer is provided, and recording / reproducing light is made to enter through the light transmission layer. With this structure, the substrate can be made extremely thin compared to the conventional structure,
It is possible to achieve a high recording density by the development. A medium having such a structure is described in, for example, JP-A-10-289489. The medium described in the publication has a light transmitting layer made of a photocurable resin.

In forming a light transmitting layer having a thickness of about 100 μm, a method of applying and curing a photocurable resin can be used. In general, various methods can be used for applying the resin, but some methods are difficult to use for forming the light transmitting layer.
For example, the screen printing method is used for printing a label surface on a conventional optical disc, and is a method having excellent productivity. However, it is difficult to use screen printing for forming the light transmitting layer. The reason is as follows.

The coating solution used for printing on the label surface exhibits thixotropic properties because it contains pigments and fillers (silica gel, alumina, etc.). Therefore, application by screen printing is easy, and a considerably thick resin layer can be formed with a relatively uniform thickness. On the other hand, since the light transmitting layer needs to be excellent in light transmitting property and homogeneous, it cannot contain a pigment or a filler. Therefore, thickness 100μ
Inconvenience occurs when a light transmission layer of about m is formed. Specifically, when the light transmitting layer is formed by one application, the resin does not show thixotropic, so that a resin having a considerably high viscosity and a plate having a coarse mesh are required. But,
If the resin has a high viscosity, troubles such as stringing and entrapment of bubbles occur when the plate is released, and the printing adequacy is deteriorated.
Also, if a low-viscosity resin is used to avoid this,
Liquid dripping occurs due to the coarse mesh, and swelling occurs due to the effect of surface tension on the coating boundary of the light transmitting layer (near the outer peripheral edge and the inner peripheral edge of the disk). The area where the swell has occurred cannot be used as a data recording area.

Therefore, in order to form a light transmitting layer by a screen printing method which is excellent in productivity, it is necessary to use a resin which does not contain a pigment or a filler and exhibits thixotropic properties. If the resin exhibits thixotropy, it is in a gel state on the plate, and when a shearing force is applied by a squeegee during printing, it becomes a sol state, flows and is transferred, and returns to a gel state again after forming a coating film. Next, by curing by ultraviolet irradiation or the like, a uniform light-transmitting layer having a uniform thickness and good transparency over the entire coating film can be obtained.

[0017]

SUMMARY OF THE INVENTION It is an object of the present invention to allow a wide range of organic media to be gelled, and to further reduce the formed gel (or viscous fluid) to a gel state (or viscous state). ) Is to provide a gelling agent capable of stabilizing the gel by polymerizing while maintaining the above condition. The application to such a gelling agent is particularly effective, and the synthesis is performed by a simple method. An object of the present invention is to provide a polymerizable functional group-containing alkylene amide derivative of a novel compound. Another object of the present invention is to obtain a coating composition having an appropriate viscosity by using the gelling agent, and to provide a coated body having a functional coating film having excellent properties such as being uniform and flat.

[0018]

Means for Solving the Problems To solve the above problems, the present invention is specified by the following items. That is, the present invention has been intensively studied on the gelling agent for improving the stability of the gel, and as a result, focused on photopolymerization as a means for strengthening the binding of the gel, and polymerized the gel formed by the low molecular weight compound to form a weak binding. To reinforce it.

(1) A polymerizable functional group-containing alkyleneamide derivative represented by the following formula (1), having an amino acid derivative segment and a polymerizable functional group.

[0020]

Embedded image

[In the formula (1), n is an integer of 2 to 30, and A ¹ and A ² each represent-(CH ₂ ) ₂ COOR
(Here, R represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a phenyl group or a benzyl group.), -CH
_{(CH 3) 2, -CH 2} CH (CH 3) 2, -CH (CH 3)
Represents C ₂ H ₅ or —CH ₂ C ₆ H ₅ , wherein B ¹ and B ² are
_{Each, -CONH (CH 2) 2 OCOC} (CH 3) =
_{CH 2, -COC (CH 3)} = CH 2 and -COCH =
Represents a vinyl-containing group or an alkyl group selected from CH ₂ , at least one of which is a vinyl-containing group. A ¹ and A ²
May be the same or different, and when both are vinyl-containing groups, B ¹ and B ² may be the same or different. m1 and m2 are each 1 or 2. (2) A gelling agent having an amino acid derivative segment and a polymerizable functional group (excluding a styryl-containing group), wherein the viscous fluid or gel is maintained in a viscous state or a gel state while maintaining a high molecular weight. A gelling agent that can be converted into a gel. (3) The gelling agent according to the above (2), which is a polymerized functional group-containing alkyleneamide derivative represented by the following formula (1).

[0022]

Embedded image

In the formula (1), n is an integer of 2 to 30, and A ¹ and A ² are each — (CH ₂ ) ₂ COOR
(Here, R represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a phenyl group or a benzyl group.), -CH
_{(CH 3) 2, -CH 2} CH (CH 3) 2, -CH (CH 3)
Represents C ₂ H ₅ or —CH ₂ C ₆ H ₅ , wherein B ¹ and B ² are
_{Each, -CONH (CH 2) 2 OCOC} (CH 3) =
_{CH 2, -COC (CH 3)} = CH 2 and -COCH =
Represents a vinyl-containing group or an alkyl group selected from CH ₂ , at least one of which is a vinyl-containing group. A ¹ and A ²
May be the same or different, and when both are vinyl-containing groups, B ¹ and B ² may be the same or different. m1 and m2 are each 1 or 2. (4) After applying the gelling agent composition for forming a coating film containing the gelling agent of (2) or (3) and an organic medium to an adherend, the composition is cured by active energy rays to provide functionality. A coated body with a coating film formed.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The gelling agent of the present invention is a compound having an amino acid derivative segment and a polymerizable functional group. The amino acid derivative segment is preferably an alkylene amide derivative of an amino acid and an alkylenediamine, and the amino acid may be a derivative as long as it has at least one terminal carboxyl group, such as glutamic acid and its ester, valine, leucine, isoleucine, phenylalanine and the like. A dimer such as valine or leucine is also preferably used. On the other hand, the polymerized functional group is preferably selected from a 2-methacryloyloxyethyl segment, a methacrylic acid segment, an acrylic acid segment, and the like. However, since the styrene segment breaks the balance between the amphiphilicity and hydrophobicity required as a gelling agent,
As the polymerization functional group, one having no styrene segment is selected.

It is sufficient that at least one polymerizable functional group is present in one molecule, but preferably 2 to 4, and particularly preferably 2 in terms of synthesis and function.

A particularly preferred gelling agent has a basic skeleton in which a terminal carboxyl group of one kind of amino acid selected from glutamic acid and its ester, valine, leucine, isoleucine, phenylalanine and the like is converted into an amidated product by alkylenediamine, In addition, at least one, and preferably both, of the amino groups at both terminals have one type of polymerization functional group selected from a 2-methacryloyloxyethyl segment, a methacrylic acid segment, an acrylic acid segment and the like introduced by an amide bond.

Although the gelling agent of the present invention can gel or thicken various organic media, it further introduces a polymerizable functional group at the molecular terminals, particularly at both molecular terminals. Irradiating light to a low molecular gel or viscous fluid formed by heating and dissolving in an organic medium has the characteristic that it can be polymerized while maintaining the gel state or viscous state. A stable gel can be obtained. Further, although the gel strength increases as the concentration of the monomer increases, the strength of the polymer gel synthesized from the high-concentration monomer gel significantly increases as compared with the monomer gel.

Utilizing such properties, it can be used not only as a gelling agent, but also as a viscosity modifier or a coating material for a coating composition, and can be used as a liquid organic medium (organic solvent, solvent) for the formed coating film. ) Is removed and cured by active energy rays, so that it can be expected to be used as various functional films. That is, a coated body having a uniform and flat functional coating film can be obtained.

Particularly, as the gelling agent of the present invention, a polymerized functional group-containing alkyleneamide derivative represented by the following formula (1) is preferable, and this is a novel compound.

[0030]

Embedded image

In the formula (1), n is an integer of 2 to 30,
Particularly, it is preferably 10 to 14.

A ¹ and A ² are each — (CH ₂ ) ₂
COOR (where R represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms (e.g., methyl, ethyl, butyl, pentyl, octyl, dodecyl, octadecyl, docosyl, etc.), a phenyl group or a benzyl group),- CH
_{(CH 3) 2, -CH 2} CH (CH 3) 2, -CH (CH 3)
It represents a C ₂ H ₅ or -CHC ₆ H _5. B ¹ and B ² are each —CONH (CH ₂ ) ₂ OCOC (CH ₃ ) = C
_{H 2, -COC (CH 3)} = CH 2 and -COCH = C
Represents a vinyl-containing group or an alkyl group selected from H ₂ , at least one of which is a vinyl-containing group, and preferably both are vinyl-containing groups. The alkyl group represented by B ¹ and B ² is a linear alkyl group having 1 to 22 carbon atoms (for example,
Methyl, butyl, octyl, octadecyl, docosyl, etc.) are preferred.

A ¹ and A ² , and B ¹ and B ² when both are vinyl-containing groups may be the same or different, but are preferably the same in terms of synthesis.

M1 and m2 are each 1 or 2
It is.

Preferred examples of the gelling agent of the present invention are shown below, but are not limited thereto. This is shown according to the expression (1).

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

The gelling agent of the present invention is used alone, but may be used in combination of two or more.

The gelling agent of the present invention can be synthesized by reacting an alkyleneamide derivative serving as an amino acid derivative segment with a polymerizable functional group-containing compound serving as a polymerizable functional group segment.

The amino acids used as the raw materials for the alkyleneamide derivatives of the present invention include those obtained by extracting a hydrolyzate of a naturally occurring protein with an acid, alkali or enzyme, those isolated from fermentation or culture products of microorganisms, Any of those obtained by a chemical synthesis method may be used. The amino acid may be either an optically active compound or a racemic compound. Preferred are branched amino acids, acidic amino acids and aromatic amino acids.

The amino acids and derivatives thereof according to the present invention include L-glutamic acid, L-glutamic acid ester, L-valine, L-valyl-L-valine, L-leucine, L-isoleucine, L-isoleucyl-L-isoleucine, L-phenylalanine and the like.

The alkylene diamine used as the starting material for the alkylene amide derivative has an alkylene chain of 2 to 3 carbon atoms.
A linear alkylene chain of 0 is preferable, and in some cases, it may contain an unsaturated bond. Specific examples of alkylenediamines include ethylenediamine, 1,3
-Propanediamine, 1,4-butanediamine, 1,5
-Pentanediamine, 1,6-hexanediamine, 1,
7-heptanediamine, 1,8-octanediamine,
1,9-nonanediamine, 1,10-decanediamine,
Examples thereof include 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, and 1,14-tetradecanediamine. Among them, alkylene diamine having 10 to 14 carbon atoms is most preferable.

The alkylene amide derivative of the present invention can be synthesized by a known method by appropriately selecting the amino acid and alkylenediamine. For example, it can be synthesized by protecting one functional group of an amino acid, forming a peptide bond with both terminal amino groups of the alkylenediamine, and then removing and removing the protecting group.

The polymerizable functional group, which is another effective segment, is obtained by converting a terminal carboxyl group into a halide from methacrylic acid or acrylic acid having a double bond at a molecular terminal, or 2-methacryloyloxy. It is introduced using a polymerized functional group-containing compound such as isocyanate such as ethyl isocyanate.

The polymerized functional group-containing alkylene amide derivative of the present invention can be synthesized by a known method using the above-mentioned alkylenediamine and the polymerized functional group-containing compound as raw materials. For example, an alkylenediamine and a polymerized functional group-containing compound in an organic medium such as tetrahydrofuran are heated at 10 to 30 °.
By reacting with C for about one day, the polymerized functional group-containing alkyleneamide derivative of the present invention can be obtained. In addition, when one terminal is an alkyl group, a conventional method may be used.

The reaction product thus obtained includes:
In some cases, unreacted raw materials remain in addition to the target compound, but they can be purified by a known method such as extraction or recrystallization. When the gelation is not affected, the mixture may be used as it is.

The polymerized functional group-containing alkylene amide derivative of the present invention can be identified by elemental analysis, infrared absorption spectroscopy (IR) and the like.

The gelling agent of the present invention which is not included in the formula (1) can be synthesized and identified in the same manner as described above.

The alkylene amide derivative having a polymerization functional group of the present invention can gel a liquid organic medium with a small addition amount. Examples of the liquid organic medium include alcohols such as 1-propanol, 2-propanol and 1-butanol; aromatics such as nitrobenzene and chlorobenzene; ketones such as cyclohexanone and propylene carbonate (propylene carbonate; PC); ,
Cyclic ethers such as 4-dioxane, nitrogen compounds such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMA), aprotic polar media such as dimethylsulfoxide (DMSO), pyridine and the like Basic media, coating monomers, and the like. The present invention is also effective for a mixture of these organic media and a medium as a main component. In this case, the use amount of the gellable organic medium is preferably 30 vol% or more of the whole.

For example, although ethylene carbonate (ethylene carbonate: EC) is a solid, it can be dissolved in the above-mentioned liquid organic medium in which it can be dissolved and subjected to gelation.
In addition, the coating monomer itself, in addition to those that are liquid, even if it is solid itself, after selecting a dissolvable medium from the liquid organic medium and dissolving,
It may be subjected to gelation. Furthermore, not only monomers but also oligomers and polymers can be used.

A gelled product can be prepared by adding the compound of the present invention to the above-mentioned liquid organic medium, heating and stirring the mixture to the boiling point of the organic medium so as to obtain a uniform state, and then allowing to stand at room temperature. The amount of the compound of the present invention to be added when preparing the gel depends on the type of the organic solvent to be gelled, but may be 5 to 1000 parts by mass of the liquid organic medium.
The amount is preferably from 50 to 50 parts by mass, more preferably about 5 to 30 parts by mass. If the amount of the compound of the present invention is too small, it will remain liquid even after dissolution in an organic medium. Even if it is too much, the gelling agent may not be completely dissolved. The hardness of the gel can be adjusted by the amount of the compound of the present invention added.

The compound of the present invention is formed into a gel (viscous state) by irradiating a gelled substance (viscous fluid) prepared by adding it to a liquid organic medium with an active energy ray (eg, ultraviolet ray UV, electron beam EB). While maintaining the above, polymerization becomes possible. Ultraviolet rays are preferably used as the active energy. By irradiating with ultraviolet light shielding light of 360 nm or more for several minutes to about two nights, it is possible to polymerize while maintaining the gel state. The amount of the compound of the present invention used in polymerizing the gel may be any amount as long as it is at least the minimum amount that can gel various organic media. The type of organic medium used for polymerizing is 1-propanol, 2-propanol, 1-butanol, cyclohexanone, propylene carbonate, 1,4-dioxane, N, N-dimethylformamide, N, N- Dimethylacetamide, dimethylsulfoxide, coating monomers are suitable.

When preparing a gelled substance for polymerizing by ultraviolet rays, it is necessary to add a polymerization initiator.
Examples of the polymerization initiator mentioned here include benzoin ethyl ether, 2,2-dimethoxy-2-phenylacetophenone, and the like. That is, when the compound of the present invention is dissolved by heating in a liquid organic medium, one kind of the above-mentioned polymerization initiator is selected and added, and both are dissolved by heating to prepare a gel.

The polymer gel obtained by the above method is
Before polymerization, it is a thermoplastic gel,
It is a thermo-irreversible gel that does not melt when heated.
Further, the obtained polymer gel does not show solubility in any organic medium.

Accordingly, the polymerized functional group-containing alkylene amide derivative of the present invention can be synthesized from industrially available raw materials by a simple method, and the above-mentioned adhesives, resins and paints containing an organic medium can be used. It is possible to control the fluidity by adding it to the like, or to polymerize in a state where the fluidity is controlled to reinforce the binding of the gel.

By using the gelling agent of the present invention, a gelling agent composition containing a gelling agent and an organic medium can be formed. It becomes possible to form a coating film on the body, and it is possible to obtain a coated body on which various functional coating films are formed.

The liquid organic medium used in the gelling agent composition of the present invention includes, in addition to the above-mentioned liquid organic medium, commonly used coating solvents, especially liquid substances of active energy ray-reactive monomers, oligomers and polymers. Or active energy ray-reactive monomers, oligomers, and polymers, including solids, in the form of a liquid organic medium (solvent).
Dissolved in the coating composition (clear coating or screen printing various functional inks,
Highly functional filler high content coating and printing paint,
Etc.) and adjust to pseudoplastic flow characteristics (viscosity, elasticity, thixotropy, etc.) that are easy to coat (including printing), perform coating (including printing), then dry and remove the solvent If it is contained, it can be removed to form various solid functional coating films. Further, by irradiating with an active energy ray such as an ultraviolet ray, the gelling agent can be fixed by reacting with a reactive monomer, an active energy ray-reactive polymer, or the like, and cured. The polymerization conditions and the like can be appropriately selected.

As a result, the composition itself has good transparency,
A high-strength coating film is obtained, and the added gelling agent is discharged to the surface or interface of the coating film (coating film), so that the original performance of the coating film is not impaired.

In the case of a coating film containing a filler having a high active energy ray shielding property such as magnetic powder, curing by electron beam irradiation is preferable.

The gelling agent of the present invention can be used for a battery in which evaporation of an electrolyte or the like is a problem, for example, an electrolyte for a dye-sensitized solar cell or a lithium battery, or a coating film for a magnetic recording medium or an optical information medium. Used for the production of

The following are examples of these applications.

The gelling agent of the present invention can be used for an electrolyte of a dye-sensitized solar cell. The dye-sensitized solar cell has a conductive support, a semiconductor fine particle film adsorbing a sensitizing dye provided on the conductive support, and a counter electrode,
An electrolyte is interposed between the semiconductor fine particle film and the counter electrode. As its general structure, a cathode provided with a semiconductor fine particle film such as titanium oxide on which a sensitizing dye is adsorbed on a conductive support such as a transparent electrode, or a conductive support such as a transparent electrode, or A sandwich type cell in which an electrolytic solution containing a redox couple is sealed between an anode having a conductive support coated with a metal film such as Pt or the like. The operating principle is
A sensitizing dye adsorbed on the semiconductor surface such as titanium oxide absorbs light, excites light, and excited electrons are quickly injected into the conduction band of the semiconductor. Electrons are taken out from the transparent electrode of the cathode, moved to the anode, and electrolyzed from the anode. A redox pair in a liquid receives electrons, and a dye that has lost electrons receives electrons from the redox pair and returns to its original state.

By adding the gelling agent of the present invention to the electrolytic solution and gelling the electrolytic solution, the volatilization of the solvent can be almost completely suppressed, and the electrolytic solution becomes extremely stable. A stable battery characteristic without deterioration over a long period of time can be obtained. In particular, a polymerized gel is effective.

Conventionally, the biggest problem of such a solar cell is the stability of the electrolytic solution. Since an organic solvent is used, deterioration of the sealant and volatilization of the solvent during use are liable to occur. However, the use of the gelling agent of the present invention solves the problem that the battery characteristics are extremely deteriorated.

The semiconductor fine particles used for the cathode are fine particles of metal chalcogenide (for example, oxides and sulfides) and perovskite. Particularly, titanium oxide which is an oxide is generally used. Will be described as a representative example.

To manufacture a titanium oxide electrode as a cathode, first, a coating solution containing titanium oxide fine particles is prepared. The finer the primary particle diameter of the titanium oxide fine particles, the more preferable.
The average value of the primary particle diameter is usually 1 to 5000.
nm, preferably 5 to 50 nm.

The dispersion containing the titanium oxide fine particles can be obtained by a method of producing and dispersing titanium oxide fine particles by a sol-gel method, or by dispersing titanium oxide fine particles in a solvent.

The titanium oxide fine particles dispersed in the solvent are dispersed in the form of primary particles. Solvents include water, organic solvents,
A mixed solution of water and an organic solvent may be used. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol and terpineol; ketones such as methyl ethyl ketone, acetone and acetylacetone; and hydrocarbons such as hexane and cyclohexane.

In order to enhance the dispersibility of the titanium oxide fine particles in the solvent, it is preferable to previously treat the surface of the titanium oxide fine particles with a dispersant, or to add a dispersant to the coating solution. If necessary, a surfactant (tr
iton X-100) and a viscosity modifier. The concentration of titanium oxide fine particles in the dispersion is 0.1 to 70.
%, Preferably 5 to 40% by mass.

Next, the above coating solution is applied on a substrate, dried, and then fired in air or an inert gas to form a titanium oxide film on the substrate. As the substrate, a substrate having at least its surface formed on a conductive surface is used. As such a substrate, a substrate formed by forming a conductive metal oxide thin film of indium oxide or tin oxide on a heat-resistant substrate such as glass or a substrate made of a conductive material such as metal is used. Such a conductive substrate is well known in the art. The lower the surface resistance, the better, and the sheet resistance is 40Ω /.
□ or less (usually 0.1 Ω / □ or more). The thickness of the substrate is not particularly limited.
5 mm. The conductive substrate may be transparent or opaque, but either the substrate and the counter electrode are transparent,
Usually, the substrate is transparent. The coating obtained by coating and drying on the substrate has a low bonding strength with the substrate and the bonding strength between the fine particles, and has a low mechanical strength. By cross-linking the titanium precursor, the mechanical strength is enhanced, and a fired product film firmly fixed to the substrate can be obtained.

The fired product film is a porous film having a thickness of at least 10 nm, preferably 500 to 30,000 nm, and a ratio of the actual surface area to the apparent surface area of 10 or more, preferably 100 or more. The upper limit of this ratio is not particularly limited, but is usually 1000 to 2000. The apparent surface area means a normal surface area. For example, when the surface shape is a rectangle, it is represented by a vertical length × a horizontal length. The actual surface area is the BE determined by the amount of krypton gas adsorbed.
T means surface area. A specific measuring method is a method in which a titanium oxide film with a substrate having an apparent surface area of 1 cm ² is adsorbed with krypton gas at a liquid nitrogen temperature by using a BET surface area measuring device (ASAP2000, manufactured by Micromeritics Co., Ltd.). The BET surface area is calculated based on the krypton gas adsorption amount obtained by this measurement method. Such a porous structure film has fine pores inside and fine irregularities on its surface. When the ratio of the actual surface area to the thickness and the apparent surface area of the fired product film is smaller than the above range, when the organic dye is adsorbed on the surface as a monomolecular film, the surface area of the organic dye monomolecular film becomes small, An electrode with good absorption efficiency cannot be obtained. The fired product film having the porous structure as described above is obtained by applying a dispersion liquid containing titanium oxide fine particles on a substrate, and firing the fine particle aggregate film formed by drying. It can be obtained by lightly baking the body film. In this case, the firing temperature is lower than 1000C, usually 300-800C,
Preferably it is 400-700 degreeC. If the firing temperature is higher than 1000 ° C., the sintering of the fired material film proceeds too much, the actual surface area becomes small, and a desired fired material film cannot be obtained.
The ratio of the actual surface area to the apparent surface area can be controlled by the particle size and specific surface area of the titanium oxide fine particles, the titanium oxide precursor concentration, the firing temperature, and the like.

Next, the organic dye is adsorbed as a single molecule on the surface of the titanium oxide film on the substrate obtained as described above. As the organic dye, a dye capable of chemically bonding to the titanium oxide film is preferable, and a dye having a carboxyl group, a sulfonic acid group, a phosphoric acid group, or a hydroxyl group in a molecule is preferable. Specifically, bipyridyl Ru complex, tar
Ru complexes such as pyridyl Ru complex, phenanthroline Ru complex, bicinchoninic acid Ru complex, eosin Y, dibromofluorescein, fluorescein, rhodamine B, pyrogallo-
And organic dyes such as dichlorofluorescein, erythrosin B, fluorescin, and mercurochrome.

To adsorb the organic dye as a single molecule on the surface of the titanium oxide film, the titanium oxide film may be immersed together with the substrate in an organic dye solution formed by dissolving the organic dye in an organic solvent. In this case, as the organic dye solution penetrates deep inside the titanium oxide film which is a porous structure film,
Prior to immersion of the film in organic dyes,
It is preferable to remove the bubbles contained in the film in advance by performing a heat treatment. The immersion time is about 30 minutes to 24 hours. Reflux treatment may be performed to efficiently adsorb the dye. Further, the immersion treatment can be repeated a plurality of times as necessary. After the immersion treatment, the titanium oxide film on which the organic dye has been adsorbed is dried at normal temperature to 80 ° C.

In the present invention, the organic dye adsorbed on the titanium oxide film does not need to be one kind, and a plurality of organic dyes having different light absorption regions can be adsorbed if necessary. Thus, light can be used efficiently. In order to adsorb a plurality of organic dyes to the film, a method of immersing the film in a solution containing a plurality of organic dyes, a method of preparing a plurality of organic dye solutions, and sequentially immersing the film in these solutions can be used. . In a solution in which an organic dye is dissolved in an organic solvent, any organic solvent can be used as long as it can dissolve the organic dye. Such materials include, for example, methanol, ethanol,
Acetonitrile, dimethylformamide, dioxane,
Dichloromethane, toluene and the like. The concentration of the organic dye in the solution is 1 to 200 mg, preferably 1 to 100 ml of the solution.
It is about 0 to 100 mg.

The amount of the dye to be used is generally 0.1 to 1 m ² of the support in order to obtain a sufficient sensitizing effect in titanium oxide.
It is preferably from 01 to 100 mmol. The amount of the dye adsorbed on the semiconductor fine particles is preferably 0.01 to 1 mol per 1 g of the titanium oxide fine particles.

The gelled electrolytic solution (gel electrolyte) has I ⁻ / I ₃
^- system or, Br - ^/ Br ₃ ^- system, the electrolyte containing a redox couple and an organic solvent such as quinone / hydroquinone system, in which the gelled by adding a gelling agent of the present invention. The addition amount of the gelling agent is as described above. The electrolyte serving as a redox _couple is I ₂ and a metal iodide such as LiI, NaI, KI, CsI, and CaI ₂ , an iodine salt of a quaternary imidazolium compound, an iodine salt of a quaternary pyridinium compound, and an iodine of a tetraalkylammonium compound. Salt, Br ₂ and LiBr,
NaBr, KBr, CsBr, metal bromide such as CaBr _2, or Br ₂ and tetraalkyl ammonium bromide, bromine salts such as quaternary ammonium compounds pyridinium bromide, ferrocyanide - ferricyanide or ferrocene - such as ferricinium ion Metal complexes, sodium polysulfide, sulfur compounds such as alkylthiol-alkyldisulfide, viologen dyes, hydroquinone-quinone, and the like can be used. Among them, I ₂ and LiI, NaI, KI, CsI, CaI ₂
Metal iodides such as iodine salts of quaternary imidazolium compounds, iodine salts of quaternary pyridinium compounds, and iodine salts of tetraalkylammonium compounds are particularly preferred. In order to ensure a sufficient function as an electron carrier, a preferable electrolyte concentration is 0.05 mol / L or more and 1.5 mol / L or less. In particular, it is preferably from 0.1 mol / L to 0.8 mol / L. When an iodine is added to the electrolyte to generate an oxidation-reduction pair in advance, a preferable addition concentration is 0.01 mol / L or more and 0.2 mol / L or less.

The solvent used is not particularly limited as long as it is electrochemically inert and can be gelled by the gelling agent of the present invention, and can be selected from the above liquid organic media. Further, a mixed solvent thereof may be used, but it is preferable that the mixed solvent contains the above liquid organic medium in an amount of 30 vol% or more. Among them, carbonate compounds such as ethylene carbonate and propylene carbonate, and nitrile compounds such as acetonitrile are particularly preferable. Two or more kinds may be used in combination.

In order to polymerize the gelling agent, the low molecular gel electrolyte is irradiated with ultraviolet rays or the like. This further increases the stability of the gel electrolyte.

As the counter electrode, any material may be used as long as it has conductivity, and any conductive material may be used. The catalyst has a catalytic activity for performing a reduction reaction of oxidized redox ions such as I ₃ ^- ions at a sufficient speed. It is preferable to use those having Examples of such a material include a platinum electrode, a material obtained by subjecting a conductive material to platinum plating or platinum vapor deposition, rhodium metal, ruthenium metal, ruthenium oxide, carbon, and the like.

In the dye-sensitized solar cell, the titanium oxide electrode, the electrolyte, and the counter electrode are housed in a case and sealed, or the whole is sealed with a resin. In this case, light is applied to the titanium oxide electrode. In a battery having such a structure, when light is applied to the titanium oxide electrode, a potential difference is generated between the titanium oxide electrode and its counter electrode, and a current flows between the two electrodes.

For a general description of such a dye-sensitized solar cell, reference can be made to JP-A-11-185836.

The gelling agent of the present invention is used as a viscosity modifier when coating a magnetic layer of a magnetic recording medium or a non-magnetic lower layer provided between a non-magnetic support and a magnetic layer. In addition, the nonmagnetic layer and the nonmagnetic lower layer are dried after coating, the solvent is removed, and then, electron beam irradiation is performed to obtain a cured coating film. It plays a role of an agent and therefore contributes to the improvement of the surface properties of the coating film. Thereafter, it is polymerized together with the resin binder by electron beam irradiation, whereby a dense, high-strength and smooth surface coating film is obtained.

The magnetic layer of the magnetic recording medium is thinned for high-density recording. However, by using the gelling agent of the present invention as a viscosity modifier, magnetic powder, particularly ferromagnetic metal powder, can be used. It is possible to enhance flow characteristics (pseudoplastic flow characteristics) in which a coating solution containing a large amount of an organic solvent can be easily applied. Therefore, not only a die coater but also a roll coater (flexo, gravure) can be used to obtain 0.5 μm.
Thus, a magnetic layer which is thin and smooth, having a thickness of not more than m, is suppressed in fluctuation of film thickness after drying, and is highly filled with magnetic powder.

On the other hand, the non-magnetic lower layer has an average particle size of 0.02
TiO ₂ granular particles of about 0.04 μm or an average major axis length of 12
Non-magnetic fine particles such as α-Fe ₂ O ₃ needle-like particles (Al, Si, etc. may be added) having an axial ratio of about 0 to 200 nm and an axis ratio of about 6 to 9, but a coating solution containing such fine particles Can be approximated to the viscosity behavior that facilitates application, and smooth and uniform application can be realized.

Since the magnetic layer is extremely thin, the surface properties of the non-magnetic lower layer are reflected. However, a smooth non-magnetic lower layer is obtained by the gelling agent of the present invention, and the magnetic layer becomes extremely smooth.

Solvents for the coating solution for each layer include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols such as methanol, ethanol, propanol and butanol; methyl acetate, ethyl acetate, butyl acetate and ethyl lactate. And esters such as ethylene glycol cenoacetate: glycol dimethyl ether, glycol monoethyl ether,
Ethers such as dioxane and tetrahydrofuran: aromatic hydrocarbons such as benzene, toluene and xylene: halogenated hydrocarbons such as methylene chloride, ethylene chloride, carbon tetrachloride, chloroform, dichlorobenzene and the like can be used. These various solvents take into account the solubility of the monomers, oligomers, and polymers used, and the balance of the boiling point and evaporation rate for drying while maintaining the smoothness of the wet coating film. Therefore, a mixture of two or more solvents, such as a gelling agent and a solvent that easily forms hydrogen bonds, etc., and a solvent that does not have much gelling ability but has excellent compatibility as a coating solvent other than the above-described gelling ability It is more effective to use it. The mixing ratio is appropriately selected.

When the gelling agent is used for the purpose of adjusting the viscosity, the amount of the gelling agent may be the same as that of the above-mentioned gelling agent, but may be added to 100 parts by mass of the above-mentioned two or more kinds of the balanced mixed solvent. On the other hand, it is preferably 0.1 to 9 parts by mass.

The coating method may be any known one.

Such a magnetic recording medium is prepared by applying a coating solution for a non-magnetic lower layer to which a gelling agent of the present invention is added on a non-magnetic support, removing the solvent by drying, and
The surface of the non-magnetic lower layer is calendered for smoothing, and further irradiated with an electron beam.After that, a coating solution for the magnetic layer containing the gelling agent of the present invention is applied, and the solvent is removed by drying. In order to increase the smoothness of the surface of the magnetic layer, a calendering process is performed, and then the electron beam irradiation is performed.

Such a magnetic recording medium has a magnetic layer containing a ferromagnetic powder, preferably a ferromagnetic metal powder, on a non-magnetic support, and at least one layer between the non-magnetic support and the magnetic layer. And a non-magnetic lower layer of
A back coat layer is provided if necessary.

As a material for forming the non-magnetic support, for example, polyethylene terephthalate, polyethylene
Polyesters such as 2,6-naphthalate, polyolefins such as polypropylene, cellulose triacetate, cellulose derivatives such as cellulose diacetate,
Plastics such as polyamide, aramid resin, polyimide resin, polyethersulfone (PES), polyalate, polyetheretherketone (PEEK), acrylic resin, and polycarbonate can be given.

The form of the non-magnetic support is not limited, and mainly includes a tape form, a film form, a sheet form, a card form, a disk form, a drum form and the like. The thickness of the non-magnetic support is not particularly limited, for example, in the case of a film or sheet,
It is usually 2 to 100 μm, preferably 3 to 50 μm, and 30 μm to 10 mm in the case of a disk or card.
In the case of a drum shape, it is appropriately selected according to a recorder or the like.

The magnetic layer preferably contains a ferromagnetic metal powder. As the ferromagnetic metal powder, any ferromagnetic metal powder can be used. Fe, Al,
It preferably contains Co and one or more rare earth elements selected from the group consisting of Sm, Nd, Y, Pr, and La.

The content of the ferromagnetic metal powder is usually 60 to 95% by mass based on the total solid content in the layer.
And preferably 70 to 90% by mass.

Typical examples of the binder contained in the magnetic layer include polyurethane, polyester, and vinyl chloride copolymers, and are of a type that is crosslinked by an active energy ray such as an electron beam. These resins _{-SO 3 M, -OSO 3 M,} -COOM, PO (O
It preferably has at least one polar group selected from M ₁ ) ₂ and a sulfobetaine group. However, in the above polar group, M represents a hydrogen atom or an alkali metal such as Na, K, Li, and M ₁ represents a hydrogen atom, Na,
Represents an alkali metal such as K or Li or an alkyl group.

The content of the binder was as follows.
The amount is usually 8 to 25 parts by mass, preferably 10 to 20 parts by mass with respect to 00 parts by mass. The binder is not limited to one kind alone, and two or more kinds can be used in combination.

To improve the quality of the magnetic layer, an abrasive,
Lubricants (fatty acids and / or fatty acid esters, etc.),
Additives such as curing agents, dispersants, antistatic agents and conductive (fine) powders can be included as other components. As described above, the thickness of the magnetic layer is 0.5 μm or less, and is usually preferably 0.05 μm or more.

The non-magnetic lower layer contains the same binder as the magnetic layer and contains a non-magnetic powder. As described above, the non-magnetic powder has an average particle size of 0.02 to 0.0
4 μm titanium oxide (TiO ₂ ) particles and an average major axis length of 12 μm
Α-Fe ₂ O ₃ needle-like particles having an axial ratio of about 0 to 200 nm and an axis ratio of about 6 to 9 (Al, Si or the like may be added) and the like are preferable. The content of the nonmagnetic powder is 50% of the total components of the nonmagnetic lower layer.
To 99% by mass, and the thickness of the nonmagnetic lower layer is preferably 0.2 to
It is preferably 2.5 μm.

For other general descriptions of such a magnetic recording medium, reference can be made to JP-A-9-35964.

Next, a case where the gelling agent of the present invention is applied to the production of an optical information medium will be described.

FIG. 1 shows a configuration example of the optical information medium. This optical information medium is a recording medium, having a recording layer 4 as an information recording surface on a support base 20, and having a light transmitting layer 2 on the recording layer 4. The laser beam for recording or playback is
Light enters through the light transmitting layer 2.

The present invention can be applied regardless of the type of the recording layer. That is, for example, even for a phase change recording medium,
The present invention can be applied to a pit formation type recording medium and a magneto-optical recording medium. In general, a dielectric layer or a reflective layer is provided on at least one side of the recording layer for the purpose of protecting the recording layer or providing an optical effect, but is not shown in FIG. Further, the present invention is not limited to the recordable type as shown in the figure, but is also applicable to a read-only type. In that case, the pit row formed integrally with the support base 20 constitutes the information recording surface. Next, a specific configuration of each unit of the medium will be described.

The support base 20 is provided to maintain the rigidity of the medium. The thickness of the support base 20 is usually 0.2
The thickness may be set to about 1.2 mm, preferably 0.4 to 1.2 mm, and may be transparent or opaque. Support base 2
0 may be made of resin as in the case of an ordinary optical recording medium, but may be made of glass. Grooves (guide grooves) 21 usually provided in an optical recording medium can be formed by transferring grooves provided in the support base 20 to respective layers formed thereon as shown in the figure. Groove 21
Is a region existing on the near side when viewed from the recording / reproducing light incident side, and a streaky convex portion existing between adjacent grooves is called a land.

The light transmitting layer 2 has a light transmitting property for transmitting a laser beam. The thickness of the light transmitting layer 2 in the present invention is preferably 30 to 200 μm, more preferably 50 to 200 μm.
more than 200 μm, more preferably 70-150 μm
m. If the light transmitting layer is too thin, the optical effect of dust adhering to the surface of the light transmitting layer will increase. In addition, high N
When A is used, the distance between the optical pickup and the medium needs to be reduced, so that the optical pickup easily comes into contact with the medium surface. However, if the light transmitting layer is thin, a sufficient protective effect against the contact of the optical pickup can be obtained. Disappears. On the other hand, if the light transmitting layer is too thick, it is difficult to achieve a high recording density by increasing the NA.

The light transmitting layer 2 is formed by applying the gelling agent composition by screen printing, and irradiating the obtained coating film with active energy rays such as ultraviolet rays. The gelling agent composition used at this time contains the gelling agent of the present invention and an active energy ray-curable composition. The active energy ray-curable composition to be used is not particularly limited, and for example, various ultraviolet-curable compositions (for example, a general-purpose acrylic resin) can be used.

The roughness of the printing plate used for printing may be appropriately selected according to various conditions such as the thickness of the light transmitting layer.

The gelled composition is prepared by adding the gelling agent to an active energy ray-curable composition having a relatively low viscosity or a solution thereof, and exhibits sufficient thixotropic properties. When a shearing force is applied by a squeegee at the time of printing, it changes to a sol state, flows and is transferred, and returns to a gel state after forming a coating film. As described above, since the plate is in a gel state, even when a plate having a coarse mesh is used to form a relatively thick resin layer, liquid dripping does not occur. In addition, since it is in a sol state at the time of printing, problems such as stringing and entrapment of bubbles do not occur when the plate is released. In addition, since the film returns to the gel state again after being formed into a coating film, it is hardly affected by surface tension, and as a result, swelling at the coating boundary of the light transmitting layer is suppressed.

In the present invention, the light transmitting layer can be formed by one application, but may be applied plural times. Further, a protective coat (organic film or inorganic film) for improving scratch resistance may be provided on the surface of the light transmitting layer.

[0118]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

First, Examples and Comparative Examples of the synthesis of the present invention and comparative compounds are shown as Production Examples.

Production Example 1 Synthesis of a Dodecanediamide Derivative Having a Styrene Segment at Both Molecular Terminals (Comparative Compound) Dodecamethylenediamide Having L-valine at Both Terminals
L-valine having a benzyloxycarbonyl group (Z) as a synthetic protecting group, that is, 6.00 g of ZL-valine
(0.024 mol) was added with 50 ml of ethyl acetate, and the mixture was stirred under ice-cooling to obtain a completely uniform solution. Where N, N '
-Dicyclohexylcarbodiimide (DCC) 5.36
g (0.026 mol) was added and the mixture was stirred for 1 hour under ice cooling. 2.40 g (0.012 mol) of 1,12-dodecanediamine was added to the cloudy liquid stirred for 1 hour, and the mixture was stirred for 2 hours under ice-cooling, then returned to room temperature for 1 hour, and further heated at 45 ° C.
While stirring at room temperature overnight. The cloudy liquid was cooled in a freezer, and the precipitate was suction-filtered and dried under reduced pressure. 540 ml of 1-propanol was added to 8.02 g of the obtained product and dissolved by heating, and N, N′-dicyclohexylurea was removed by hot filtration. The filtrate was cooled overnight in a freezer, after suction filtration was dried under reduced pressure, alkylene amide derivatives of the Z-L-valine and 1,12-dodecane diamine (hereinafter [Z-L-Val-NH (CH 2) 6] to obtain a ₂ abbreviated) 6.15 g.

[ZL-Val-NH (CH ₂ ) ₆ ] ₂ 6
15 g (0.0092 mol) was dissolved by heating in 200 ml of 2-methoxyethanol, and 1 tablespoon of palladium carbon was added as a catalyst.
Reduced for a time to remove the Z group. After confirming the removal of the Z group by silica gel thin layer chromatography, the catalyst was filtered off. The filtrate is concentrated under reduced pressure to dry tetrahydrofuran 60
After dissolving by heating, insoluble matter was removed. The solution after removing the insolubles was concentrated under reduced pressure, 100 ml of hexane was added to thoroughly wash the product, suction filtration was performed, and then dried under reduced pressure to remove the Z group. The alkylenediamide derivative of L-valine and 1,12-dodecanediamine. (Hereinafter [L-Val-NH (C
H _{2) 6] 2} abbreviated) was obtained 2.54 g.

Having a styrene segment at both ends of the molecule
Synthesis of Dodecanediamide Derivative [L-Val-NH (CH ₂ ) ₆ ] ₂ 2.60 g (0.00
(65 mol) was added with 60 ml of dry tetrahydrofuran and stirred to obtain a completely uniform solution. While cooling using an ice bath, 1.99 ml (1.4 ml) of triethylamine was added thereto.
5g: 0.0143 mol) and stirred, and then 2.17 g (0.04 g) of p-vinylbenzoyl chloride under ice-cooling.
13 mol) was added dropwise and stirred. The reaction was carried out by stirring in an ice bath for 3 hours and at room temperature overnight. The obtained cloudy liquid was concentrated under reduced pressure to completely remove the medium, and methanol 100m was added thereto.
1 was added to crush the reaction product to remove triethylamine hydrochloride. After crushing well and washing with methanol, the product was suction-filtered and dried under reduced pressure overnight. 400 ml of 1-propanol was added to 3.35 g of the obtained product and dissolved by heating. The product was hot-filtered for recrystallization. The filtrate was cooled in a freezer and suction-filtered. Drying under reduced pressure was performed overnight to obtain 2.92 g of a dodecanediamide derivative having styrene segments at both molecular terminals.

The compound was identified by elemental analysis and IR. The results are shown below.

[0124] IR 3293, 2925, 2852, 1631, 1503, 1467, 1154, 987 (c
m ^-1 )

Production Example 2 Synthesis of a dodecanediamide derivative (compound No. 1) having a 2-methacryloyloxyethyl segment at both molecular terminals [L-Val-NH (CH ₂ ) ₆ ] ₂ 1.2 as in Production Example 1
100 g of toluene was added to 0 g (0.0030 mol) and dissolved by heating. 0.85 ml of 2-methacryloyloxyethyl isocyanate (0.93 g: 0.0
060 mol) was added dropwise, and the mixture was stirred and refluxed at 80 ° C., and reacted for 0.5 hour. The reaction product was cooled to room temperature, and 100 ml of hexane was added to the reaction product to crush the product and precipitate crystals. The precipitate was suction filtered and dried under reduced pressure overnight. To 1.99 g of the obtained product, 150 ml of 1-propanol was added and dissolved by heating, and recrystallization was performed by hot filtration. The filtrate was cooled in a freezer overnight, and then suction-filtered. Drying under reduced pressure was performed overnight to obtain 1.22 g of a dodecanediamide derivative having a 2-methacryloyloxyethyl segment at both ends of the molecule.

The compound was identified by elemental analysis and IR. The results are shown below.

[0127] IR 3290, 3089, 2926, 2853, 1649, 1617, 1469, 1372, 11
56, 1036 (cm ^-1 )

The outline of the reaction steps of Production Examples 1 (Comparative Example) and 2 (Example of the present invention) can be represented by the following formulas (2) and (3).

[0129]

Embedded image

[0130]

Embedded image

Production Example 3 Synthesis of dodecanediamide derivative (compound No. 95) having methacrylic acid and 2-methacryloyloxyethyl isocyanate at both molecular terminals respectively 51.81 g (0.116 mol) of ZL-leucine.DCHA ( Dicyclohexylamine) salt into a separatory funnel, 300 ml of diethyl ether and 150 ml
After shaking by adding a _{1mol / l (2N) H 2} SO 4, and the aqueous layer was discarded. The ether layer was washed four times with 150 ml of H ₂ O, the ether layer was separated, anhydrous magnesium sulfate was added, and the mixture was subjected to gravity filtration. Thereafter, the ether was removed by distillation under reduced pressure and completely dried with a vacuum pump to obtain 24.24 g of ZL-leucine.

6.37 g of ZL-leucine (0.024
mol), and stirred under ice-cooling to obtain a completely homogeneous solution. Here, 5.36 g (0.026 mol) of N, N'-dicyclohexylcarbodiimide
Was added and stirred for 1 hour under ice cooling. 2.40 g (0.012) of 1,12-dodecanediamine was added to the cloudy liquid stirred for 1 hour.
mol), and the mixture was stirred under ice-cooling for 2 hours, then returned to room temperature for 1 hour, and further stirred overnight at 45 ° C. The cloudy liquid was cooled in a freezer, and the precipitate was suction-filtered and dried under reduced pressure. To 8.34 g of the obtained product, 1-
540 ml of propanol was added and dissolved by heating, and N, N'-dicyclohexylurea was removed by hot filtration. The filtrate was cooled overnight in a freezer, suction-filtered and dried under reduced pressure to obtain an alkylenediamide derivative of ZL-leucine and 1,12-dodecanediamine (hereinafter referred to as “ZL-Le”).
was obtained _{u-NH (CH 2) 6} ] referred to as ₂₎ 5.84 g.

[ZL-Leu-NH (CH ₂ ) ₆ ] ₂ 6
39 g (0.0092 mol) was heated and dissolved in 200 ml of 2-methoxyethanol, and 1 tablespoon of palladium carbon was added as a catalyst.
Reduced for a time to remove the Z group. After confirming the removal of the Z group by silica gel thin layer chromatography, the catalyst was filtered off. The filtrate is concentrated under reduced pressure to dry tetrahydrofuran 60
After dissolving by heating, insoluble matter was removed. The solution after removing the insolubles was concentrated under reduced pressure, 100 ml of hexane was added to thoroughly wash the product, suction filtration was performed, and the resultant was dried under reduced pressure to remove the Z group, and an alkylenediamide derivative of L-leucine and 1,12-dodecanediamine. (Hereinafter [L-Leu-NH (C
H _{2) 6] 2} abbreviated) was obtained 2.75 g.

[L-Leu-NH (CH ₂ ) ₆ ] ₂ 2.78
g (0.0065 mol) in dry tetrahydrofuran 6
0 ml was added and stirred to obtain a completely homogeneous solution. While cooling using an ice bath, 1 ml of triethylamine is added here.
(0.73 g: 0.0072 mol) and stirred,
Further, 0.63 ml of methacrylic acid chloride (0.
(68 g: 0.0065 mol) was added dropwise and stirred. The reaction was carried out by stirring in an ice bath for 3 hours and at room temperature overnight. The obtained cloudy liquid was concentrated under reduced pressure to completely remove the medium, and 100 ml of methanol was added thereto to crush the reaction product to remove triethylamine hydrochloride. After crushing well and washing with methanol, the product was suction-filtered and dried under reduced pressure overnight. 1-propanol 20 was added to 1.51 g of the obtained product.
0 ml was added and dissolved by heating. The resulting solution was filtered hot and recrystallized. The filtrate was cooled in a freezer and filtered by suction. After drying under reduced pressure overnight, 2-methacryloyl-L-Leu-NH
1.21 g of (CH ₂ ) ₁₂ -L-Leu was obtained.

2-methacryloyl-L-Leu-NH
(CH ₂ ) ₁₂ -L-Leu 1.21 g (0.0026 m
ol) in 50 ml of toluene by heating and dissolving the solution at 80 °
C was kept. 0.36 ml of 2-methacryloyloxyethyl isocyanate (0.40 g: 0.0026
mol) was added dropwise and stirred for 0.5 hour. After completion of the reaction, 50 ml of hexane was added to thoroughly wash the product, suction-filtered, and dried under reduced pressure overnight. 1.45 g of product obtained
The mixture was heated and dissolved by adding 100 ml of 1-propanol to the solution, and the solution was filtered by hot filtration to carry out recrystallization. The filtrate was cooled in a freezer and filtered by suction. After drying under reduced pressure overnight, the dodecane diamide derivative having methacrylic acid and 2-methacryloyloxyethyl isocyanate at both molecular terminals, respectively.
2 g were obtained.

The compound was identified by elemental analysis and IR. The results of the elemental analysis are shown below.

[0137]

Production Example 4 Synthesis of a Dodecaneamide Derivative Having Acrylic Acid at Both Molecular Ends (Compound No. 157) 7.42 g of ZL-glutamic acid ethyl ester (0.4 g)
024 mol), 60 ml of ethyl acetate was added, and the mixture was stirred under ice-cooling to obtain a completely uniform solution. Here, 5.36 g of N, N'-dicyclohexylcarbodiimide (0.026 m
ol) and stirred under ice cooling for 1 hour. 4.81 g of 1,12-dodecanediamine (0.41 g) was added to the cloudy liquid stirred for 1 hour.
024 mol), and the mixture was stirred under ice-cooling for 2 hours, then returned to room temperature for 1 hour, and further stirred at 45 ° C overnight. The cloudy liquid was cooled in a freezer, and the precipitate was suction-filtered and dried under reduced pressure. Product obtained 12.39
540 ml of 1-propanol was added to g and dissolved by heating, and N, N'-dicyclohexylurea was removed by hot filtration. The filtrate was cooled in a freezer overnight, suction-filtered, dried under reduced pressure, and ZL-Glu (OEt) -NH
4.72 g of (CH ₂ ) ₁₂ NH ₂ were obtained.

2.55 g of ZL-isoleucine (0.0
(096 mol), and 50 ml of ethyl acetate was added thereto, followed by stirring under ice-cooling to obtain a completely uniform solution. Here, 2.27 g of N, N'-dicyclohexylcarbodiimide (0.011 m
ol) and stirred under ice cooling for 1 hour. 1 hour stirred cloudy solution Z-L-Glu (OEt) -NH (CH 2) 1 2
4.72 g (0.0096 mol) of NH ₂ was added, and the mixture was stirred for 2 hours under ice-cooling, then returned to room temperature for 1 hour and further 4 hours.
The mixture was stirred overnight while keeping the temperature at 5 ° C. The cloudy liquid was cooled in a freezer, and the precipitate was suction-filtered and dried under reduced pressure.
250 m of 1-propanol was added to 7.79 g of the obtained product.
l, heat and dissolve, and filter by hot filtration to obtain N, N'-
Dicyclohexylurea was removed. The filtrate was cooled overnight in a freezer, suction-filtered and dried under reduced pressure, and an alkylenediamide derivative having ZL-glutamic acid ethyl ester and ZL-isoleucine at both ends, respectively (hereinafter referred to as Z).
-L-Glu (OEt) -NH ( CH 2) 12 NH-Z-
L-Ile) (4.82 g) was obtained.

ZL-Glu (OEt) -NH (C
H ₂ ) ₁₂ NH-ZL-Ile 4.82 g (0.006
5 mol) in 200 ml of 2-methoxyethanol, add 1 tablespoon of palladium carbon as a catalyst, reduce at room temperature for 6 hours while injecting hydrogen gas and Z
The group was removed. Z by silica gel thin layer chromatography
After confirming the removal of the group, the catalyst was filtered off. The filtrate was concentrated under reduced pressure, 60 ml of dry tetrahydrofuran was added, and after heating and dissolution, insolubles were removed. The solution after removing the insolubles was concentrated under reduced pressure, and 100 ml of hexane was added to thoroughly wash the product.
L-glutamic acid ethyl ester from which Z group has been removed by vacuum filtration and vacuum drying after suction filtration, and an alkylenediamide derivative of L-isoleucine and 1,12-dodecanediamine (hereinafter referred to as L
_{-Glu (OEt) -NH (CH 2} ) 12 NH-L-Il
e) 2.37 g were obtained.

L-Glu (OEt) -NH (CH ₂ ) ₁₂
To 2.37 g (0.0050 mol) of NH-L-Ile, 60 ml of dry tetrahydrofuran was added and stirred to obtain a completely uniform solution. While cooling using an ice bath, 1.52 ml of triethylamine (1.11 g: 0.01
1 mol), and the mixture is stirred and further cooled under ice-cooling with 0.81 ml of acrylic acid chloride (0.91 g: 0.010 mol).
Was added dropwise and stirred. The reaction was carried out by stirring in an ice bath for 3 hours and at room temperature overnight. The obtained cloudy liquid was concentrated under reduced pressure to completely remove the medium, and 100 ml of methanol was added thereto to crush the reaction product to remove triethylamine hydrochloride. After crushing well and washing with methanol, the product was suction-filtered and dried under reduced pressure overnight. 2.42 g of product obtained
Was added to 200 ml of 1-propanol and dissolved by heating. The resulting solution was filtered hot and recrystallized. The filtrate was cooled in a freezer and filtered by suction. Drying under reduced pressure was performed overnight to obtain 2.17 g of a dodecanediamide derivative having acrylic acid at both molecular terminals.

This compound was identified by elemental analysis and IR. The results of the elemental analysis are shown below.

[0143] Next, examples of the gelling agent will be described.

Example 1 The compounds obtained in Production Examples 1 (Comparative Example) and 2 (Example of the present invention) were tested for gelling ability with respect to a typical organic medium by the following test method. Table 1 shows the results.

The compounds of the present invention and comparative compounds were
10 mg each was precisely weighed and added to a test tube with a lid, and 1 ml of each organic medium was put therein and the lid was heated until a complete homogeneous solution was obtained. After dissolution, the gel was left at room temperature to completely form the gel, and then allowed to stand in a thermostat at 25 ° C. for 2 hours, and the state of the gel was visually observed. If the gelation is incomplete, add the compound of the present invention. If the gelation is complete, add the organic medium and add the minimum amount (mg) of the compound required to gel 1 ml of each organic medium. I asked. However, the maximum amount of the compound to be added was up to 100 mg per 1 ml of the organic medium, and in this state, the solution was evaluated as "no gelation".

Example 2 The compounds obtained in Production Examples 1 (Comparative Example) and 2 (Example of the present invention) were subjected to a polymerization test by the following test method. Table 1 shows the polymerization results.

The compounds of the present invention and comparative compounds were
1 ml of each organic medium is precisely weighed twice as much as the minimum amount (mg) that can be gelled and placed in a sample bottle.
And heated until a complete homogeneous solution was obtained.
After dissolution, the gel was allowed to stand at room temperature until the gel was completely formed. After the gel was formed, the gel was irradiated with ultraviolet light shielding light of 360 nm or more for 2 nights. The portion that did not dissolve by heating the gel after light irradiation was judged to be a polymerized gel by photopolymerization, and a gel obtained with such a gel was "○", such a gel was not obtained Those were evaluated as "x".

[0148]

[Table 1]

From Table 1, it can be seen that the polymerized functional group-containing alkylenediamide derivative of the present invention can be gelled by adding a small amount of a wide variety of liquid organic media as compared with the comparative polymerized functional group-containing alkylenediamide derivative. . It is also clear that gels made from various types of organic media can be polymerized by ultraviolet irradiation.

Further, the following has become clear. The gel obtained by UV irradiation does not melt on any heating. Also, when the polymerized gel was stored at room temperature for half a year and observed, it was confirmed that the gel was uniform without any change from the initial state and stable even after long-term storage with no liquid part generated. Was done. That is, the gel polymerized by ultraviolet irradiation has thermal stability,
Excellent long-term stability.

Therefore, it was found that the compound of the present invention can gel many organic media and can highly differentiate the gel.

Next, application examples of the gelling agent of the present invention will be described.

Example 3 Preparation of Titanium Oxide Aqueous Dispersion Titanium oxide aqueous dispersion was prepared by hydrolyzing titanium isopropoxide as follows.

125 ml of titanium isopropoxide was added to 0.1mo
It was added to 750 ml of 1 / l nitric acid aqueous solution while stirring. This is 80
Stir vigorously at 8 ° C. for 8 hours. The obtained liquid was autoclaved in a titanium pressure vessel at 220 ° C. and 20 atm for 12 hours. The aqueous dispersion containing the precipitate was resuspended by stirring. By suction filtration, the precipitate which did not resuspend was removed,
The aqueous dispersion was concentrated by an evaporator until the titanium oxide concentration became 11% by mass. In order to improve paintability on the substrate,
One drop of Triton X-100 was added.

10.0 g of polyethylene glycol having a molecular weight of 20,000 was added to the titanium oxide aqueous dispersion in order to prevent the occurrence of cracks during the firing of the titanium oxide film and the peeling of the film from the conductive surface.

Transparent electrode supporting sensitizing dye-adsorbed titanium oxide film
Preparation of (Titanium Oxide Electrode: Cathode) Next, a conductive glass substrate (F-doped SnO ₂ , sheet resistance 10 Ω / □) having a length of 3.0 cm, a width of 3.0 cm and a thickness of 1 mm was placed on the conductive film surface side. , 0.5cm long, 0.5cm wide with a thickness of 7
A masking tape of 0 μm was attached, and the aqueous titanium oxide dispersion (average particle diameter of primary particles of titanium oxide: 10 nm) was added to the end of the hole with a pipette. The sol was spread on a substrate by stretching using a glass plate having a flat edge. The film thus spread was dried in air for 30 minutes, and after drying, the masking tape was peeled off. Next, baking was performed at 500 ° C. for 30 minutes using an electric furnace. The heating rate is 2 ° C /
min.

After the firing, when the substrate temperature was lowered to 80 ° C., (4,4′-dicarboxylic acid-
It was immersed in a solution of 2,2'-bipyridine) ruthenium (II) diisothianate in 3 × 10 ^-4 mol / l anhydrous ethanol solution and left to stand for 12 hours. After standing, the titanium oxide electrode was taken out and washed with anhydrous acetonitrile. The titanium oxide film on the substrate became deep red due to the adsorbed ruthenium dye.

The thickness of the titanium oxide film was 10,000 nm, and the amount of dye adsorbed on 1 g of titanium oxide was 180 mmol.
Met.

Preparation of Counter Electrode (Anode) Platinum was deposited on the conductive film side of a conductive glass substrate (F-doped SnO ₂ , sheet resistance 10 Ω / □) having a length of 3.0 cm, a width of 3.0 cm and a thickness of 1 mm. Evaporated to a thickness of 2 nm.

Preparation of Gel Electrolyte Tetrapropylammonium iodide (0.4 mol / l)
The gelling agent of Production Example 2 (a dodecanediamide derivative having a 2-methacryloyloxyethyl segment at both molecular terminals: compound No. 1) was added to propylene carbonate containing iodine (0.04 mol / l) and iodine (0.04 mol / l). An electrolytic solution was prepared. Further, 2,2-dimethoxy-2-phenylacetophenone was added as a polymerization initiator. The amounts of the gelling agent and the polymerization initiator were 15 mg and 0.45 mg, respectively, per 1 ml of propylene carbonate. The heating was performed until the gelling agent and the polymerization initiator were uniformly dissolved, and then used for producing the battery.

Preparation of Battery A 2.5 cm long, 3.0 cm wide, 70 μm thick spacer having a hole of 0.5 cm long and 0.5 cm wide was measured. And placed on a titanium oxide electrode so as to be in close contact with the electrode. A gel electrolyte was placed on the hole, a counter electrode was placed thereon, and the periphery was sealed with an epoxy resin to produce a battery.

Thereafter, the gel was irradiated with ultraviolet rays shielding light of 360 nm or more from the counter electrode side for 5 minutes to carry out photopolymerization of the gel, and polymerized while maintaining the gel state.

This is designated as Battery Sample No. 1.

For comparison, a battery sample No. 2 in which photopolymerization was not performed by irradiation with ultraviolet light was prepared. further,
Battery sample No. 3 was prepared using an electrolyte solution without adding a gelling agent and a polymerization initiator instead of the gel electrolyte.

Evaluation of Battery Using a solar simulator of AM1.5 (1000 W / m ² ), open-circuit voltage (Voc), photocurrent density (Jsc), form factor (FF), conversion efficiency ( η) was measured to evaluate the battery characteristics. Table 2 shows the measurement results immediately after the battery was manufactured and after the battery was left for 200 days.

[0166]

[Table 2]

From the above results, it can be seen that long-term stability of battery characteristics is improved by gelling the electrolytic solution using the gelling agent of the present invention. In addition, photopolymerization of the electrolyte solution gel is very effective in further improving the stability of the gel and improving the stability of battery characteristics. On the other hand, in the sample containing no gelling agent, the deterioration of the sealant and the volatilization of the solvent occur, and the long-term stability is very poor.

Example 4 A paint for a magnetic layer, a nonmagnetic paint for a nonmagnetic lower layer, and a backcoat for a backcoat layer having the following compositions were prepared. Unless otherwise specified, "parts" in the following
"Parts by mass".

Magnetic paint Fe-Al-based ferromagnetic metal powder 100 parts (magnetic powder) Fe: Al: Co: Y = 100: 10: 40: 8 (mass ratio) Hc: 174 kA / m (2200 Oe), BET: 58m^Two/ G, σs: 145 Am ^Two / kg (145 emu / g), crystallite size: 12 nm, axial ratio 6.5 average major axis length 100 nm Potassium sulfonate group-containing vinyl chloride resin (MR-1 10 manufactured by Nippon Zeon Co., Ltd.) Modified product 10 parts Electron beam crosslinked modified product of sodium sulfonate group-containing polyurethane resin (UR-8700 manufactured by Toyobo Co., Ltd.) 10 parts Carbon black (number average particle diameter 90 nm) 0.5 part α-alumina (number average particle 3 parts Stearic acid 1 part Butyl stearate 1 part Cyclohexanone 100 parts Methyl ethyl ketone 100 parts Toluene 100 parts Gelling agent (dodecanediamide derivative having 2-methacryloyloxyethyl segments at both molecular terminals: compound No. 1) 1 copy

Non-magnetic paint Non-magnetic powder [α-Fe ₂ O ₃ needle-like particles (containing 0.2% by mass of Si with respect to α-Fe ₂ O ₃ and 0.5% by mass of Al), average major axis Length: 160 nm, crystallite size: 18 nm, axis ratio: 8] 100 parts Potassium sulfonate group-containing vinyl chloride resin (MR-110, manufactured by Zeon Corporation) electron beam crosslinked type modified product 12 parts Sodium sulfonate group-containing polyurethane Modified electron beam-crosslinked resin (UR-8700 manufactured by Toyobo Co., Ltd.) 8 parts α-alumina (number average particle diameter 0.2 μm) 5 parts Carbon black (number average particle diameter 15 nm) 10 parts Stearic acid 1 Part Butyl stearate 1 part Cyclohexanone 100 parts Methyl ethyl ketone 100 parts Toluene 100 parts Gelling agent (dodecanediamide derivative having 2-methacryloyloxyethyl segments at both molecular terminals: Compound No. 1) 2 parts

Backcoat paint Carbon black 1 (number average particle diameter 23 nm) 45 parts Carbon black 2 (number average particle diameter 50 nm) 5 parts Barium sulfate (average particle diameter 200 nm) 1 part Nitrocellulose 25 parts Polyurethane resin 25 parts ( N-2301 manufactured by Nippon Polyurethane Co., Ltd. 10 parts of polyisocyanate compound (Coronate L manufactured by Nippon Polyurethane Co., Ltd.) 400 parts of cyclohexanone 250 parts of methyl ethyl ketone 250 parts of toluene

A non-magnetic paint was applied on a polyethylene-2,6-naphthalate film having a thickness of 5 μm, dried to remove the solvent, calendered, and then irradiated with an electron beam (15 Mrad). A non-magnetic lower layer having a thickness of 1.5 μm was formed. Then, a magnetic paint was applied thereon, dried, and the solvent was removed. Then, a calendar treatment was performed, and electron beam irradiation (15 Mrad) was further performed to form a magnetic layer having a thickness of 0.10 μm.

Further, the surface (back surface) of the polyethylene-2,6-naphthalate film opposite to the magnetic layer
Was coated with a backcoat paint, dried, calendered, and then heat-cured to form a 0.8 μm thick backcoat layer.

A video tape obtained by slitting this was designated as magnetic tape sample No. 1.

[0175] Sample No. 2 was prepared in the same manner as in Sample No. 1, except that no gelling agent was added to the magnetic paint and the non-magnetic paint.

The following evaluation was performed on these samples. Table 3 shows the results.

{Electromagnetic conversion characteristics} 7 MHz and 6 MHZ using an 8 mm video camera CCDV-900 manufactured by Sony Corporation.
The output difference (dB) from z was measured, and the C / N ratio was 7 MHz.

{Center line average surface roughness (Ra)} JIS-
The measurement was performed using a three-dimensional surface roughness tester (SE-3FK) manufactured by Kosaka Laboratory Co., Ltd. according to the method described in Section 5 of B0601 (cutoff was 0.25 mm).

{Coating Characteristics} The coating characteristics were visually observed for streaks in the longitudinal direction.

{Overwrite Characteristics} A 2 MHz signal was recorded at a saturation level, and then a 9 MHz signal was recorded (overwritten) to determine the residual output level of the 2 MHz signal. It is assumed that the lower the residual output level, the better the overwrite characteristics.

[0181]

[Table 3]

It can be seen that the sample of the present invention has good surface properties and excellent characteristics.

Example 5 A reflective film made of Al was formed by a sputtering method on the surface of a disk-shaped support substrate (made of polycarbonate, having a diameter of 120 mm, an inner diameter of 15 mm, and a thickness of 1.2 mm) on which pits for carrying information were formed.

Next, a resin layer having a thickness of 100 μm was formed on the surface of the reflection film by screen printing, and the resin layer was irradiated with ultraviolet rays and cured to form a light transmitting layer, thereby obtaining an optical disk sample. The ink used for printing was UV curable resin (UV made by Teikoku Ink Mfg. Co., Ltd.)
-OPT-550), 3% of the above compound No. 1 as a gelling agent
(% By mass). The plate used for printing had 100 meshes per inch (2.54 cm) and an emulsion film thickness of 100 μm. The printing range is an area having a radius of 19.5 to 59.5 mm. No liquid dripping from the plate was observed during printing.

The thickness distribution of the light transmitting layer thus formed was measured by a laser focus displacement meter. The thickness was measured in the radial direction of the light transmitting layer by two.
Performed at mm intervals. As a result, the average thickness of the light transmitting layer is 10
0 μm, and the difference between the maximum thickness and the minimum thickness was 6 μm. No swelling was observed near the outer periphery and the inner periphery of the light transmitting layer.

A comparative sample was prepared in the same manner as the above sample except that no gelling agent was added to the ink. When printing the resin layer, liquid dripping from the plate was observed. For this comparative sample, the same measurement as the above sample was performed. As a result, the average thickness of the light transmitting layer was 102 μm, and the difference between the maximum thickness and the minimum thickness was 20 μm.
However, the thickness distribution was significantly increased. In addition, swelling was observed near the outer periphery and the inner periphery of the light transmitting layer.

[0187]

According to the present invention, it has become possible to thicken or gel a wide variety of liquid organic media with a small amount of addition. Further, by irradiating the generated gel with ultraviolet rays, it was possible to polymerize the gel while maintaining the gel state. In addition, various functional coating films can be formed by using a gelling agent as a viscosity modifier or a coating material.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view illustrating a configuration example of an optical information medium.

[Explanation of symbols]

 2 light transmission layer 20 support base 21 groove 4 recording layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 7/18 CER C08J 7/18 CER CEZ CEZ C09K 3/00 103 C09K 3/00 103M // C08L 101: 00 C08L 101: 00 (72) Inventor Seiji Arafuka 1685-12 Hata-cho, Higashi-Chikuma-gun, Nagano Prefecture (72) Inventor Yuichi Kubota 1-13-1 Nihonbashi, Chuo-ku, Tokyo Inside TDK Corporation (72) Inventor Hideki Hirata 1-1-13 Nihonbashi, Chuo-ku, Tokyo TDK Corporation (72) Inventor Atsushi Kadota 1-13-1 Nihonbashi, Chuo-ku, Tokyo Fterm in TDK Corporation 4F073 BA03 BA08 BA23 BA24 BA26 BA27 BA29 BA30 BA31 BA32 BB01 CA45 FA03 4H006 AA01 AB90 4J011 CA01 CA08 CC04 CC10 QA03 QA1 8 QA19 QA35 QA38 SA06 SA34 UA01 VA01 WA02 WA10 4J100 AL66P AM23P BA16P BA20P BA34P BA37P CA01 JA01

Claims (4)

[Claims] 1. A polymerized functional group-containing alkylene amide derivative represented by the following formula (1) having an amino acid derivative segment and a polymerized functional group. Embedded image [In Formula (1), n is an integer of 2 to 30, A ¹ and A ² are each — (CH ₂ ) ₂ COOR (where R is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms) , A phenyl group or a benzyl group.), -CH (C
_{H 3) 2, -CH 2 CH} (CH 3) 2, -CH (CH 3) C 2
Represents H ₅ or _{-CH 2 C 6 H 5, B} 1 and B ^2, _{respectively, -CONH (CH 2) 2 OCOC} (CH 3) = C
_{H 2, -COC (CH 3)} = CH 2 and -COCH = C
Represents a vinyl-containing group or an alkyl group selected from H ₂ , at least one of which is a vinyl-containing group. A ¹ and A ² may be the same or different, and when both are vinyl-containing groups, B ¹ and B ² may be the same or different. m1 and m2 are each 1 or 2
It is. ] 2. A gelling agent having an amino acid derivative segment and a polymerizable functional group (excluding styryl-containing groups), wherein the viscous fluid or gel is maintained at a high level while maintaining a viscous state or a gel state. Gelling agent that can be molecularized. 3. The gelling agent according to claim 2, which is a polymerized functional group-containing alkyleneamide derivative represented by the following formula (1). Embedded image [In Formula (1), n is an integer of 2 to 30, A ¹ and A ² are each — (CH ₂ ) ₂ COOR (where R is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms) , A phenyl group or a benzyl group.), -CH (C
_{H 3) 2, -CH 2 CH} (CH 3) 2, -CH (CH 3) C 2
Represents H ₅ or _{-CH 2 C 6 H 5, B} 1 and B ^2, _{respectively, -CONH (CH 2) 2 OCOC} (CH 3) = C
_{H 2, -COC (CH 3)} = CH 2 and -COCH = C
Represents a vinyl-containing group or an alkyl group selected from H ₂ , at least one of which is a vinyl-containing group. A ¹ and A ² may be the same or different, and when both are vinyl-containing groups, B ¹ and B ² may be the same or different. m1 and m2 are each 1 or 2
It is. ] 4. A functional coating film obtained by applying the gelling agent composition for forming a coating film containing the gelling agent according to claim 2 or 3 to an adherend, followed by curing with an active energy ray. Coated body formed.