JP2003313244A - Organic polymer having parabanic acid skeleton - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new compound which can impart hydrophilicity to an organic polymer, a polymerizable composition containing the compound, and an organic polymer obtained by polymerizing the composition. <P>SOLUTION: This organic polymer having high hydrophilicity is obtained by polymerizing a polymerizable composition containing a compound having at least one parabanic acid skeleton represented by partial structural formula (1) and at least one reactive group. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a highly hydrophilic organic polymer having a parabanic acid skeleton in its molecule. More specifically, a novel compound having a parabanic acid skeleton in the molecule that gives the organic polymer, a polymerizable composition containing the compound, a molded product made of an organic polymer having a parabanic acid skeleton in the molecule, and the molding Regarding the use of the body.

[0002]

2. Description of the Related Art At present, various environmental problems have become apparent, and clean products and processes that do not pollute the environment have been required in all fields.

For example, a curing system for resins and coating materials is no exception, and by shifting from a conventional thermal curing system to a new radiation curing system, more energy saving, shorter time, simplification, and de-VOC (low volatility) are achieved. Organic compounds), low catalysts and low additives are being actively used to reduce the burden on the environment.

Taking the movement of VOC removal as an example, 196
VOCs that originated from air pollution problems in the United States in the 0's
The problem was activated by RC (Responsible Care) activities that started in Canada, and is now being promoted on a global scale in the form of emission control of organic solvents.

The current total VOC emissions worldwide are about 20.
It is estimated to be 1,000,000 tons / year, of which 1000 is from a car
10,000 tons / year (mainly diesel vehicles) and 3.5 million tons / year from painting {Industrial materials, 48 (5) , 28-3
5 (2000)}. As a method of reducing VOCs from painting, conversion to water-based coating materials that use water instead of solvent or powder coating materials that use neither solvent nor water is extremely effective.
At present, the transition to water-based coating materials by making the materials highly hydrophilic and the transition to powder coating materials by increasing the melting point are progressing at a rapid pace {industrial materials, 48 (5) , 28-35 (2000)}. .

The water contact angle is widely known as a representative physical property value which is an index of hydrophilicity of a material (Weting Technology Handbook, Techno System Publishing, 2001), and the water contact angle is 0.
It is said that the material has a higher hydrophilicity as it gets closer to °, that is, a material (hydrophilic material) that wets well with water.

By using the above-mentioned VOC-free coating material and the hydrophilic material for the outer wall of the building, dirt (hydrophobic substance, etc. outside air) adhering to the coating surface or outer wall is removed by rainfall and water spraying. Contamination (self-cleaning) can be improved {polymer, 44 (5),
307, Chemical Daily, August 24, 2001}, with the improvement of hydrophilicity, the antifouling property is also improved, and the water contact angle is about 5
It has been reported that when it becomes 0 ° or less, it will not become dirty {future material, 2 (1), 36-41}.

In particular, it has been reported that when the water contact angle is 20 ° or less, it is possible to substantially prevent the fog and dew condensation that are seen on window glasses, mirrors, building interior materials, vinyl sheets for agriculture, spectacle lenses, camera lenses and the like. (Wet Technology Handbook, Techno System Publishing, 2001).

Furthermore, the high hydrophilicity suppresses the drop in heat exchange efficiency due to the formation of droplets and the attachment of contaminants that occur in cooling fins and the like (Japanese Patent Application Laid-Open No. 07-18458) and improves the wearing feeling of contact lenses {SEED. Co. , Lt
d Product name Seed S-1 (Medical device approval number 21100
BZZ00557000) pamphlet} has also been reported.

By the way, in these applications, large size, complicated structure, precision required, productivity, operability, product flexibility and safety are required. In many cases, it is difficult to satisfy these requirements with inorganic materials, such as the need for properties and luster, and the fact that coloring or dyeing is preferred, and there is an increasing demand for organic materials.

As the hydrophilic organic polymer, polyvinyl alcohol (water contact angle 36 °, superhydrophilic and superhydrophobic technology, published by Technical Information Society, 2001), polyisopropylacrylamide (water contact angle about 44 °, Langmuir, 11,
2301, 1995), polyacrylonitrile (water contact angle 53
°, Desalination, 72, 263, 1989) and other polymers,
An unusual thing is that the agar gel (water contact angle is about 20
°, Langmuir, 10, 2435, 1994) is known.

However, since these known organic polymers have insufficient hydrophilicity and have a linear structure, they also have physical and chemical properties such as mechanical strength, heat resistance, water resistance and chemical resistance. It was not enough, and there was room for further improvement.

On the other hand, as a method for imparting hydrophilicity to the surface of an organic material, a method of providing a photocatalytic reaction layer of titanium oxide on the surface of the material (JP-A-11-58629 and JP-A-1-58629).
No. 1-1659), and a method of applying a coating agent using a silanol group (JP-A-9-40907, JP-A-9-40907).
-40908, JP-A-11-21826), a method of providing a layer of polyvinyl alcohol with a silyl group and an ionic hydrophilic group (carboxyl group) after corona discharge treatment (JP-A-9-76428), morpholyl group Method of applying the contained fluorosilicone linear oligomer (Japanese Patent Laid-Open No. 09-241331) and method of forming a layer using a quaternary ammonium salt group (Japanese Patent Laid-Open No. 10-29)
6895), a method of forming a large number of fine depressions on the surface by etching treatment (JP-A-7-198290), active hydrogen groups such as amide groups, carboxyl groups, hydroxyl groups by graft copolymerization, sodium sulfonate, etc. Method of introducing ionic functional groups of
lym. Sci., part A: polym.chem., 32, 1569, 1994, Mac
romlecules, 25, 6842, 1992), a method of treating the surface with a mixed solution of chloric acid and potassium chlorate (Polymer (Korea), 2
4, 877, 2000) etc. are known.

However, in the method of imparting hydrophilicity to the surface of the organic material, high water wettability can be realized in some cases, but decomposition of the material interface due to release of active oxygen and insufficient light intensity (indoor, dark place). Etc.) resulting in loss of water wettability, generation of interference fringes, insufficient strength and durability of the coating layer and treated surface, generation of alcohol by hydrolysis of alkoxysilyl group, reaction caused by active hydrogen group and ionic group, etc. It is easy to cause various problems such as performance and quality deterioration.

In addition, these surface modification methods usually require special devises and special devices, and it is necessary to once manufacture a molded product and perform pretreatment, which results in efficient production. It was not a target, and it tended to be costly, and in some cases safety was a question that remained questionable.

[0016]

DISCLOSURE OF THE INVENTION The present invention provides a novel compound capable of imparting hydrophilicity to an organic polymer, which is useful for solving the problems of the above-mentioned known methods for hydrophilicity, and a heavy compound containing the compound. It is an object to propose a combined composition and an organic polymer obtained by polymerizing the polymerizable composition.

In the course of various investigations by the present inventors in order to find a new organic polymer having a high hydrophilicity which has never been obtained, the organic polymer obtained using a compound having a parabanic acid skeleton in the molecule is high. It was found to have hydrophilicity. As a result of intensive investigations by the present inventors based on this finding,
The inventors have also found that the organic polymer has properties suitable for the use of the hydrophilic material described above, and have completed the present invention.

[0018]

That is, the present invention is [1] Partial structural formula (1)

[0019]

[Chemical 5]

An organic polymer having a parabanic acid skeleton represented by in the molecule and having a water contact angle of 30 ° or less. [2] A molded product made of the organic polymer as described in [1] above. [3] A film made of the organic polymer as described in [1] above. [4] At least one partial structural formula (1) in the same molecule

[0021]

[Chemical 6]

A compound having a parabanic acid skeleton represented by and at least one or more acryloyl group or methacryloyl group. [5] General formula (2)

[0023]

[Chemical 7]

(R₁~ R₆Are each independently hydrogen
Represents an atom or a methyl group. However, R ₁~ R_FourIs hydrogen
Part or all of the atoms or methyl groups are hydroxy groups
May be replaced with. X₁, X_TwoAre each independent
, O, S, NH, or NCH _ThreeRepresents a and b are
Each independently represents an integer of 0 or 1. c, d
Each independently represents an integer of 2 to 6. e, f
Each independently represent an integer of 0 to 3. )
The compound according to the above [4]. [6] General formula (3)

[0025]

[Chemical 8]

[0026] (R ₁ to R ₄ each independently represent a hydrogen atom or a methyl group. However, some or all of the hydrogen atom or a methyl group, may be substituted with a hydroxy group .Y _1, Y ₂ is independently O, S, N
Represents H or NCH ₃ . c and d each independently represent an integer of 2 to 6. g and h each independently represent an integer of 1 to 3. ) The compound represented by. [7] A polymerizable composition containing the compound according to [4] or [5]. [8] An organic polymer obtained by polymerizing the compound according to [4] or [5] or the polymerizable composition according to [7].

[9] The organic polymer as described in [8] above, which has a water contact angle of 30 ° or less. [10] The above [8] or the above

A molded product comprising the organic polymer described in [9]. [11] The above [8] or the above

A film comprising the organic polymer described in [9].

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION The organic polymer of the present invention is characterized by having a parabanic acid skeleton represented by the partial structural formula (1) in the molecule and having a water contact angle of 30 ° or less. Therefore, the organic polymer of the present invention may be any polymer as long as it has a parabanic acid skeleton represented by the partial structural formula (1) in the molecule and has a water contact angle of 30 ° or less. .

By introducing the parabanic acid skeleton represented by the partial structural formula (1) into the organic polymer, it is possible to impart high hydrophilicity to the organic polymer.

The organic polymer having the parabanic acid skeleton represented by the partial structural formula (1) in the molecule includes at least one parabanic acid skeleton represented by the partial structural formula (1) and at least one in the same molecule. It can be obtained by using a compound having one or more reactive groups.

The reactive group is not limited, but examples of the reactive group include (meth) acryloyl group, (thio) epoxy group, iso (thio) cyanate group, carbon-carbon unsaturated double bond and mercapto group. Group, amino group, hydroxyl group, allyl carbonate group and the like. These reactive groups may be present in the same molecule in at least one or more identical or different groups.

In producing an organic polymer, a compound having at least one or more parabanic acid skeleton represented by the partial structural formula (1) and at least one or more of the above-mentioned reactive groups in the same molecule is The compounds belonging to this can be used alone, or two or more compounds can be used in combination. Also, compounds having reactive groups having different reactive groups existing in the same molecule can be used in combination.

At least one or more parabanic acid skeleton represented by the partial structural formula (1) in the same molecule and at least one
Various organic polymers having the parabanic acid skeleton represented by the partial structure (1) can be obtained by using a compound having one or more of the above reactive groups. For example,
As a compound having at least one or more parabanic acid skeleton represented by the partial structural formula (1) and at least one or more reactive groups in the same molecule, a compound having a (meth) acryloyl group as the reactive group By using a poly (meth) acrylate-based polymer, similarly by using a compound having a (thio) epoxy group as a reactive group, a (thio) epoxy resin-based polymer and a carbon-carbon unsaturated double bond as a reactive group can be used. By using a compound having a bond, a polyolefin polymer, by using a compound having an iso (thio) cyanate group as a reactive group, a poly (thio) urethane polymer, by using a compound having a carbon-carbon unsaturated double bond as a reactive group By using a compound having a bond and a mercapto group, a polyene-polythiol polymer, a carbon-carbon unsaturated double bond as a reactive group, and Polyenes by using a compound having an amino group - it is possible to introduce a parabanic acid skeleton represented by various organic polymers in the partial structural formula of the polyamine polymer and the like (1). In addition, as described later, an organic polymer is prepared by using a compound having at least one or more parabanic acid skeleton represented by the partial structural formula (1) and at least one or more reactive groups in the same molecule. At the time of obtaining, a reactive compound which reacts with this to give an organic polymer may be used in combination.

At least one or more parabanic acid skeleton represented by the partial structural formula (1) in the same molecule and at least one
Examples of the compound having at least one reactive group include, for example, a compound having one parabanoic acid skeleton represented by the partial structural formula (1) and one reactive group in the same molecule, and one compound in the same molecule. And a compound having a parabanic acid skeleton represented by the partial structural formula (1) and two reactive groups.

At least one parabanic acid skeleton represented by the partial structural formula (1) and at least one in the same molecule.
Among the compounds having at least one reactive group, the compound having a (meth) acryloyl group as a reactive group is preferable because the rapid polymerization is easy and the pot life is relatively long. In particular, as a compound having at least one or more parabanic acid skeleton represented by the partial structural formula (1) and at least one or more (meth) acryloyl group in the same molecule,
The compound represented by the general formula (2) is particularly preferable.

Since the compound represented by the general formula (2) can be obtained by using the compound represented by the general formula (3), the compound represented by the general formula (3) is represented by the general formula (2). It is useful as a precursor for the represented compounds. Further, since the compound represented by the general formula (3) has the above-mentioned reactive group, the compound represented by the general formula (3) is used to convert the parabanic acid skeleton represented by the partial structure (1) into an organic compound. It can be introduced into coalescence.

Represented by the general formula (2) or the general formula (3)
In the compound₁~ R₆Each independently,
Represents a hydrogen atom or a methyl group. However, R₁~ R_FourIs
Some or all of the hydrogen atoms or methyl groups are
It may be substituted with a sil group. In this case, the hydroxyl group
May optionally be attached to a methylene group, but the same methyl
No more than one hydroxyl group attached to the len group
Is preferred. X₁, X _Two, Y₁, Y_TwoAre independent
Then O, S, NH, or NCH_ThreeRepresents Costly
Is preferably O. a and b are independent
And represents an integer of 0 or 1, and c and d are respectively
Independently, it represents the integer of 2-6. c and d are independent
2 to 4 is preferable, and 2 to 3 is more preferable.
Good If either c or d is 1, it is subject to hydrolysis
Since it has a pancreatic hemiacetal structure, c and d should be 2 or more.
Preferably. e and f are each independently 0 to
Represents an integer of 3, and g and h are each independently 1 to 3
Represents the integer.

A compound having a parabanic acid skeleton represented by one partial structural formula (1) and one reactive group in the same molecule, wherein the reactive group is a (meth) acryloyl group, the same molecule As a compound having one parastructural skeleton represented by the partial structural formula (1) and two reactive groups therein, a compound represented by the general formula (2) and a compound represented by the general formula (3) The compounds belonging to the compounds will be specifically exemplified below.

The compound having a parabanic acid skeleton represented by the partial structural formula (1) and a (meth) acryloyl group in the same molecule is, for example, N-methyl-N '-{(meth).
Acryloyl} -parabanic acid, N-methyl-N'-
{(Meth) acryloyloxy-ethyl} -parabanic acid, N-methyl-N '-{3- (meth) acryloyloxy-propyl} -parabanic acid, N-methyl-N'-
{2- (meth) acryloyloxy-propyl} -parabanic acid, N-methyl-N '-{3- (meth) acryloyloxy-2-propyl} -parabanic acid, N-methyl-
N '-{4- (meth) acryloyloxy-butyl}-
Parabanic acid, N-methyl-N '-{3- (meth) acryloyloxy-2-butyl} -parabanic acid, N-methyl-N'-{5- (meth) acryloyloxy-3-oxapentyl} -paraban Acid, N-methyl-N '-{8-
(Meth) acryloyloxy-3,6-dioxaoctyl} -parabanic acid, N-methyl-N '-{5- (meth)
Acryloyloxy-3-oxa-1,4-dimethyl-
Pentyl} -parabanic acid, N-methyl-N ′-{8-
(Meth) acryloyloxy-3,6-dioxa-1,
4,7-Trimethyl-octyl} -parabanic acid, N-methyl-N '-{5- (meth) acryloyloxy-3-
Thiapentyl} -parabanic acid, N-methyl-N '-{8
-(Meth) acryloyloxy-3,6-dithiaoctyl} -parabanic acid, N-methyl-N '-{5- (meth)
Acryloyloxy-3-azapentyl} -parabanic acid, N-methyl-N '-{8- (meth) acryloyloxy-3,6-diazaoctyl} -parabanic acid, N-methyl-N'-{5- (meth) Acryloyloxy-3-
Aza-3-methyl-pentyl}}-parabanic acid, N-methyl-N ′-{8- (meth) acryloyloxy-3,
6-diaza-3,6-dimethyl-octyl} -parabanic acid, N-methyl-N ′-{(meth) acryloylthio-
Ethyl} -parabanic acid, N-methyl-N '-{3- (meth) acryloylthio-propyl-1-}-parabanic acid, N-methyl-N'-{2- (meth) acryloylthio-propyl-1. -}-Parabanic acid, N-methyl-N '
-{3- (meth) acryloylthio-propyl-2-}
-Parabanic acid, N-methyl-N '-{4- (meth) acryloylthio-butyl-1-}-parabanic acid, N-methyl-N'-{3- (meth) acryloylthio-butyl-
2-}-parabanic acid, N-methyl-N '-{5- (meth) acryloylthio-3-oxapentyl-1-}-
Parabanic acid, N-methyl-N '-{8- (meth) acryloylthio-3,6-dioxaoctyl-1-}-parabanic acid, N-methyl-N'-{5- (meth) acryloylthio- 3-oxa-1,4-dimethyl-pentyl-1
-}-Parabanic acid, N-methyl-N '-{8- (meth)
Acryloylthio-3,6-dioxa-1,4,7-trimethyl-octyl-1-}-parabanic acid, N-methyl-N ′-{5- (meth) acryloylthio-3-thiapentyl-1-}- Parabanic acid, N-methyl-N '-{8
-(Meth) acryloylthio-3,6-dithiaoctyl-1-}-parabanic acid, N-methyl-N '-{5- (meth) acryloylthio-3-azapentyl-1-}-parabanic acid, N-methyl -N '-{8- (meth) acryloylthio-3,6-diazaoctyl-1-}-parabanic acid, N-methyl-N'-{5- (meth) acryloylthio-3-aza-3-methyl- Pentyl} -1-}-parabanic acid, N-methyl-N ′-{8- (meth) acryloylthio-3,6-diaza-3,6-dimethyl-octyl-1-}-parabanic acid, N-methyl -N '-{(meta)
Acryloylamino-ethyl} -parabanic acid, N-methyl-N '-{3- (meth) acryloylamino-propyl-1-}-parabanic acid, N-methyl-N'-{2-
(Meth) acryloylamino-propyl-1-}-parabanic acid, N-methyl-N '-{3- (meth) acryloylamino-propyl-2-}-parabanic acid, N-methyl-N'-{4- (Meth) acryloylamino-butyl-
1-}-parabanic acid, N-methyl-N '-{3- (meth) acryloylamino-butyl-2-}-parabanic acid, N-methyl-N'-{5- (meth) acryloylamino-3- Oxapentyl-1-}-parabanic acid, N-
Methyl-N '-{8- (meth) acryloylamino-
3,6-Dioxaoctyl-1-}-parabanic acid, N-
Methyl-N '-{5- (meth) acryloylamino-3
-Oxa-1,4-dimethyl-pentyl-1-}-parabanic acid, N-methyl-N '-{8- (meth) acryloylamino-3,6-dioxa-1,4,7-trimethyl-octyl- 1-}-parabanic acid, N-methyl-N'-
{5- (meth) acryloylamino-3-thiapentyl-1-}-parabanic acid, N-methyl-N '-{8- (meth) acryloylamino-3,6-dithiaoctyl-1
-}-Parabanic acid, N-methyl-N '-{5- (meth)
Acryloylamino-3-azapentyl-1-}-parabanic acid, N-methyl-N '-{8- (meth) acryloylamino-3,6-diazaoctyl-1-}-parabanic acid, N-methyl-N'- {5- (meth) acryloylamino-3-aza-3-methyl-pentyl} -1-}-parabanic acid, N-methyl-N '-{8- (meth) acryloylamino-3,6-diaza-3 , 6-Dimethyl-octyl-1-}-parabanic acid, N-methyl-N '-{(meth) acryloyl-N-methyl-amino-ethyl} -parabanic acid, N-methyl-N'-{3- ( (Meth) acryloyl-N-methyl-amino-propyl-1-}-parabanic acid, N-methyl-N '-{2- (meth) acryloyl-N-methyl-amino-propyl-1-}-parabanic acid, N -Methyl-N '-{3- (Meth) acryloyl-
N-methyl-amino-propyl-2-}-parabanic acid,
N-methyl-N '-{4- (meth) acryloyl-N-
Methyl-amino-butyl-1-}-parabanic acid, N-methyl-N '-{3- (meth) acryloyl-N-methyl-amino-butyl-2-}-parabanic acid, N-methyl-
N '-{5- (meth) acryloyl-N-methyl-amino-3-oxapentyl-1-}-parabanic acid, N-methyl-N'-{8- (meth) acryloyl-N-methyl-amino- 3,6-Dioxaoctyl-1-}-parabanic acid, N-methyl-N '-{5- (meth) acryloyl-N-methyl-amino-3-oxa-1,4-dimethyl-pentyl-1- } -Parabanic acid, N-methyl-N'-
{8- (meth) acryloyl-N-methyl-amino-
3,6-Dioxa-1,4,7-trimethyl-octyl-1-}-parabanic acid, N-methyl-N ′-{5- (meth) acryloyl-N-methyl-amino-3-thiapentyl-1- } -Parabanic acid, N-methyl-N '-{8-
(Meth) acryloyl-N-methyl-amino-3,6-
Dithiaoctyl-1-}-parabanic acid, N-methyl-
N '-{5- (meth) acryloyl-N-methyl-amino-3-azapentyl-1-}-parabanic acid, N-methyl-N'-{8- (meth) acryloyl-N-methyl-
Amino-3,6-diazaoctyl-1-}-parabanic acid, N-methyl-N '-{5- (meth) acryloyl-
N-methyl-amino-3-aza-3-methyl-pentyl} -1-}-parabanic acid, N-methyl-N '-{8-
(Meth) acryloyl-N-methyl-amino-3,6-
Diaza-3,6-dimethyl-octyl-1-}-parabanic acid, N-ethyl-N ′-[3-{(meth) acryloyloxy} -2-hydroxypropyl] -parabanic acid,
N-ethyl-N '-[6-((meth) acryloyloxy} -2-hydroxy (4-oxahexyl)]-parabanic acid, N-ethyl-N'-[6-{(meth) acryloyloxy}- 2-hydroxy (4-thiahexyl)]
-Parabanic acid, N-ethyl-N '-[6-{(meth) acryloyloxy} -2-hydroxy (4-azahexyl)]-parabanic acid, N-ethyl-N'-[6-{(meth) acryloyl Oxy} -2-hydroxy (4-methyl-4-azahexyl)]-parabanic acid, N-ethyl-
N '-[3-{(meth) acryloylthio} -2-hydroxypropyl] -parabanic acid, N-ethyl-N'-
[6-{(meth) acryloylthio} -2-hydroxy (4-oxahexyl)]-parabanic acid, N-ethyl-
N '-[6-{(meth) acryloylthio} -2-hydroxy (4-thiahexyl)]-parabanic acid, N-ethyl-N'-[6-{(meth) acryloylthio} -2-
Hydroxy (4-azahexyl)]-parabanic acid, N-
Ethyl-N '-[6-((meth) acryloylthio}-
2-Hydroxy (4-methyl-4-azahexyl)]-
Parabanic acid, N-ethyl-N '-[3-{(meth) acryloylamino} -2-hydroxypropyl] -parabanic acid, N-ethyl-N'-[6-{(meth) acryloylamino} -2- Hydroxy (4-oxahexyl)]
-Parabanic acid, N-ethyl-N '-[6-{(meth) acryloylamino} -2-hydroxy (4-thiahexyl)]-parabanic acid, N-ethyl-N'-[6-{(meth) acryloyl Amino} -2-hydroxy (4-azahexyl)]-parabanic acid, N-ethyl-N ′-[6-
{(Meth) acryloylamino} -2-hydroxy (4
-Methyl-4-azahexyl)]-parabanic acid, N-ethyl-N '-[3-{(meth) acryloyl-methylamino} -2-hydroxypropyl] -parabanic acid, N-
Ethyl-N '-[6-{(meth) acryloyl-methylamino} -2-hydroxy (4-oxahexyl)]-
Parabanic acid, N-ethyl-N '-[6-{(meth) acryloyl-methylamino} -2-hydroxy (4-thiahexyl)]-parabanic acid, N-ethyl-N'-[6-
{(Meth) acryloyl-methylamino} -2-hydroxy (4-azahexyl)]-parabanic acid, N-ethyl-N '-[6-{(meth) acryloyl-methylamino} -2-hydroxy (4-methyl) -4-Azahexyl)]-parabanic acid, N-isopropyl-N '-{(meth) acryloyloxy-ethyl} -parabanic acid, N-
n-propyl-N '-{(meth) acryloyloxy-
Ethyl} -parabanic acid, Nn-butyl-N '-{(meth) acryloyloxy-ethyl} -parabanic acid, N-
Mono (meth) acrylates such as methoxyethyl-N '-{(meth) acryloyloxy-ethyl} -parabanic acid, N-methyl-N'-[2,3-bis {(meth) acryloyloxy} -propyl] -Parabanic acid, N-methyl-N '-[2,6-bis {(meth) acryloyloxy} -4-oxahexyl] -parabanic acid, N-methyl-N'-[2,6-bis {(meth ) Acryloyloxy} -4-thiahexyl] -parabanic acid, N-methyl-
N '-[2,6-bis {(meth) acryloyloxy}
-4-azahexyl] -parabanic acid, N-methyl-N '
-[2,6-bis {(meth) acryloyloxy} -4
-Methyl-4-azahexyl] -parabanic acid, N-methyl-N '-[3-{(meth) acryloylthio} -2
-(Meth) acryloyloxy-propyl] -parabanic acid, N-methyl-N '-[6-((meth) acryloylthio} -2- (meth) acryloyloxy- (4-oxahexyl)]-parabanic acid, N-methyl-N '-[6
-{(Meth) acryloylthio} -2- (meth) acryloyloxy- (4-thiahexyl)]-parabanic acid,
N-methyl-N '-[6-{(meth) acryloylthio} -2- (meth) acryloyloxy- (4-azahexyl)]-parabanic acid, N-methyl-N'-[6-
{(Meth) acryloylthio} -2- (meth) acryloyloxy- (4-methyl-4-azahexyl)]-parabanic acid, N-methyl-N '-[3-{(meth) acryloylamino} -2- (Meth) acryloyloxy-propyl] -parabanic acid, N-methyl-N '-[6-
{(Meth) acryloylamino} -2- (meth) acryloyloxy- (4-oxahexyl)]-parabanic acid, N-methyl-N '-[6-{(meth) acryloylamino} -2- (meth) Acryloyloxy- (4-thiahexyl)]-parabanic acid, N-methyl-N '-[6
-{(Meth) acryloylamino} -2- (meth) acryloyloxy- (4-azahexyl)]-parabanic acid, N-methyl-N '-[6-{(meth) acryloylamino} -2- (meth) Acryloyloxy- (4-methyl-4-azahexyl)]-parabanic acid, N-methyl-N '-[3-{(meth) acryloyl-methylamino} -2- (meth) acryloyloxy-propyl]-
Parabanic acid, N-methyl-N '-[6-{(meth) acryloyl-methylamino} -2- (meth) acryloyloxy- (4-oxahexyl)]-parabanic acid, N-
Methyl-N '-[6-{(meth) acryloyl-methylamino} -2- (meth) acryloyloxy- (4-thiahexyl)]-parabanic acid, N-methyl-N'-[6
-{(Meth) acryloyl-methylamino} -2- (meth) acryloyloxy- (4-azahexyl)]-parabanic acid, N-methyl-N '-[6-{(meth) acryloyl-methylamino} -2 Examples include poly (meth) acrylates such as-(meth) acryloyloxy- (4-methyl-4-azahexyl)]-parabanic acid.

As the compound represented by the general formula (2),
For example, N, N'-bis {(meth) acryloyl} -parabanic acid, N, N'-bis {2- (meth) acryloyloxy-1-ethyl} -parabanic acid, N, N'-bis {3- (Meth) acryloyloxy-1-propyl}-
Parabanic acid, N, N'-bis {2- (meth) acryloyloxy-1-propyl} -parabanic acid, N, N'-bis {(meth) acryloyloxy-butyl} -parabanic acid, N, N'- Bis {4- (meth) acryloyloxy-1-butyl} -parabanic acid, N, N'-bis {3-
(Meth) acryloyloxy-2-butyl} -parabanic acid, N, N'-bis {5- (meth) acryloyloxy-1- (3-oxapentyl)}-parabanic acid, N,
N'-bis {8- (meth) acryloyloxy-1-
(3,6-Dioxaoctyl)}-parabanic acid, N,
N'-bis {5- (meth) acryloyloxy-1-
(3-Thiapentyl)}-parabanic acid, N, N′-bis {8- (meth) acryloyloxy-1- (3,6-dithiaoctyl)}-parabanic acid, N, N′-bis {5-
(Meth) acryloyloxy-1- (3-azapentyl)}-parabanic acid, N, N′-bis {8- (meth) acryloyloxy-1- (3,6-diazaoctyl)}
-Parabanic acid, N, N'-bis [5- (meth) acryloyloxy-1- {3-methyl-3-azapentyl}]
-Parabanic acid, N, N'-bis [8- (meth) acryloyloxy-1- {3,6-dimethyl-3,6-diazaoctyl}]-parabanic acid, N, N'-bis {3- (meth ) Acryloyloxy-2-hydroxy-1-propyl} -parabanic acid, N, N′-bis {6- (meth) acryloyloxy-2-hydroxy-1- (4-oxahexyl)}-paravanic acid, N, N'-bis {6- (meth) acryloyloxy-2-hydroxy-1- (4-
Thiahexyl)}-parabanic acid, N, N'-bis {6-
(Meth) acryloyloxy-2-hydroxy-1-
(4-Azahexyl)}-parabanic acid, N, N′-bis
[6- (meth) acryloyloxy-2-hydroxy-
1- {4-methyl-4-azahexyl}]-parabanic acid, N, N'-bis {2- (meth) acryloylthio-
1-ethyl} -parabanic acid, N, N'-bis {3- (meth) acryloylthio-1-propyl} -parabanic acid,
N, N'-bis {2- (meth) acryloylthio-1-
Propyl} -parabanic acid, N, N'-bis {(meth) acryloylthio-butyl} -parabanic acid, N, N'-bis {4- (meth) acryloylthio-1-butyl} -parabanic acid, N, N'-bis {3- (meth) acryloylthio-2-butyl} -parabanic acid, N, N'-bis {5
-(Meth) acryloylthio-1- (3-oxapentyl)}-parabanic acid, N, N'-bis {8- (meth) acryloylthio-1- (3,6-dioxaoctyl)}
-Parabanic acid, N, N'-bis {5- (meth) acryloylthio-1- (3-thiapentyl)}-parabanic acid,
N, N'-bis {8- (meth) acryloylthio-1-
(3,6-Dithiaoctyl)}-parabanic acid, N, N ′
-Bis {5- (meth) acryloylthio-1- (3-azapentyl)}-parabanic acid, N, N'-bis {8-
(Meth) acryloylthio-1- (3,6-diazaoctyl)}-parabanic acid, N, N′-bis [5- (meth)]
Acryloylthio-1- {3-methyl-3-azapentyl}]-parabanic acid, N, N′-bis [8- (meth) acryloylthio-1- {3,6-dimethyl-3,6-diazaoctyl}] -Parabanic acid, N, N'-bis {3-
(Meth) acryloylthio-2-hydroxy-1-propyl} -parabanic acid, N, N′-bis {6- (meth) acryloylthio-2-hydroxy-1- (4-oxahexyl)}-parabanic acid, N, N'-bis {6- (meth) acryloylthio-2-hydroxy-1- (4-thiahexyl)}-parabanic acid, N, N'-bis {6-
(Meth) acryloylthio-2-hydroxy-1- (4
-Azahexyl)}-parabanic acid, N, N'-bis [6
-(Meth) acryloylthio-2-hydroxy-1-
{4-methyl-4-azahexyl}]-parabanic acid,
N, N'-bis {2- (meth) acryloylamino-1
-Ethyl} -parabanic acid, N, N'-bis {3- (meth) acryloylamino-1-propyl} -parabanic acid, N, N'-bis {2- (meth) acryloylamino-1-propyl}- Parabanic acid, N, N'-bis {4-
(Meth) acryloylamino-1-butyl} -parabanic acid, N, N'-bis {3- (meth) acryloylamino-2-butyl} -parabanic acid, N, N'-bis {5-
(Meth) acryloylamino-1- (3-oxapentyl)}-parabanic acid, N, N′-bis {8- (meth) acryloylamino-1- (3,6-dioxaoctyl)}-paravanic acid, N, N'-bis [3-{(meta)
Acryloyl-amino} -2-hydroxy-1-propyl] -parabanic acid, N, N'-bis [2-{(meth) acryloyl (methylamino)}-1-ethyl] -parabanic acid, N, N'- Bis [3-{(meth) acryloyl (methylamino)}-1-propyl] -parabanic acid,
N, N'-bis [2-{(meth) acryloyl (methylamino)}-1-propyl] -parabanic acid, N, N'-
Bis [4-{(meth) acryloyl (methylamino)}
-1-Butyl] -parabanic acid, N, N'-bis [3-
{(Meth) acryloyl (methylamino)}-2-butyl} -parabanic acid, N, N'-bis [5-{(meth) acryloyl (methylamino)}-1- (3-oxapentyl)]-paraban Acid, N, N'-bis [8-{(meth) acryloyl (methylamino)}-1- (3,6-
Dioxaoctyl)]-parabanic acid, N, N'-bis [3-{(meth) acryloyl- (methylamino)}-
Examples include poly (meth) acrylates such as 2-hydroxy-1-propyl] -parabanic acid.

As the compound represented by the general formula (3),
For example, N, N'-bis {2-hydroxy-1-ethyl} -parabanic acid, N, N'-bis {3-hydroxy-
1-Propyl} -parabanic acid, N, N'-bis {2-hydroxy-1-propyl} -parabanic acid, N, N'-bis {hydroxy-butyl} -parabanic acid, N, N'-bis {4 -Hydroxy-1-butyl} -parabanic acid, N,
N'-bis {3-hydroxy-2-butyl} -parabanic acid, N, N'-bis {5-hydroxy-1- (3-oxapentyl)}-parabanic acid, N, N'-bis {8- Hydroxy-1- (3,6-dioxaoctyl)}-parabanic acid, N, N′-bis {5-hydroxy-1- (3-
Thiapentyl)}-parabanic acid, N, N'-bis {8-
Hydroxy-1- (3,6-dithiaoctyl)}-parabanic acid, N, N′-bis {5-hydroxy-1- (3-
Azapentyl)}-parabanic acid, N, N′-bis {8-
Hydroxy-1- (3,6-diazaoctyl)}-parabanic acid, N, N′-bis [5-hydroxy-1- {3-
Methyl-3-azapentyl}]-parabanic acid, N, N ′
-Bis [8-hydroxy-1- {3,6-dimethyl-
3,6-Diazaoctyl}]-parabanic acid, N, N'-
Bis {3-hydroxy-2-hydroxy-1-propyl} -parabanic acid, N, N'-bis {6-hydroxy-
2-hydroxy-1- (4-oxahexyl)}-parabanic acid, N, N′-bis {6-hydroxy-2-hydroxy-1- (4-thiahexyl)}-parabanic acid, N,
N'-bis {6-hydroxy-2-hydroxy-1-
(4-Azahexyl)}-parabanic acid, N, N′-bis
[6-Hydroxy-2-hydroxy-1- {4-methyl-4-azahexyl}]-parabanic acid, N, N′-bis {2-mercapto-1-ethyl} -parabanic acid, N,
N'-bis {3-mercapto-1-propyl} -parabanic acid, N, N'-bis {2-mercapto-1-propyl} -parabanic acid, N, N'-bis {mercapto-butyl} -parabanic acid , N, N'-bis {4-mercapto-
1-Butyl} -parabanic acid, N, N′-bis {3-mercapto-2-butyl} -parabanic acid, N, N′-bis {5-mercapto-1- (3-oxapentyl)}-parabanic acid , N, N'-bis {8-mercapto-1-
(3,6-Dioxaoctyl)}-parabanic acid, N,
N'-bis {5-mercapto-1- (3-thiapentyl)}-parabanic acid, N, N'-bis {8-mercapto-1- (3,6-dithiaoctyl)}-paravanic acid,
N, N'-bis {5-mercapto-1- (3-azapentyl)}-parabanic acid, N, N'-bis {8-mercapto-1- (3,6-diazaoctyl)}-paravanic acid,
N, N'-bis [5-mercapto-1- {3-methyl-
3-azapentyl}]-paravanic acid, N, N′-bis [8
-Mercapto-1- {3,6-dimethyl-3,6-diazaoctyl}]-parabanic acid, N, N'-bis {3-mercapto-2-hydroxy-1-propyl} -parabanic acid, N, N ' -Bis {6-mercapto-2-hydroxy-1- (4-oxahexyl)}-parabanic acid, N,
N'-bis {6-mercapto-2-hydroxy-1-
(4-Thiahexyl)}-parabanic acid, N, N′-bis {6-mercapto-2-hydroxy-1- (4-azahexyl)}-parabanic acid, N, N′-bis [6-mercapto-2- Hydroxy-1- {4-methyl-4-azahexyl}]-parabanic acid, N, N′-bis {2-amino-1-ethyl} -parabanic acid, N, N′-bis {3-amino-1- Propyl} -parabanic acid, N, N'-bis {2-amino-1-propyl} -parabanic acid, N, N '
-Bis {amino-butyl} -parabanic acid, N, N'-bis {4-amino-1-butyl} -parabanic acid, N, N '
-Bis {3-amino-2-butyl} -parabanic acid, N,
N'-bis {5-amino-1- (3-oxapentyl)}-parabanic acid, N, N'-bis {8-amino-1
-(3,6-dioxaoctyl)}-parabanic acid, N,
N'-bis {5-amino-1- (3-thiapentyl)}
-Parabanic acid, N, N'-bis {8-amino-1-
(3,6-Dithiaoctyl)}-parabanic acid, N, N ′
-Bis {5-amino-1- (3-azapentyl)}-parabanic acid, N, N'-bis {8-amino-1- (3,6
-Diazaoctyl)}-parabanic acid, N, N'-bis
[5-amino-1- {3-methyl-3-azapentyl}]
-Parabanic acid, N, N'-bis [8-amino-1-
{3,6-Dimethyl-3,6-diazaoctyl}]-parabanic acid, N, N′-bis {3-amino-2-hydroxy-1-propyl} -parabanic acid, N, N′-bis {6
-Amino-2-hydroxy-1- (4-oxahexyl)}-parabanic acid, N, N'-bis {6-amino-2
-Hydroxy-1- (4-thiahexyl)}-parabanic acid, N, N'-bis {6-amino-2-amino-1-
(4-Azahexyl)}-parabanic acid, N, N′-bis
[6-Amino-2-amino-1- {4-methyl-4-azahexyl}]-parabanic acid, N, N′-bis {2-
(Methylamino) -1-ethyl} -parabanic acid, N,
N'-bis {3- (methylamino) -1-propyl}-
Parabanic acid, N, N'-bis {2- (methylamino)-
1-propyl} -parabanic acid, N, N'-bis {(methylamino) -butyl} -parabanic acid, N, N'-bis {4- (methylamino) -1-butyl} -parabanic acid,
N, N'-bis {3- (methylamino) -2-butyl}
-Parabanic acid, N, N'-bis {5- (methylamino)
-1- (3-oxapentyl)}-parabanic acid, N,
N'-bis {8- (methylamino) -1- (3,6-dioxaoctyl)}-parabanic acid, N, N'-bis {5
-(Methylamino) -1- (3-thiapentyl)}-parabanic acid, N, N'-bis {8- (methylamino) -1
-(3,6-dithiaoctyl)}-parabanic acid, N,
N'-bis {5- (methylamino) -1- (3-azapentyl)}-parabanic acid, N, N'-bis {8- (methylamino) -1- (3,6-diazaoctyl)}-paraban Acid, N, N'-bis [5- (methylamino) -1-
{3-Methyl-3-azapentyl}]-parabanic acid,
N, N'-bis [8- (methylamino) -1- {3,6
-Di (methylamino) -3,6-diazaoctyl}]-
Parabanic acid, N, N'-bis {3-methylamino} -2
-Hydroxy-1-propyl} -parabanic acid, N, N '
-Bis {6-methylamino} -2-hydroxy-1-
(4-oxahexyl)}-parabanic acid, N, N′-bis {6-methylamino} -2-hydroxy-1- (4-
Thiahexyl)}-parabanic acid, N, N'-bis {6-
Methylamino} -2-amino-1- (4-azahexyl)}-parabanic acid, N, N′-bis [6-methylamino] -2-amino-1- {4-methyl-4-azahexyl}]- Parabanic acid etc. are mentioned.

The compounds belonging to the compounds represented by the general formulas (2) and (3) may be used either individually or in combination of two or more when obtaining an organic polymer.

The compound having at least one or more parabanic acid skeleton represented by the partial structural formula (1) and at least one or more reactive groups in the same molecule is
er Organischen Chemie (1971, Vierte Auflage Herausg
egeben von Eugen Muller) and new experimental chemistry course (19
75, The Chemical Society of Japan) and the like, and can be synthesized by utilizing many general reactions as described in general books on organic synthesis.

Next, a typical synthetic method thereof will be described by taking a compound having one parabanic acid skeleton represented by the partial structural formula (1) and two reactive groups in the same molecule as a specific example.

[0044]

[Chemical 9]

Is a reaction for introducing a hydroxyalkyl group into the nitrogen atom of parabanic acid. Examples of the hydroxyalkylating agent include halogenoethanols such as chloroethanol and bromoethanol, alkylene carbonates,
Alkylene oxides are typical.

In this reaction, a base is preferably used as a reaction accelerator. As the base, for example, caustic soda, caustic potassium, magnesium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, magnesium hydride, potassium hydride, sodium , Magnesium, calcium, potassium, sodium methylate, potassium t-butoxy, triethylamine, tributylamine, pyridine, dimethylaniline, triethylenediamine, hexamethylenetetramine and the like. When a strong base is required as a reaction accelerator, a relatively strong base such as caustic soda, potassium caustic, sodium methylate, potassium t-butoxy, sodium hydride or sodium may be used. These bases can be used alone or in combination.

Is the epoxidation reaction of parabanic acid. As an epoxidizing agent, epihalohydrin such as epichlorohydrin and epobromohydrin is preferably used.

Also in this reaction, an interlayer transfer catalyst is preferably used in addition to the same base as the reaction accelerator. Examples of the interlayer transfer catalyst include tetraethylammonium halide, tetraethylammonium hydroxide, tetrabutylammonium halide, trimethylbenzylammonium halide, trimethylbenzylammonium hydroxide and the like.
Among these, trimethylbenzylammonium halide and trimethylbenzylammonium hydroxide may give preferable results.

These reaction accelerators may be used not only alone, but also in various types in necessary amounts within a range where there is no problem.

Is a ring-opening reaction of an epoxy group with acrylic acid, methacrylic acid, or a halogenocarboxylic acid. This ring opening reaction is also used as a chain extension reaction,
For example, a mercapto compound such as mercapto alcohol,
Alternatively, a method of reacting an amino compound such as amino alcohol is used.

This reaction is also preferably used as or as a reaction accelerator, a base and an interlayer transfer catalyst.

Examples of the chain extension reaction include a method of reacting a corresponding hydroxyl group, mercapto group or amino group with halogeno alcohols, alkylene carbonates and alkylene oxides.

Is a (meth) acrylate reaction for reacting a hydroxyl group with an acrylic acid halide or a methacrylic acid halide. Usually, an acrylic acid halide or a methacrylic acid halide is directly reacted.

When the hydroxyl group is a compound in which a mercapto group, an amino group or a methylamino group is replaced, it is converted to a (meth) acryloyl-thio group, a (meth) acryloyl-amino group or a (meth) acryloyl-methylamino group. To be done. For the conversion into these groups, an acrylic acid halide or a methacrylic acid halide may be directly reacted in the same manner as in the case of the hydroxy group, but usually, in order to suppress the yield decrease due to Michael addition, once the A method can be used in which a halogenocarboxylic acid halide such as propionic acid chloride is reacted to form a halogenocarboxylic acid ester, and then a base such as a tertiary amine is added to carry out dehydrohalogenation. In the case of an amino group or a methylamino group, depending on the case, in order to reduce the reactivity, a mineral acid salt such as a hydrochloride is reacted, or a transesterification reaction with an alkyl (meth) acrylate is used. You can also

For example, when a mercapto group is synthesized for the purpose of synthesizing a (meth) acryloyl-thio group, a conversion reaction from a hydroxy group is often used.

For example, the hydroxy group can be replaced by thionyl chloride,
Sulfuryl chloride, phosphorus pentachloride, phosphorus tribromide, hydrochloric acid, hydrobromic acid, hydroiodic acid, methanesulfonyl chloride,
It is converted to an electron withdrawing group such as halogen or sulfonate by reacting with a reagent such as trifluoromethanesulfonyl chloride, benzenesulfonyl chloride, tosyl chloride.

Then, for example, alkali metal sulfides such as sodium hydrosulfide, potassium hydrosulfide and sodium sulfide are reacted, thiourea is reacted to hydrolyze to an isothiuronium salt, or sodium thiosulfate is reacted. Bunte salt can be hydrolyzed or N,
N-dialkyldithiocarbamic acid alkali metal salt is reacted for hydrolysis, dithiocarbonic acid O-alkyl alkali metal salt is reacted for hydrolysis, Grignard reagent is reacted, and then sulfur is reacted, Finally, a method of hydrolyzing or reducing, a method of once reacting thiols to synthesize sulfides, and then cleaving with an alkali metal or the like is used.
Among these, the method via an isothiuronium salt is relatively preferably used.

Next, a (meth) acryloyl-amino group,
When synthesizing an amino group or a methylamino group for the purpose of synthesizing a (meth) acryloyl-methylamino group,
The following method is used.

For example, a method of synthesizing N, N-bis (3-aminopropyl) parabanic acid by addition reaction of acrylonitrile to parabanic acid and then reducing it, and electron-withdrawing group conversion of hydroxy group as in the case of mercapto group. And then reacting with ammonia, a metal amide or methylamine, the Gabriel method, the Delpine method, or the converted amino group is reacted with a methylating agent such as methyl iodide or dimethylsulfate to methylaminate. Methods and the like.

In the above synthetic reaction, in addition to the above-mentioned base and interlayer transfer catalyst, sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, boron trifluoride, aluminum chloride, alumina, dibutyltin dioxide,
An acid catalyst such as dibutyltin dilaurate or tetrabutyltin can be used as a reaction accelerator. These acid catalysts can be used alone or in combination.

Similarly, a solvent can be used in the above synthesis reaction. The solvent is not limited as long as it does not react with the reaction substrate, reaction reagent, product, catalyst or the like. Examples of the solvent include water, methanol, acetonitrile, dichloromethane, dichloroethane, chloroform, THF, dioxane, glyme, diglyme, dimethylformamide, N, N′-dimethyl-ethyleneurea, dimethylsulfoxide, sulfolane, benzene, toluene, xylene, Examples thereof include chlorobenzene, dichlorobenzene, hexane and cyclohexane.

As a specific compound, N, N'-bis (2-hydroxy-3) which is a compound represented by the general formula (2) is used.
-Acryloyloxy-propyl) -parabanic acid will be described. After reacting parabanic acid with epichlorohydrin in a large excess (5 to 10 times mol) in the presence of an interlayer transfer catalyst, sodium hydroxide is added to effect ring closure. Then, N, N′-diglycidyl-parabanic acid is synthesized.

Then, the obtained N, N'-diglycidyl-
Parabanic acid is reacted with chloropropionic acid in the presence of an interlayer transfer catalyst, and then triethylamine is added to carry out a dehydrochlorination reaction to obtain a desired N, N′-bis (2-hydroxy-3-acryloyloxy-propyl). ) -Synthesizing parabanic acid.

A compound having at least one or more parabanic acid skeleton represented by the partial structural formula (1) and at least one or more reactive groups in the same molecule obtained by utilizing the above reaction is Although it can be used alone, it can be polymerized by reacting with a compound having at least one or more parabanic acid skeleton represented by the partial structural formula (1) and at least one or more reactive groups in the same molecule. It is also possible to polymerize in combination with a reactive compound having a functional group that gives a polymer.

At least one parabanic acid skeleton represented by the partial structural formula (1) and at least one in the same molecule.
Examples of the reactive compound that can be used in combination with the compound having one or more reactive groups include a compound having at least one carbon-carbon double bond, a (thio) epoxy compound, a mercapto compound, an amino compound, and the like. Among these, compounds having at least one carbon-carbon double bond are preferable from the viewpoint of pot life. Also,
Epoxy compounds are preferred when it is desired to improve the generally required adhesiveness when coating glass or metal.

Typical examples of the reactive compound include styrene, isopropenylbenzene, divinylbenzene, diisopropenylbenzene, bis {(meth) acryloyloxy} -benzene, and the like.
Bis {(meth) acryloyloxymethyl} -benzene, 2,2-bis {(meth) acryloyloxy-ethyloxy-ethyloxy-phenyl} -propane, 2,
Aromatic unsaturated compounds such as 2-bis {(meth) acryloyloxy-ethyloxy-phenyl} -propane, ethylene glycol diallyl carbonate, diethylene glycol diallyl carbonate, glycidyl methacrylate, isocyanatoethyl methacrylate, 3-isopropenyl-α, α -Dimethyl-benzyl isocyanate, vinyl acetate, vinyl alcohol, allyl alcohol, acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, triethylene glycol di (meth)
Acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Bis {(meth) acryloyloxymethyl} -cyclohexane, bis {(meth) acryloyloxymethyl}-
Tricyclo [5.2.1.0.26] decane, trimethylolpropane tris {(meth) acrylate}, N, N ',
N ″ -tris (allyl) -isocyanurate, N,
N ′, N ″ -tris {(meth) acryloyloxy-
Ethyl} -isocyanurate, aliphatic unsaturated compounds such as 1-imidazolidinepropanoic acid-3-methyl-α-methylene-2,4,5-trioxo-diphenylmethyl ester, N-vinyl-oxazolidone, N-allyl -Oxazolidone, N-allyloxycarbonyl-oxazolidone, N- (meth) acryloyl-oxazolidone, N
-Oxazolidone-based unsaturated compounds such as allyloxycarbonyloxyethyl-oxazolidone and N- (meth) acryloyloxyethyl-oxazolidone, N-vinyl-pyrrolidone, N-allyl-pyrrolidone, N-allyloxycarbonyl-pyrrolidone, N- Pyrrolidone-based unsaturated compounds such as (meth) acryloyl-pyrrolidone, N-allyloxycarbonyloxyethyl-pyrrolidone and N- (meth) acryloyloxyethyl-pyrrolidone,
N-vinyl-N-methyl-acetamide, N-allyl-
N-methyl-acetamide, N-allyloxycarbonyl-N-methyl-acetamide, N- (meth) acryloyl-N-methyl-acetamide, N-allyloxycarbonyloxyethyl-N-methyl-acetamide, N
Amide unsaturated compounds such as-(meth) acryloyloxyethyl-N-methyl-acetamide, N, N-dimethyl- (meth) acrylamide, N, N-dimethyl-vinylamide, N, N-dimethyl-acrylamide, divinyl Sulfone-based unsaturated compounds such as sulfone and diallyl sulfone, and urea-based unsaturated compounds such as N, N′-dimethyl-N, N′-divinylurea and N, N′-dimethyl-N, N′-diallylurea , N-methyl-N'-vinyl-ethylene urea, N-methoxyethyl-N'-vinyl-ethylene urea, N, N'-divinyl-ethylene urea, N-methyl-N'-allyl-ethylene urea, N- Methoxyethyl-N'-allyl-ethyleneurea, N, N'-diallyl-ethyleneurea, N-allyloxycarbonyl-N'-
Methyl-ethylene urea, N, N'-bis (allyloxycarbonyl) -ethylene urea, N, N'-bis (2-hydroxy-3-acryloyloxy-propyl) -ethylene urea, N, N'-bis {6 -(N-methyl-imidazolidinonyl-N '-)-2- (methacryloyloxy) -4-thiahexyl} -ethyleneurea, N-methacryloyloxy-N'-methyl-ethyleneurea, N-
(Acryloyloxy-ethyl) -N'-methyl-ethyleneurea, N- (methacryloyloxy-ethyl)-
N'-methyl-ethyleneurea, N- (acryloyloxy-ethyl) -N'-methoxyethyl-ethyleneurea,
N- (methacryloyloxy-ethyl) -N'-methoxyethyl-ethylene urea, N- (glycidyl-oxy-
Ethyl) -N'-methoxyethyl-ethylene urea, N-
(Acryloylthio-ethyl) -N'-methoxyethyl-ethyleneurea, N- (allyloxycarbonylthio-
Ethyl) -N'-methoxyethyl-ethylene urea, N,
N'-bis (acryloyloxy-ethyl) -ethylene urea, N, N'-bis (methacryloyloxy-ethyl) -ethylene urea, N, N'-bis (allyloxycarbonyloxy-ethyl) -ethylene urea, N, N'-
Bis (acryloylthio-ethyl) -ethylene urea,
Ethyleneurea unsaturated compounds such as N, N'-bis (allyloxycarbonylthio-ethyl) -ethyleneurea, bis (4-glycidyloxy-phenyl) -methane, bis (4-glycidyloxy-cyclohexyl)-
Methane, 2,2-bis (4-glycidyloxy-phenyl) -propane, 2,2-bis (4-glycidyloxy-cyclohexyl) -propane, bis (4-glycidyloxy-phenyl) -ether, 4,4 ' -Bis (glycidyloxy) -2,2 ', 6,6'-tetramethyl-
Biphenyl, 1,5-bis (glycidyloxy) -naphthalene, diglycidyl-1,2-cyclohexanedicarboxylate, trimethylolpropane-tris (glycidyl ether), neopentyl glycol-bis (glycidyl ether), butanediol-bis ( Glycidyl ether), N, N-diglycidyl-N-phenyl-
Amine, N- (glycidyl) -N'-methyl-ethyleneurea, N, N'-bis (glycidyl-oxy-ethyl)
-Ethylene urea, N, N'-bis (glycidyl-thio-
Ethyl) -ethylene urea, epoxy compounds such as N, N-diglycidyl-parabanic acid, bis (thioglycidyl)
-Sulfide, bis (thioglycidyl) -disulfide, 1,2-bis (thioglycidylthio) -ethane, trimethylolpropane-tris (thioglycidyl ether), neopentyl glycol-bis (thioglycidyl ether), butanediol-bis (Thioglycidyl ether), N, N′-bis (thioglycidyl-thio-ethyl) -ethyleneurea and other thioepoxy compounds, ethanedithiol, butanedithiol, 1,2-dimercapto-3-propanol, 1,2-xylyl Dilenthiol, 1,3-xylylenedithiol, 1,4-xylylenedithiol, 2,5-bis (mercaptomethyl)-
1,4-dithiane, 1,2,3-trimercaptopropane, 4- (mercaptomethyl) -3,6-dithiaoctane-1,8-dithiol, 4,8-bis (mercaptomethyl) -3,6,9 -Trithia undecane-1,11-
Dithiol, ethylene glycol-bis (thioglycolate), butanediol-bis (thioglycolate),
Trimethylolpropane-tris (thioglycolate), pentaerythritol-tetrakis (thioglycolate), ethylene glycol-bis (3-mercaptopropionate), butanediol-bis (3-mercaptopropionate), trimethylolpropane -Tris (3-mercaptopropionate), pentaerythritol-tetrakis (3-mercaptopropionate)
Mercapto compounds such as cyclohexylamine, benzylamine, 1,2-ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,6
-Hexamethylenediamine, 1,3-xylidylenediamine, 1,3-bis (aminomethyl) -cyclohexane,
Isophoronediamine, bis (4-aminocyclohexyl) -methane, bis (aminomethyl) -norbornane,
N, N-bis (2-aminoethyl) piperazine-2,3
-Amine compounds such as dione and the like.

The above reactive compounds can be used in combination of two or more when obtaining an organic polymer.

In a polymerizable composition containing at least one or more parabanic acid skeleton represented by the partial structural formula (1) and at least one or more reactive group-containing compound in the same molecule, In the case where a compound having at least one or more parabanic acid skeleton represented by the partial structural formula (1) and at least one or more reactive group is used in combination with the reactive compound, the composition ratio thereof is particularly limited. Rather, it can be determined depending on the properties required of the obtained organic polymer.

As the method for polymerizing the above-mentioned polymerizable composition,
A general polymerization method can be used, and for example, solution polymerization, melt polymerization and the like can be used.

Typical polymerization methods are thermal polymerization and radiation polymerization, and they are appropriately selected according to the purpose. The polymerization method is
Each of these methods can be carried out independently, but it is also possible to carry out a combination of thermal polymerization and radiation polymerization.

As the polymerization method, for example, thermal polymerization is likely to be selected in the case of a large molded product, and radiation polymerization is likely to be selected in the case of manufacturing a molded product in a small size and in a short time.
In the case of a very large-scale coating represented by an outer wall coating or the like, radiation polymerization using sunlight is easily selected, and thermal polymerization and radiation polymerization are preferable for a relatively small-scale coating.

Thermal polymerization is performed by melting a polymerizable composition containing at least one or more parabanic acid skeleton represented by the partial structural formula (1) and a compound having at least one or more reactive groups in the same molecule. The heating is carried out at a temperature above the temperature above the Tg point of the target organic polymer or above about 300 ° C., but the temperature may be raised gradually from around room temperature (25 ° C.).

In carrying out the thermal polymerization, a radical polymerization catalyst, an anion polymerization catalyst or a cation polymerization catalyst can be used, if necessary. These polymerization catalysts can be used alone or in combination. The selection of the polymerization catalyst and the combination thereof can be appropriately determined depending on the compounds present in the polymerizable composition, the composition ratio and the like.

For example, a compound or a reactive compound having at least one or more parabanic acid skeleton represented by the partial structural formula (1) and at least one or more reactive groups in the same molecule can be used as a reactive group. When the (meth) acryloyl group and the carbon-carbon double bond are present, it is preferable to use a radical polymerization catalyst. When a (meth) acryloyl group and a (thio) epoxy group are present as reactive groups, it is preferable to use a radical polymerization catalyst and an anionic polymerization catalyst or a radical polymerization catalyst and a cationic polymerization catalyst in combination. When a (meth) acryloyl group and a mercapto group are present as reactive groups, it is preferable to use a radical polymerization catalyst and an anionic polymerization catalyst together. When a (meth) acryloyl group and an amino group are present as reactive groups, it is preferable to use a radical polymerization catalyst or a radical polymerization catalyst and an anionic polymerization catalyst in combination. Carbon as a reactive group
When a carbon double bond, a (thio) epoxy group, a mercapto group and an amino group are present, it is preferable to use a radical polymerization catalyst and an anionic polymerization catalyst together.

Specific examples of the above-mentioned polymerization catalyst include radical catalysts such as azobisisobutyronitrile, benzoyl peroxide, di-3-methoxybutylperoxydicarbonate and diisopropylperoxydicarbonate. , Α-cumylperoxy neodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5, -trimethylhexanoate, dicumyl peroxide, 1,1 -Di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide and the like can be mentioned.

As the anion catalyst, for example, tetrabutylammonium chloride, tetrabutylammonium hydroxide, 1,6-hexamethylenediamine,
1,3-xidylylenediamine, 1,3-bis (aminomethyl) -cyclohexane, isophoronediamine, bis (4-aminocyclohexyl) -methane, bis (aminomethyl) -norbornane, 4-amino-2,2,2. 6,
6, -Tetramethylpiperidine, triethylamine, tributylamine, pyridine, N-methylpyrrolidone, piperazine, trifelphosphine, tributylphosphine, triethanolamine, methyldiethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone, 2- Dimethylaminoethylbenzoic acid, ethyl dimethylaminobenzoate, isoamyl dimethylaminobenzoate, (n-butoxy) ethyl dimethylaminobenzoate, isoamyl 2-dimethylaminoethylbenzoate, 2-ethylhexyl 2-dimethylaminoethylbenzoate, Sodium acetate, potassium phosphate, sodium methoxide, 2-methyl-imidazole, 2-ethyl-imidazole, 2-phenyl-imidazole, dicyandiamide, trade name Amicure VDH {Ajinomoto Co., Inc.}, trade name Amicure LDH {Ajinomoto Co., Ltd.}, trade name Amicure UDH {Ajinomoto Co., Ltd.}, trade name Amicure PN-23 {Ajinomoto Co., Ltd.}, trade name Amicure PN-24 {Ajinomoto Co., Inc.}, trade name Amicure MY-24 {Ajinomoto Co., Ltd.}, trade name Curezol HZ {Shikoku Chemical Industry Co., Ltd.}, trade name Curesol CN {Shikoku Chemical Industry Co., Ltd.}, trade name Curezol AZINE {Shikoku Chemicals Co., Ltd.} 2,4,6-tris (N, N-dimethylaminomethyl) -phenol, dimethylbenzylamine,
1,8-diazabicyclo (5,4,0) undecane (D
Abbreviated as BU. ), Tetrabutylphosphonium benzotriazolate {Nippon Kagaku Kogyo KK, trade name Hishicolin PX-4BT} and the like.

Examples of the cation catalyst include sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, phosphoric acid, acetic acid, propionic acid,
Dibutyltin dioxide, dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, tetrabutyltin, boron trifluoride, boron trifluoride / diethyl ether complex, boron trifluoride / ethylamine salt, boron trifluoride / piperidine salt, Tetraethoxy titanium,
Titanium oxide, aluminum oxide, aluminum fluoride, trade name Opton CP-66 {Asahi Denka Kogyo Co., Ltd.}, trade name Opton CP-77 {Asahi Denka Kogyo Co., Ltd.} and the like can be mentioned.

The amount of these thermal polymerization catalysts to be added cannot be limited because it varies depending on the composition ratio of the compounds present in the polymerizable composition, etc., but each catalyst is added to the polymerizable composition in an amount of about 0.0001 to about 0.0001. It is preferably used in the range of 10 wt%. It is more preferable to use it in the range of 0.001 to 5 wt%.

In the case of radiation polymerization, the polymerization is very fast and can be completed in only a few seconds. In particular, sunlight can be said to be an industrially extremely valuable polymerization method because it can easily carry out polymerization over a wide area such as on a rooftop.

Radiation polymerization comprises at least one in the same molecule.
A compound having a parabanic acid skeleton represented by the above partial structural formula (1) and at least one or more reactive groups, or the reactive group present in the reactive compound is a (meth) acryloyl group, an epoxy group, It can be used when it is an allyl carbonate group, a mercapto group and an amino group.

Examples of the radiation include visible light having a wavelength of 400 to 800 nm, ultraviolet rays having a wavelength of 400 nm or less, and electron beams. Usually, relatively inexpensive ultraviolet rays or visible rays are preferably used rather than an electron beam which is expensive for the apparatus. . However, the electron beam is extremely effective when ultraviolet rays or visible rays are not transmitted.

In the case of electron beam polymerization, a polymerization catalyst may not be necessary in some cases, but a photopolymerization catalyst may be added within the range where there is no problem.

When polymerization is carried out using ultraviolet rays, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a pulse xenon lamp, an ultraviolet laser,
A light source such as an electrodeless discharge lamp is preferably used.

In the radiation polymerization, in addition to the photopolymerization catalyst,
A radical polymerization catalyst, an anionic polymerization catalyst, or a cationic polymerization catalyst used in the above thermal polymerization can also be used in combination.

As the photopolymerization catalyst, a photo radical generator,
Examples thereof include photo anion generators and photo cation generators, with photo radical generators and photo cation generators being preferred.

As the photo-radical generator, for example, 2,
2-dimethyl-2-hydroxy-acetophenone, 4-
Phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, diethoxyacetophenone, 2
-Hydroxy-2-methyl-1-phenylpropane-1
-One, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- ( 2-hydroxy-2-propyl)
Ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- {4- (methylthio) phenyl}
-2-morpholyl propane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone , Allylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide-3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 -Dichlorothioxanthone,
2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 1-phenyl 1,2-propanedione-2 (O-ethoxycarbonyl) oxime, 2,4 6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, dibenzyl, 9,10-phenanthrenequinone, dibenzsuberone, 2-ethylanthraquinone, 4 ′, 4 ″ -diethylisophthaloquinone, 3,3 ′ , 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and the like.

The photocation generator is a compound having at least one or more parabanic acid skeleton represented by the partial structural formula (1) and at least one or more reactive groups in the same molecule, and The reactive group is (meth)
It is preferably used when radiation-polymerizing a compound having an acryloyl group or a carbon-carbon double bond in the presence of oxygen. In addition, it can be used as a photopolymerization catalyst when radiation-polymerizing a compound whose reactive group is an epoxy group.

Examples of the photo cation generator include aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, Bronsted acid onium salts, iron aromatic compound salts, and the like. Aromatic sulfonium salts, Aromatic iodonium salts and iron aromatic compound salts of Bronsted acids are preferred.

As the aromatic sulfonium salt, for example,
Triphenylsulfonium boron tetrafluoride salt, triphenylsulfonium hexafluorophosphonium salt, triphenylsulfonium hexafluoroarecenium salt, triphenylsulfonium hexafluoroantimonium salt, diphenyliodonium boron tetrafluoride salt,
Examples thereof include diphenyliodonium hexafluorophosphonium salt, diphenyliodonium hexafluoroarecenium salt, and diphenyliodonium hexafluoroantimonium salt. In addition, a trade name “Cyracure UVI-6974” (U, which is commercially available as an improved version of an aromatic sulfonium salt which also generates a free radical.
CC), "Cyracure UVI-6990" (U
CC), "Optomer SP150" (Asahi Denka Kogyo),
"Optomer SP170" (Asahi Denka Kogyo) and the like are also included.

As the iron aromatic compound salt of Bronsted acid, there is a trade name "CG24-061" (Ciba Gei).
gy).

The addition amount of these photopolymerization catalysts cannot be limited because it varies depending on the compounds present in the polymerizable composition and the composition ratio thereof, but the amount of each catalyst is about 0.0001 with respect to the polymerizable composition. It is preferably used in the range of 10 wt%. It is more preferable to use it in the range of 0.001 to 5 wt%.

Visible light polymerization can also be carried out using a photopolymerization catalyst and a thermal polymerization catalyst in combination. When the polymerization rate is slow and the desired polymerization rate cannot be obtained, it is easy to improve the polymerization rate by adding a photosensitizer such as camphorquinone.

At least one parabanic acid skeleton represented by the partial structural formula (1) and at least one in the same molecule.
By heat-polymerizing or radiation-polymerizing a polymerizable composition containing a compound having one or more reactive groups in a mold having various shapes, a molded product having a shape corresponding to the shape of the mold can be obtained. Further, it is possible to coat a surface of an object to be coated with a coating film by applying a coating composition containing the polymerizable composition onto the surface of the object to be coated and polymerizing the composition by irradiation with radiation or heating.

At least one or more parabanic acid skeleton represented by the partial structural formula (1) in the same molecule and at least one
Among the organic polymers obtained using a polymerizable composition containing a compound having at least one reactive group, the hydrophilicity is higher than known organic polymers, that is, an organic polymer having a small water contact angle is used. It became clear that there was something that could be obtained.

For example, as a compound having at least one parabanic acid skeleton represented by the partial structural formula (1) and a (meth) acryloyl group in the same molecule, a compound represented by the general formula (2) is contained. By using the polymerizable composition described above, it is possible to obtain an organic polymer having a very high hydrophilicity and a water contact angle of 30 ° or less.

As the organic polymer having a parabanic acid skeleton represented by the partial structural formula (1) in the molecule and having a water contact angle of 30 ° or less, a known organic polymer having hydrophilicity is used. It can be expected to be applied to existing hydrophilic materials.

By utilizing the property that the organic polymer of the present invention has high hydrophilicity and is easily wetted by water, water-insoluble components that adhere to the surface and cause stains, external air hydrophobic substances, automobile and factory exhaust Coke components such as gas, lipophilic pollutants such as sebum, proteins, etc. are lifted and desorbed by self-cleaning (rainfall), or water droplets are formed on the surface under high humidity conditions, The function of suppressing the occurrence of fogging and dew condensation is applied to the outer wall of a building, the inner wall / interior of a room, the exterior / interior of an automobile, and the function of suppressing the adhesion of Fujitsubo to the bottom of the ship, forming droplets and It can be expected that the surface of the cooling fin is provided with a function of suppressing a decrease in heat exchange efficiency due to adhesion of contaminants.

Examples of materials required to have such a function include stain-proof materials, anti-fog materials, anti-condensation materials and ship bottom coating materials, as well as eyeglass lenses, contact lenses,
Camera lenses, pip-up lenses, transparent films, optical materials such as organic glass, water-based coating materials or powder coating materials aiming at VOC elimination, and more specifically,
Contains water retention materials, waste water (liquid) absorption materials, gauze, first aid bandages, body fluid absorption materials such as diapers, external patches such as ships, and agents such as fragrances used for desert greening or promotion of general plant growth. Adhesive material, gel material for ice pack, road anti-freezing material, concrete additive material, (light) adhesive material, tape material, photo-curing dental material, display partition material, hair styling additive, shampoo conditioner・ Additives for surfactants such as body cleaners,
Surfactants, (photo-curing) inks, printing letterpress materials, inkjet additive materials, inkjet sheet / copy paper additives, (color) toner materials, magnetic disk / magnetic tape binders, photoresist materials, Examples include film resist materials, superconducting material matrix materials, blood storage containers, plastic molded material, and the like.

It is to be noted that a polymerizable composition containing at least one or more parabanic acid skeleton represented by the partial structural formula (1) and a compound having at least one or more reactive groups in the same molecule is preferable. Depending on the physical properties, characteristics, purpose and use, etc., a chain extender, a crosslink density improver, a curing agent, a photosensitizer, a retarder, a polymerization inhibitor, an ultraviolet absorber, a stabilizer, a dye, a paint, a pigment, Dye, ink, photosensitizer, luminescent agent, fragrance, germicide, binder, filler, polymer, filler, glass, metal, metal oxide, organic metal, salt, extender, release agent, surfactant, foaming agent It is also possible to add organic / inorganic compounds such as carbon dioxide gas, air, inert gas, water and solvent.

The transparency is impaired by adding a metal such as silver or lithium, an organic metal salt such as an alkali metal salt of acrylic acid or methacrylic acid, or an iodine and iodonium salt as the above-mentioned additive. In some cases, it is possible to significantly change the properties of the organic polymer of the present invention, such as imparting sterilization and antibacterial properties, or imparting a new function.

[0101]

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

Unless otherwise specified, a series of operations during polymer synthesis were performed at room temperature.

The water contact angle is measured by Kyowa Interface Science CA.
The measurement was performed at room temperature (25 ° C.) using the -V type, and the average value of the measurement results at arbitrary 5 points for the water droplets on the measurement target material was taken as the measurement result.

Example 1 Synthesis of N, N'-bis (2-hydroxy-ethyl) -parabanic acid "HEP" A reaction flask was charged with 24.0 g (0.210 mol) of parabanic acid and 500 ml of tetrahydrofuran (THF). 20 g of 60 wt% sodium hydride while cooling
(0.52 mol) was gradually added at 35 to 40 ° C., and then 5
Heated at 0 ° C. for 3 hours.

Then, while adjusting the internal temperature to 40 to 60 ° C., 65.0 g (0.52 mol) of 2-bromoethanol was added dropwise over 1 hour, and then the mixture was kept under heating under reflux (66 ° C.) for 6 hours. did.

After cooling to room temperature, the mixture was filtered, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 30.1 g of 98% pure N, N′-bis (2-hydroxy-ethyl) -parabanic acid “HEP”.
Obtained (pure exchange yield = 69%) was obtained.

The identification data of HEP are as follows. 13 C-NMR → see FIG. 1 Example 2 N, N′-bis (methacryloyl-oxy-ethyl)-
Synthesis of parabanic acid “MEP” N, N′-bis (2-hydroxy-ethyl) having a purity of 98%
-29.2 g (0.14 mol) of parabanic acid "HEP"
To the above, 29.4 g (0.29 mol) of triethylamine and 100 ml of acetonitrile were added, and while cooling, 30.4 g (0.29 mol) of methacrylic acid chloride was added in an amount of 10 to 25.
The mixture was added dropwise at 1 ° C over 1 hour and aged at 25 ° C for 4 hours.

The reaction solution was filtered, the filtrate was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain 97% pure N, N'-bis (methacryloyl-
8.9 g of (oxy-ethyl) -parabanic acid “MEP” was obtained (pure conversion yield = 18%).

The identification data of MEP are as follows. 13 C-NMR → See FIG.

Reference Example 1 Synthesis of N, N-bis (methacryloyloxy-ethyl) -methanesulfonamide "SAMD" A reaction flask was charged with 400 ml of methanol, and the internal temperature was adjusted to 50 to 50 in a warm water bath.
Methanesulfonyl chloride 31 while adjusting to 60 ℃
After 0.0 g (2.62 mol) was added dropwise over 1 hour, it was heated and kept under reflux (78 to 80 ° C.) for 3 hours.

Subsequently, under heating under reflux (78 to 80 ° C.),
N, N-bis (2-hydroxyethyl) amine 262.
8 g (2.50 mol) was added dropwise over 1 hour, and the mixture was heated for 1 hour while distilling off methanol (80-130 ° C).
And further heated at 130 ° C. for 1 hour.

After cooling to 40 ° C., 2, as a polymerization inhibitor,
6-di-t-butyl-4-methyl-phenol 0.22
g and 4-hydroxy-2,2,6,6-tetramethyl-
0.10 g of piperidine-oxyl was added, and 565.0 g (5.40 mol) of methacrylic acid chloride was added at an internal temperature of 40-
The mixture was added dropwise at 50 ° C. over 3 hours and kept at 45 ° C. for 3 hours.

After cooling to room temperature, dichloroethane 1500
ml, K ₂ CO ₃ and 10 wt% Na ₂ C under ice-water bath
O ₃ water was gradually added to neutralize (about 7 with pH test paper), the separated aqueous layer was discarded, and anhydrous magnesium sulfate (drying agent) was added to the organic layer to dry the organic layer.

Next, 0.40 g of 2,6-di-t-butyl-4-methyl-phenol and 4-hydroxy-2,2,6,6-tetramethyl were added to the organic layer separated from the desiccant through a filter. -0.40 g of piperidine-oxyl was added and concentrated under reduced pressure to obtain a concentrated liquid. The concentrated liquid was purified by silica gel column chromatography to obtain a fraction containing the desired product. 2,6-di-t-butyl-4-in the fraction containing the desired product
0.4 g of methyl-phenol and 4-hydroxy-2,
2,6,6-Tetramethyl-piperidine-oxyl 0.
04 g was added and concentrated under reduced pressure.

The concentrated residue was recrystallized from a mixed solution of toluene / hexane / chloroform, filtered and the obtained crystal was dried under reduced pressure to give 177.0 g of a 97% purity SADM.
Obtained (pure exchange yield = 22%). The melting point of this SADM by DSC was 85-93 ° C.

Reference Example 2 Synthesis of methacrylic acid 2- [acetyl- (2-acetylaminoethyl) -amino] -ethyl ester "DACAM" In a reaction flask, 104.2 g (1.0 mol of 2- (aminoethylamino) ethanol was added. ) Was charged, and 255.2 g (2.50 mol) of acetic anhydride was cooled to 1 at 25-35 ° C under cooling.
The solution was added dropwise over a period of time and heated at 65 to 70 ° C. for 4 hours.

To this reaction solution, 20 g of water was added dropwise to decompose excess acetic anhydride, and then 250 g of 40% sodium hydroxide aqueous solution was gradually added to neutralize.

The neutralized solution was concentrated under reduced pressure, and 500 ml of acetonitrile was added to the residual solution. The precipitated crystals were separated by filtration, and the filtrate was concentrated again under reduced pressure.

The concentrated residue was purified by silica gel column chromatography to obtain colorless and transparent N- {2-
149 g of [acetyl- (2-hydroxyethyl) amino] ethyl} acetamide “AHEAA” was obtained.

95 g of AHEAA obtained in a reaction flask
(0.50 mol) and 53.6 g of triethylamine (0.
53 mol) and 100 ml of acetonitrile were charged, and under ice cooling, 55.4 g (0.53 mol) of methacrylic acid chloride.
Was added dropwise at 5 to 15 ° C over 1 hour. After aging at 10 to 20 ° C. for 2 hours, the mixture was filtered, and the obtained filtrate was concentrated under reduced pressure. The residual liquid was purified by silica gel column chromatography to obtain 95.4 g of pale yellow high-viscosity liquid methacrylic acid 2- [acetyl- (2-acetylaminoethyl) -amino] -ethyl ester "DACAM" (purity 98. %
Pure conversion yield = 72%).

Example 3 Preparation of Polymerization Composition-1 5.0 g of N, N'-bis (methacryloyl-oxy-ethyl) -parabanic acid "MEP" having a purity of 97% and N-vinyl-N'-methyl-ethylene. To a mixed solution of 5.0 g of urea "MVI", 2,2-dimethyl-2-hydroxy-acetophenone 100 mg (1.0 wt%) as a photoinitiator,
100 mg (1.0 wt%) of t-butylperoxy-2-ethylhexanoate as a radical catalyst, and bis (5-n-butoxy-1,4-dimethyl-) as an internal release agent.
20 mg (0.2 wt%) 3-oxapentyl) phosphoric acid
Was added to prepare a polymerizable composition.

Example 4 Production of Polymer-1 9.0 g of the polymerizable composition of Example 3 was placed in a 100 ml transparent sample bottle, and after defoaming, the strength was 50 to 120 m.
Irradiate with UV light of W / cm2 to cure, 80 ~ 120
Heated at ° C. After cooling, the sample bottle was broken and the molded body was taken out.

The obtained molded product was transparent and had a water contact angle of 20.
It was °. The results are listed in Table 1.

Example 5 Preparation of polymerization composition-2 5.0 g of N, N'-bis (methacryloyl-oxy-ethyl) -parabanic acid "MEP" having a purity of 97%, DACA
M4.0 g, N, N-bis (glycidyl) -ethyleneurea 1.0 g, and 2,2-dimethyl-2-hydroxy-acetophenone 50 mg (0.5
wt%), 4,4'-bis {di (3-hydroxyethoxy) phenylsulfonio} phenylsulfide-bis-hexafluoroantimonate (Asahi Denka Kogyo, trade name Optomer SP-170) 100 as a photocation generator.
mg (1.0 wt%), t-butylperoxy-3,5,5-trimethylhexanoate 100 mg (1.0 wt%) as a radical catalyst, and bis (5-n-butoxy-1) as an internal mold release agent. 20 mg (0.2 wt%) of 4,4-dimethyl-3-oxapentyl) phosphoric acid was added to prepare a polymerizable composition.

Example 6 Production of Polymer-2 9.0 g of the polymerizable composition of Example 5 was placed in a 100 ml transparent sample bottle, and after defoaming, the strength was 50 to 120 m.
Irradiate with UV light of W / cm2 to cure, 80 ~ 120
Heated at ° C. After cooling, the sample bottle was broken and the molded body was taken out.

The obtained molded product was transparent and had a water contact angle of 29.
It was °. The results are listed in Table 1.

Example 7 Preparation of Polymer-3 1.0 g of N, N'-bis (methacryloyl-oxy-ethyl) -parabanic acid "MEP" having a purity of 97% and SADM.
Charge 9.0 g into a 100 ml transparent sample bottle and
After melting at 0 ° C., it was heated at 100 to 120 ° C. for 24 hours for curing. After cooling, the sample bottle was broken and the molded body was taken out.

The obtained molded product was transparent and had a water contact angle of 13
It was °. The results are listed in Table 1.

Example 8 Formation of Coating Film To 10.0 g of the polymerizable composition prepared in the same manner as in Example 5,
Disperse dye MLP Red-2 (Mitsui BASF dye) 5
0 mg (0.5 wt%) was added, and the paint was prepared by filtering.

Next, this paint is applied to wood to obtain a strength of 50.
The coating was cured by irradiating it with ultraviolet rays of 120 mW / cm @ 2 and annealed at 60.degree. The obtained coating film firmly adhered to wood and was red and transparent.

Comparative Examples 1 to 4 The contact angle between a commercially available slide glass and a general-purpose resin was measured.
The results are shown in Table-2.

Comparative Examples 5 to 7 The monomers shown in Table 1 were mixed with 30 mg of 2,2-dimethyl-2-hydroxy-acetophenone (0.
3 wt%), 30 mg (0.3 wt) of t-butylperoxy-2-ethylhexanoate as a radical catalyst
%), Bis (5-n-butoxy-1, as an internal release agent,
4-Dimethyl-3-oxapentyl) phosphoric acid 20 mg
(0.2 wt%) was added and polymerization was carried out under the same conditions as in Example 6. The physical properties of the obtained resin are shown in Table 2.

Comparative Example 8 Acrylic acid was tried to be resinified under the same conditions as in Comparative Examples 5 to 7, but it was polymerized, but the obtained resin had numerous cracks and cracks and foamed. The contact angle could not be measured.

[0134]

[Table 1]

[0135]

[Table 2]

[0136]

According to the present invention, it is possible to provide a highly hydrophilic organic polymer having a parabanic acid skeleton and a novel compound having a parabanic acid skeleton which is a monomer thereof and an acryloyl group or a methacryloyl group. Further, by utilizing the high hydrophilicity of the present organic polymer, it is possible to provide a novel antifouling material, antifogging material, coating material, dew condensation preventing material, optical material and the like.

[Brief description of drawings]

FIG. 1 shows the N, N′-bis (amino-containing compound obtained in Example 1.
It is a 13 C-NMR chart of ethyl) -parabanic acid “HEP”.

2] N, N'-bis (methacryloyl-oxy-ethyl) -parabanic acid "MEP" 13 obtained in Example 2
It is a C-NMR chart.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 1/10 C08L 33:00 // C08L 33:00 G02B 1/10 Z F term (reference) 2K009 CC32 EE02 EE05 4F071 AA32 AA33 AA76 AF04Y AH04 AH14 4J038 CG141 CH191 NA06 4J100 AB02Q AB16Q AC08P AD02Q AD03Q AF11P AJ02 JA03 JA38 JA25 JA03 JA33 JA03QAJAQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQQ JA51

Claims (11)

[Claims] 1. A partial structural formula (1): An organic polymer having a parabanic acid skeleton represented by the formula and having a water contact angle of 30 ° or less. 2. A molded product comprising the organic polymer according to claim 1. 3. A film comprising the organic polymer according to claim 1. 4. At least one or more partial structural formulas (1) in the same molecule: A compound having a parabanic acid skeleton represented by and at least one or more acryloyl group or methacryloyl group. 5. The general formula (2) [Chemical 3] (R₁~ R₆Are each independently a hydrogen atom or
Represents a chill group. However, R ₁~ R_FourIs a hydrogen atom or
Part or all of the chill group is substituted with a hydroxy group
Good. X₁, X_TwoAre each independently O, S, N
H or NCH _ThreeRepresents a and b are independent of each other
Represents an integer of 0 or 1. c and d are independent
And represents an integer of 2 to 6. e and f are independent
And represents an integer of 0 to 3. ) It represents with Claim 4 represented by
Compound. 6. A compound represented by the general formula (3): (R ₁ to R ₄ each independently represent a hydrogen atom or a methyl group. However, some or all of the hydrogen atom or a methyl group, may be substituted with a hydroxy group .Y _1,
Y ₂ is each independently O, S, NH, or NC
Represents H ₃ . c and d each independently represent an integer of 2 to 6. g and h each independently represent an integer of 1 to 3. ) The compound represented by. 7. A polymerizable composition containing the compound according to claim 4 or claim 5. 8. An organic polymer obtained by polymerizing the compound according to claim 4 or 5, or the polymerizable composition according to claim 7. 9. The organic polymer according to claim 8, which has a water contact angle of 30 ° or less. 10. A molded product comprising the organic polymer according to claim 8 or 9. 11. A film comprising the organic polymer according to claim 8 or 9.