JP2000336122A - CURABLE COMPOSITION CONTAINING (CO)POLYMER OF N-(METH) ACRYLOYL-beta-HYDROXYASPARTIC ACID AND ITS CURED PRODUCT - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition containing a (co)polymer of an N-(meth)acryloyl-β-hydroxyaspartic acid free from organic solvent and useful for coating use, etc., by using a (co)polymer composed mainly of a specific aspartic acid and a specific water-soluble compound as the raw materials. SOLUTION: The objective composition contains (A) a polymer of an N-(meth) acryloyl-β-hydroxy-aspartic acid or a copolymer of the aspartic acid copolymerized with a copolymerizable monomer or their salts obtained by the neutralization of the carboxyl group and (B) a water-soluble compound having >=2 functional groups reactive with carboxyl group. Preferably, the above copolymer is a copolymer produced by the copolymerization of N-(meth) acryloyl-β-hydroxy-aspartic acid and a vinyl monomer copolymerizable therewith or its salt and having a molecular weight of 1,000-500,000 and the component B is a polyhydric alcohol, a polyvalent epoxy compound, a polyvalent amine or a polyvalent iso(thio)cyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cured product-forming composition. More specifically, a polymer of N- (meth) acryloyl-hydroxy-aspartic acid or a copolymer of a monomer copolymerizable therewith or a salt thereof and two or more functional groups capable of reacting with a carboxyl group are used. The present invention relates to a cured product-forming composition containing a water-soluble compound.

[0002]

2. Description of the Related Art Conventionally, in the field of coating and molding using a polymer, an organic solvent and a monomer dissolved therein are often used, and from the viewpoint of the health of workers and environmental pollution. Are also very problematic, and there is a strong demand for a more secure method.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a cured product-forming composition which is useful for painting and the like and does not contain an organic solvent.

[0004]

Means for Solving the Problems The present inventors have proposed poly-N-
After forming an aqueous solution containing a (co) polymer mainly composed of (meth) acryloyl-β-hydroxy-aspartic acid and a water-soluble compound having two or more functional groups capable of reacting with a carboxyl group, the film is dried by heating. Then, it was found that a crosslinked structure was formed by an ester bond or the like, and a water-insoluble cured product was obtained, thereby completing the invention. That is, the present invention relates to (1) a polymer of N- (meth) acryloyl-β-hydroxy-aspartic acid, a copolymer obtained by copolymerizing the polymer with a monomer copolymerizable therewith, or a carboxyl group of these is neutralized. A cured product-forming composition comprising a salt and a water-soluble compound having two or more functional groups capable of reacting with a carboxyl group, (2) the copolymer is N- (meth) acryloyl-β-hydroxy-asparagine A cured product-forming composition according to the above (1), which is a copolymer or a salt thereof obtained by copolymerizing an acid and a vinyl monomer copolymerizable therewith, (3) N- (meth) acryloyl-β The cured product-forming composition according to the above (1) or (2), wherein the polymer or copolymer of -hydroxy-aspartic acid or a salt thereof has a molecular weight of 1,000 to 500,000, (4) The cured product-forming composition according to any one of the above (1) to (3), wherein the water-soluble compound is a polyhydric alcohol, a polyvalent epoxy, a polyvalent amine or a polyvalent iso (thio) cyanate, (5) A) a paint, a coating material, an air barrier film or a molded product containing the cured product-forming composition according to any one of the above (1) to (4); A cured product of the cured product-forming composition according to any one of the above.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
N- (meth) acryloyl used as a raw material in the present invention
β-hydroxy-aspartic acid is disclosed in
007 can be obtained. Specifically, an active esterification method, a mixed acid anhydride method, an azide method, an acid chloride method, a symmetric acid anhydride method, a DCC method, a DCC method are used from β-hydroxy-aspartic acid and (meth) acryloyl acid.
It can be obtained by an amide bond synthesis method such as a C-active method and a carbonylimidazole method.

Of these methods, the acid chloride method comprising reacting β-hydroxy-aspartic acid with (meth) acryloyl chloride is preferred. In this specification, the term “(meth) acryloyl” refers to methacryloyl or acryloyl. The method of homopolymerizing N- (meth) acryloyl-β-hydroxy-aspartic acid or copolymerizing it with a monomer copolymerizable therewith is not particularly limited.
What is necessary is just to follow the method of the gazette No. 7. Specifically, N-
(Meth) acryloyl-β-hydroxy-aspartic acid (or a mixture thereof with a monomer copolymerizable therewith) can be used, for example, azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), acetyl peroxide, persulfate A method of polymerizing in the presence of a polymerization initiator such as a conventionally known radical polymerization agent such as a salt may be used. The polymerization reaction may be performed in a solid phase (bulk polymerization).
Chlorobenzene, dimethylformamide, methanol,
Polymerization can also be performed in a liquid phase using water or the like.

In the polymerization reaction, the monomer copolymerizable with N- (meth) acryloyl-β-hydroxy-aspartic acid includes a compound having a functional group capable of polymerizing with a (meth) acryloyl group, for example, a vinyl group. Examples of the compound having a vinyl group include vinyl monomers such as acrylic acid, methacrylic acid, vinyl acetate, methyl methacrylate, and styrene. In the present invention, N
When a copolymer of (meth) acryloyl-β-hydroxy-aspartic acid and the above monomer is used, N-
With one molecule of (meth) acryloyl-β-hydroxy-aspartic acid monomer as one unit, a copolymer is prepared so that the amount of this monomer unit is usually about 90 to 10% by weight. Hereinafter, one unit refers to a unit corresponding to one molecule of a monomer in the polymer.

[0008] The (co) polymer thus obtained is an N-
The (meth) acryloyl-β-hydroxy-aspartic acid unit has two carboxyl groups. still,
The N- (meth) acryloyl-β-hydroxy-aspartic acid unit in the (co) polymer is an L-threo compound,
It may have any structure of -threo body, L-erythro body, and D-erythro body. The (co) polymer may be used as it is or as a salt (partially) neutralized by adding an alkali such as sodium hydroxide or potassium hydroxide. When a (partially) neutralized salt is used, coloring of a cured product due to heat may be suppressed in some cases. When a (partially) neutralized salt is used, for example, the pH of a 10% by weight aqueous solution of the (co) polymer can be adjusted to 2 to 10, preferably 2 to 8, before use. The number average molecular weight of the (co) polymer is not particularly limited, but is usually 1,000 to 500,000, preferably 2,000 to 250,000. Molecular weight of 1,000
If it is smaller than 0, the physical properties of the cured product are reduced, and
If it exceeds 0, the viscosity of the aqueous solution increases, which may not be preferable.

The water-soluble compound used in the present invention is a compound which has a functional group capable of reacting with two or more carboxyl groups in the molecule and is soluble or suspended in water. Examples of such a functional group include a hydroxyl group, a glycidyl group, an amino group, and an iso (thio) cyanate group. Examples of the compound having such a functional group include a polyhydric alcohol, a polyepoxy, a polyamine, and a polyiso (thio) cyanate.

[0010] In the above, the polyhydric alcohol means a low molecular weight compound such as ethylene glycol, diethylene glycol (DEG), glycerin, sucrose and the like.
For example, it contains an alcohol-based polymer such as polyvinyl alcohol (PVA) and water-soluble starches. PVA has a saponification degree of usually 50% or more, preferably 7%.
0 to 99.5%, and the average degree of polymerization is usually 300 to 1,
Those having a value of 500 are preferably used.

[0011] Polyhydric epoxy refers to two or more epoxy groups and one or more water-solubility-imparting groups in the molecule (a functional group having a property of imparting water-solubility (or hydrophilicity) to polyepoxy). For example, it refers to a compound having a hydroxyl group, and specific examples include glycerol polyglycidyl ether and polyglycerol polyglycidyl ether.

The polyamine is a linear olefin polymer having a primary amino group in a side chain, and is a cationic polymer which is positively charged in water. As such polyamines, those having a molecular weight of about 1 to 100,000 are commercially available, and those having a molecular weight of about 1 to 50,000, for example, polyallylamine (trade name, Nitto Boseki Co., Ltd.) and the like are preferable.

The polyvalent iso (thio) cyanate is
A compound in which a functional group capable of reacting with a carboxyl group is chemically blocked so as not to react with water at room temperature, or a compound whose reactivity has been adjusted, and isocyanate or isothiocyanate usually suspended or dissolved in water. Dispersible polyisocyanate, Takenate (trade name, Takeda Pharmaceutical Co., Ltd.) and aqueous isocyanate-based crosslinking agent CR-60N
(Trade name, Dainippon Ink and Chemicals, Inc.) are commercially available.

The cured product-forming composition of the present invention can be obtained usually as an aqueous solution or a water-based suspension of the (co) polymer of N- (meth) acryloyl-β-hydroxy-aspartic acid and the water-soluble compound. it can. N- (meth) acryloyl-β-hydroxy- in the cured product-forming composition of the present invention
The concentration of the (co) polymer of aspartic acid is usually from 1 to 60.
% By weight, preferably 5 to 40% by weight.

In the cured product-forming composition of the present invention, when the water-soluble compound is a low molecular weight compound, the carboxyl group in the (co) polymer of poly (N- (meth) acryloyl-β-hydroxy-aspartic acid) On the other hand, the water-soluble compound is blended so that the functional group capable of reacting therewith is usually 0.1 to 2.0 equivalents.

When the water-soluble compound is a high molecular compound, it can be mixed with the poly (N- (meth) acryloyl-β-hydroxy-aspartic acid) (co) polymer at any ratio. However, it is preferable to mix such that one of the carboxyl group in the (co) polymer and the carboxyl group-reactive functional group in the water-soluble compound is 0.01 to 1 mol times the other.

The cured product-forming composition of the present invention can be used as a paint, a coating material, an air barrier film or a molded product formed into a desired shape. When used as a paint, a commonly used water-soluble or water-dispersible dye, pigment, or the like can be mixed with the cured product-forming composition of the present invention and used. When the cured product-forming composition of the present invention is used as a coating material or for obtaining a molded product, a method for forming a film or a molded product is not particularly limited.
For example, a solution casting method in which the cured product-forming composition of the present invention is cast on a support such as a glass plate, an aluminum plate, or a wooden plate and dried to form a film or a plate-like product, or a high-concentration curing process. There is an extraction method in which the material-forming composition is cast into a film or plate from the slit while applying discharge pressure by an extruder, and the water-containing film is dried on a rotating drum or belt. In addition, the material of the object to be coated or the object to be coated is the glass listed above,
There is no particular limitation other than aluminum, wood, and the like. As the air barrier film, a film prepared in the same manner as above may be used as it is, or another film such as a polyethylene or vinyl chloride film may be used in combination. Further, in order to form a molded product, after processing into a plate shape, heat treatment may be performed until curing shrinkage disappears, and the molded product may be completely cured by placing it in a mold.

The cured product-forming composition of the present invention can be easily converted into a water-insoluble cured product by forming into a film or a molded product as described above and then heating and drying. This cured product does not dissolve in most organic solvents. This is because the reaction between the carboxyl group and the carboxyl group-reactive functional group, such as esterification, amidation, or urethane reaction, was accelerated by heating, and a crosslinked product was formed. As described above, the cured product cured by the heat treatment has a crosslinked structure of 3
It is dimensional and has excellent heat resistance. This crosslinked structure can be confirmed from an infrared absorption spectrum. The heating conditions are not particularly limited, but generally, if the heating temperature is low, the heating time is long, and if the heating temperature is high,
The heating time may be short. Heating temperature is usually 100-200
° C, preferably from 120 ° C to 180 ° C. The heating time is usually 0.1 to 5 hours, preferably 0.2 to 3 hours.

[0019]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 Poly N- (meth) acryloyl-β-hydroxy-aspartic acid (poly N-methacryloyl-DL-threo-
β-hydroxy-aspartic acid, average molecular weight: 40,
To a 5 g (4 units mmol) of an 18% aqueous solution of 000 to 50,000 (hereinafter PMAH) was added 0.44 g (4 mmol) of diethylene glycol (hereinafter referred to as DEG) as a polyhydric alcohol to obtain a cured product-forming composition of the present invention. Prepared. About 1 ml of this composition (aqueous solution) was applied to a glass plate, an aluminum plate, and a wooden plate, respectively. After air-drying the applied material overnight,
As a result of heating and curing at 150 ° C. for 2 hours, a transparent film insoluble in water and slightly colored was obtained on each plate.

Example 2 As a polyhydric alcohol, polyvinyl alcohol (PV
A) The same operation as in Example 1 was performed except that 0.36 g (8.2 units mmol) was used, and a steel plate, a glass plate, an aluminum plate, and a wooden plate were used as objects to be coated. The PVA used had a degree of polymerization of about 400 to 600 and a degree of saponification of 96.
% Or more. As a result, a dark brown film insoluble in water was formed on each plate.

Example 3 As a polyhydric alcohol, polyvinyl alcohol (PV
A, the same operation as in Example 1 was carried out except that 5.74 g (120 units mmol) of a Teflon plate was used as an object to be coated. When the film peeled from the Teflon plate was placed in a steel mold at 150 ° C. and cooled down, a predetermined molded product was obtained. When the thermal decomposition temperature of one part of this film was examined, the thermal decomposition onset temperature was 284 ° C. In addition, JIS K
The oxygen permeability measured according to 7126 is 1.0 cm ³
/ ^M was 2 · 24h · atm or less.

Example 4 PMAH in PMAH aqueous solution used in Example 1
Was carried out in the same manner as in Example 2, except that 1.2 ml of a 2N aqueous solution of sodium hydroxide was added so that 30% was partially neutralized, and a glass plate and a wooden plate were used as objects to be coated. As a result, a slightly colored water-insoluble coating was formed on each plate.

Example 5 Denacol EX-313 (trade name, water-soluble epoxy manufactured by Nagase Kasei Co., Ltd.), 20 units mmol, was used as a polyepoxy, and glass plates, steel plates, aluminum plates, and polyester films were used as objects to be coated. The same operation as in Example 1 was performed except that was used. As a result, an ocher coating is formed on each plate or film,
Good adhesion was shown. In addition, adhesion is JISK-54.
8.5.3 of X00 was evaluated by the X-cut tape method.

Example 6 As a water-soluble compound, 4 units of PAA-L (trade name, water-soluble polyallylamine manufactured by Nitto Boseki Co., Ltd.) and 40 units of PVA used in Example 2 were mixed and used. The same operation as in Example 1 was performed except that a glass plate was used as the material. As a result, a faint white film was formed on the plate, showing good adhesion.

[0026]

The cured product-forming composition of the present invention is environmentally preferable because it forms a film showing good adhesion to all materials and does not use an organic solvent. The cured product-forming composition of the present invention is not only a coating material,
It is extremely useful for paints and heat-resistant molded products.

Continued on the front page F term (reference) 4J038 CC031 CF021 CG031 CG141 CH031 CH121 CH151 CH201 DB002 DG242 DG262 GA03 GA06 GA09 JA20 JA21 JA69 JB01 KA03 MA08 NA08 NA14 NA27 PC02 PC03 PC06 4J100 AB02Q AG04Q AJ02Q AL03PAM01P01

Claims (6)

[Claims] 1. A polymer of N- (meth) acryloyl-β-hydroxy-aspartic acid, a copolymer obtained by copolymerizing the polymer with a monomer copolymerizable with N- (meth) acryloyl-β-hydroxy-aspartic acid, a salt having a carboxyl group neutralized and a carboxyl group A cured product-forming composition containing a water-soluble compound having two or more functional groups capable of reacting with a group. 2. The method according to claim 1, wherein the copolymer is N- (meth) acryloyl-β.
The cured product-forming composition according to claim 1, which is a copolymer obtained by copolymerization of -hydroxy-aspartic acid and a vinyl monomer copolymerizable therewith, or a salt thereof. 3. The curing method according to claim 1, wherein the polymer or copolymer of N- (meth) acryloyl-β-hydroxy-aspartic acid or a salt thereof has a molecular weight of 1,000 to 500,000. Product forming composition. 4. The cured product-forming composition according to claim 1, wherein the water-soluble compound is a polyhydric alcohol, a polyhydric epoxy, a polyvalent amine or a polyvalent iso (thio) cyanate. 5. A coating material, a coating material, and a coating composition containing the composition for forming a cured product according to any one of claims 1 to 4.
Air barrier film or molded product. 6. A cured product of the cured product-forming composition according to any one of claims 1 to 4.