JP2003040923A - Water-dispersible and ultraviolet-curable polymer, and use and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-dispersible and ultraviolet-curable polymer, and to provide a method for producing this polymer in water only, a hydrophilic solvent only or a mixed solvent thereof. SOLUTION: (a) A part of a carboxy group of a polymer composed of a repeating unit having the carboxy group, is neutralized with a base or (b) a monomer having the carboxy group and a monomer having the carboxy group neutralized with an alkali are copolymerized and thereafter a compound having an unsaturated carbon-carbon bond is added to a part of free carboxy groups in water only, the hydrophilic solvent only or the mixed solvent thereof.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a water-dispersible UV-curable polymer compound, its use and a method for producing the same.

[0002]

2. Description of the Related Art Recently, it is possible to polymerize a polymer compound having a carboxyl group with a group which can be added to the carboxyl group (for example, an isocyanato group, an epoxy group, an aziridinyl group, a hydroxyl group, an acid anhydride group) by radiation or heat. A reactive polymer obtained by adding a compound having a group (a group having a carbon-carbon unsaturated bond, such as an acryloyl group or a methacryloyl group) has been developed and put on the market.
The reactive polymer has 1) a small volume contraction rate due to the characteristics of its skeleton, and 2) a number average molecular weight of 5,000 to 1.00.
Since it is difficult to penetrate with 50,000 polymers, it can be applied to porous substrates. 3) Adhesion to substrates is better than oligomers and monomers. 4) Various polymer skeletons. Can introduce various functional groups, elasticity, antistatic property,
Various functions such as anti-fog property and hard coat property can be easily imparted. 5) It has excellent curability. 6) When the monomer or oligomer is overcoated on the surface of the reactive polymer, it will not be cured. It has various advantages such as its excellent adhesion to the topcoat. By utilizing these characteristics, it can be widely applied to electronic materials, woodworking, paper, and the like.

However, when the above-mentioned addition reaction is carried out in a water-containing solvent, the compound having a group capable of being added to the above-mentioned carboxyl group and a group capable of being polymerized by radiation and heat becomes unstable, and furthermore, the reaction system is resinified and added. The reaction is inhibited.
Therefore, a water-containing solvent was not suitable as a solvent for producing a reactive polymer. Usually, the addition reaction is carried out in a solvent other than the water-containing solvent, and there is a concern that it may affect the environment.
Therefore, it is desired to develop a method capable of producing a reactive polymer in water alone, a water-soluble solvent alone or a mixed solvent thereof. Up to now, there have been UV-curable oligomers having a group (for example, an acryloyl group) that reacts upon irradiation with UV light and capable of being dispersed in water, but no polymer compound. Therefore, development of a water-dispersible UV-curable polymer compound is desired.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a water-dispersible UV-curable polymer compound and its use. Further, another object of the present invention relates to a method for producing the water-dispersible UV-curable polymer compound in water alone, a water-soluble solvent alone or a mixed solvent thereof.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor adds a carbon-carbon unsaturated bond-containing compound as shown in the following (a) and (b). As a raw material, by using a polymer compound containing a repeating unit having a carboxyl group neutralized with a base in addition to a repeating unit having a carboxyl group, water alone, a water-soluble solvent alone or a carbon mixture in a mixed solvent thereof. It was found that the compound containing a carbon unsaturated bond is stabilized, and the addition reaction proceeds, and that the addition reaction, which could be performed only in an organic solvent, can be performed in water alone, a water-soluble solvent alone or a mixed solvent thereof. The present invention has been completed.

This is because, by using a polymer compound having a repeating unit having a neutralized carboxyl group, the polymer compound acts as a surfactant and a compound containing a carbon-carbon unsaturated bond, particularly an epoxy ring. The compound containing a carbon-carbon unsaturated bond is emulsion-stabilized in water alone, a water-soluble solvent alone or a mixed solvent thereof, and the neutralized carboxyl group in the polymer compound acts as a catalyst for the addition reaction to be added. It is considered that the reaction proceeds. (A) After neutralizing a part of the carboxyl groups of a polymer compound containing a repeating unit having a carboxyl group with a base, one of the free carboxyl groups in water alone, a water-soluble solvent alone or a mixed solvent thereof is used. A carbon-carbon unsaturated bond-containing compound is added to the part. (B) after copolymerizing a monomer having a carboxyl group and a monomer having a carboxyl group neutralized with a base,
The carbon-carbon unsaturated bond-containing compound is added to a part of the free carboxyl group in water alone, the water-soluble solvent alone or a mixed solvent thereof.

That is, the present invention is as follows. (1) In a polymer compound containing a repeating unit having a carboxyl group, a part of the carboxyl group is neutralized with a base, and a part of the carboxyl group is a carbon-carbon unsaturated bond-containing functional group. A water-dispersible UV-curable polymer compound, which is added with a group. (2) The polymer compound according to (1) above, wherein 10 to 95% of the carboxyl groups are neutralized. (3) The polymer compound according to (1) above, wherein the base is an amine compound or an alkali metal compound. (4) The polymer compound according to (1) above, wherein the carbon-carbon unsaturated bond is derived from an acryloyl group or a methacryloyl group. (5) a carboxyl group added with a carbon-carbon unsaturated bond-containing functional group has the formula

[0008]

[Chemical 2]

The polymer compound according to (1) above, which is a group represented by the formula (wherein R represents a hydrogen atom or a methyl group). (6) Weight average molecular weight of 5,000 to 1,000,000
The polymer compound of (1) above, which is 0. (7) The polymer compound according to any one of (1) to (6) above, which is for a water-dispersible coating material. (8) (a) after neutralizing a part of the carboxyl groups of a polymer compound containing a repeating unit having a carboxyl group with a base, or (b) a carboxyl neutralized with a monomer having a carboxyl group and a base. After copolymerizing a monomer having a group, a carbon-carbon unsaturated bond-containing compound is added to a part of the free carboxyl group in water alone, a water-soluble solvent alone or a mixed solvent thereof, an aqueous dispersion. For producing a high-polymerizable ultraviolet-curable polymer compound. (9) After neutralizing a part of the carboxyl groups of the polymer compound containing a repeating unit having a carboxyl group with a base, one of the free carboxyl groups in water alone, a water-soluble solvent alone or a mixed solvent thereof is used. The method according to (8) above, wherein a carbon-carbon unsaturated bond-containing compound is added to the part. (10) Neutralize 10 to 95% of carboxyl groups, above
The manufacturing method of (9). (11) The production method of (9) above, wherein the base is an amine compound or an alkali metal compound. (12) The carbon-carbon unsaturated bond-containing compound is glycidyl methacrylate or glycidyl acrylate,
The method according to (9) above. (13) After copolymerizing a monomer having a carboxyl group and a monomer having a carboxyl group neutralized with a base,
The method according to (8) above, wherein the carbon-carbon unsaturated bond-containing compound is added to a part of the free carboxyl group in water alone, a water-soluble solvent alone or a mixed solvent thereof. (14) The carboxyl group in the copolymer obtained after the copolymerization: 90:10 to 5:95 as the neutralized carboxyl group.
The method according to (13) above. (15) The production method of (13) above, wherein the base is an amine compound or an alkali metal compound. (16) the carbon-carbon unsaturated bond-containing compound is glycidyl methacrylate or glycidyl acrylate,
The manufacturing method according to (13) above.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
First, the definition of terms will be described. (Meta) in the present invention
The acryloyl group includes an acryloyl group and a methacryloyl group.

The water-soluble solvent in the present invention means a solvent having a solubility in water of preferably about 7% by volume (30 ° C.) or more, and specifically, an alcohol solvent (eg, methanol, ethanol, isopropyl). Alcohol, methyl cellosolve, ethyl cellosolve, etc.) and the like, and from the viewpoint of having a low boiling point, methanol and isopropyl alcohol are preferable, and isopropyl alcohol is particularly preferable.

As the base in the present invention, for example, an amine compound (the amine compound in the present invention is
It also includes quaternary ammonium as well as secondary and tertiary amines; for example NH ₄ OH, triethylamine,
Diethanolamine, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, allylamine, diallylamine, triallylamine, etc., alkali metal compounds (eg KOH, NaOH)
Etc.) and the like, and NH ₄ OH and KOH are preferable. From the viewpoint that the water resistance and UV curing property of the coating film are dramatically improved, it is possible to improve the water resistance and UV curing property of dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, allylamine, diallylamine, triallylamine and the like. An amine compound having a saturated bond is preferable, and dimethylaminoethyl methacrylate is particularly preferable.

In the present invention, (a) after neutralizing a part of the carboxyl group of the polymer compound containing a repeating unit having a carboxyl group with a base (hereinafter referred to as neutralization step (a)), or (B) After copolymerization of a monomer having a carboxyl group and a monomer having a carboxyl group neutralized with a base (hereinafter referred to as a copolymerization step (b)), in water alone, a water-soluble solvent alone or a mixed solvent thereof. A water-dispersible UV-curable polymer compound is produced by adding a carbon-carbon unsaturated bond-containing compound to a free carboxyl group. The polymer compound obtained in the neutralization step (a) and the polymer compound obtained in the copolymerization step (b) are both characterized by having a free carboxyl group and a neutralized carboxyl group, It is an essential requirement of the present invention that these polymer compounds have such characteristics.

First, the neutralization step (a) will be described.
The “polymer compound containing a repeating unit having a carboxyl group (hereinafter, referred to as polymer compound A)” in the neutralization step (a) refers to a monomer having a carboxyl group and a monomer that produces a carboxyl group by polymerization. It is a polymer compound obtained by polymerizing one kind or two or more kinds. Examples of such a monomer include (meth)
Acrylic acid, alkyl (meth) acrylate (wherein the alkyl part is a linear or branched alkyl having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms; for example, methyl,
Ethyl, n-propyl, isopropyl, n-butyl, 2
-Ethylhexyl, lauryl, stearyl, cyclohexyl, etc.), crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, β- (meth) acryloyl Examples thereof include oxyhydrogen succinic acid, β- (meth) acryloyloxyhydrogenphthalic acid, and acrylic acid dimer, with acrylic acid, ethyl acrylate, and 2-ethylhexyl acrylate being preferred.

In addition to the above monomers, the following monomers are blended for the purpose of imparting a functional group to the polymer compound A:
This is important for producing the water-dispersible UV-curable polymer compound of the present invention. For example, acid anhydride group, optionally substituted amino group, alkyl-rolled amino group, hydroxyl group, epoxy group (including alicyclic epoxy group)
Examples thereof include monomers having a functional group such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, (meth) acrylamide, N-methylmethacrylamide, and methylolated (meth ) Acrylamide, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, β-hydroxy (meth) acrylate, polyethylene glycol monoacrylate, glycidyl ( Examples thereof include (meth) acrylate, alicyclic glycidyl monoacrylate, and acrylonitrile.

As the polymer compound A, (meth) acrylic acid, alkyl (meth) acrylate, β- (meth) acryloyloxyhydrogensuccinic acid, β- (meth)
Acryloyloxyhydrogenphthalic acid, acrylic acid dimer, etc. are polymerized with one kind or two or more kinds, or with them, crotonic acid, o-vinylbenzoic acid, m
-Vinylbenzoic acid, p-vinylbenzoic acid, maleic acid,
Fumaric acid, itaconic acid, citraconic acid, β- (meth) acryloyloxyhydrogen succinic acid, β- (meth)
An acrylic polymer compound (water-soluble or aqueous polymer compound) obtained by polymerizing acryloyloxyhydrogenphthalic acid, acrylic acid dimer or the like is preferable. Specifically, a copolymer of acrylic acid and ethyl acrylate,
Examples thereof include a copolymer of acrylic acid and 2-ethylhexyl acrylate.

The polymer compound A can be produced by a conventional method, for example, emulsion polymerization, solution polymerization (including the case of using water as a solvent) and the like. As a solvent for solution polymerization, in addition to water and a water-soluble solvent, for example, an ester solvent (eg, ethyl acetate), a ketone solvent (eg, acetone, methyl ethyl ketone, etc.), an aromatic solvent (eg, benzene, toluene, etc.) ) And the like, and a solvent having a low boiling point or a water-soluble solvent is preferable, and acetone and methyl ethyl ketone are particularly preferable. In the present invention,
Since the addition step is carried out in water alone, in the water-soluble solvent alone or in a mixed solvent thereof, water, a water-soluble solvent and a mixed solvent thereof are used as a solvent for the solution polymerization. Is not necessary and the cost can be reduced, which is preferable. In addition, in solution polymerization and emulsion polymerization using a mixed solvent of water and a water-soluble solvent, it is preferable to mainly use water as a solvent.

The polymer compound A can be obtained, for example, by polymerizing one or more of the above monomers in the presence of a polymerization initiator in a solvent. The solvent is not particularly limited, but in consideration of the subsequent addition reaction, the solvent used in the addition reaction is preferable because the desolvation step becomes unnecessary. The amount of solvent used is not particularly limited as long as stirring can be performed. The polymerization temperature is
It is usually 30 to 120 ° C, preferably 60 to 90 ° C.

The polymerization initiator in the present invention is not particularly limited as long as it is usually used, and examples thereof include persulfate, azobis type, peroxide type and the like, and the half-life and reactivity are practically used. Considering the above, ammonium persulfate is preferable among the persulfates, and 4,4′-azobis-4-cyanovaleric acid and 2,2′-azobis (2-amidinopropane) salt are preferable among the azobis compounds. When water is used as a solvent, potassium persulfate or ammonium persulfate, which are water-soluble initiators, can be used, and when an organic solvent is used, azobisisobutyronitrile or peroxide is used. Examples thereof include benzoyl.

When emulsion polymerization is carried out, an emulsifier is generally used, but when the obtained polymer compound is processed into a product or a coating film is formed on a substrate, the product is generally used. Since a problem such as bleeding of the emulsifier on the surface of the membrane or the membrane occurs, it is preferable to decide what kind of emulsifier in consideration of what purpose it is finally used for. For example, when used as an ultraviolet curable coating material, it is preferable to use a reactive emulsifier.

As the emulsifier, for example, the following formulas (1) to
(4) and (5) (provided that M ² represents —SO ₃ Na)
An anionic surfactant such as the following formula (5) (provided that M
² represents a hydrogen atom) to (7) and the like nonionic surfactants, sulfate ester salts of the following formula (5) and cationic surfactants such as formula (8).

[0022]

[Chemical 3]

(In the formula, R ¹ is an alkyl group having 2 to 18 carbon atoms, R ² is an alkyl group having 2 to 18 carbon atoms, R ³ and R ⁴ are the same or different, and Number 2
18 represents an alkyl group, R ⁵ represents a C 1-18 alkyl group, R ⁶ represents a C 1-18 alkyl group, and R ⁷ represents a C 1-18 alkyl group. Shows,
R ⁸ represents an alkyl group having 1 to 4 carbon atoms, M ¹ is —S
Indicates O ₃ Na or sodium, m is 1 to 100,
n ¹ is 1 to 100, n ² is 1 to 100, n ³ is 1 to
100 and n ⁴ represent 1 to 100)

Examples of the reactive emulsifier include those having the basic structure of the above formula (5) and a radically polymerizable propenyl group introduced into a hydrophobic group. Other than this, known reactive surfactants can be used, for example,
Acrylic surfactants such as JP-B-5-75002, JP-A-54-144317, JP-A-62-15202, JP-A-62-34947, JP-A-56-28208 and JP-A-55-98201; 5-75001, Japanese Patent Publication 4
9-46291, JP-A-58-203060, JP-A-4
-53802, JP-A-4-50204, JP-A-60-7.
Allyl-based surfactants such as 8947; JP-A-62-22
803, JP-A-49-40388, JP-A-52-134
658, maleic acid type surfactants such as JP-A-50-98484; JP-B-46-34874 and JP-A-40-40.
388 and reactive surfactants such as itaconic acid-based surfactants of JP-A-50-98484 and the like, among which those disclosed in JP-B-5-75002 are particularly preferable.

The neutralization step (a) is a step of neutralizing a part of the polymer compound A with a base. Specifically, for example, the polymer compound A and the base are added to a reaction solvent and stirred. . The reaction solvent is not particularly limited as long as it does not inhibit the step, and examples thereof include a solvent that can be used in the production of the polymer compound A. The solvent used in the next addition step is desolvation. It is preferable because the process becomes unnecessary. The amount of the reaction solvent used is not particularly limited as long as it does not inhibit stirring.

In the neutralization step (a), a base is used as a part of the carboxyl group contained in the polymer compound A, preferably 1
It is essential to add 0 to 95%, more preferably 10 to 80% in an amount to neutralize. When the neutralized carboxyl group is less than 10%, when the carbon-carbon unsaturated bond-containing compound is added to the polymer compound A, the carbon-carbon unsaturated bond-containing compound is likely to become unstable, resulting in a reaction. It also causes gelation of the system. 95 neutralized carboxyl groups
If it exceeds 0.1%, the curing rate of the obtained polymer compound by irradiation with ultraviolet rays becomes slow, and the crosslinking rate becomes low, so that the physical properties such as water resistance, alkali resistance, and acid resistance of the obtained coating film deteriorate. This is because the ratio of the number of carboxyl groups added by the carbon-carbon unsaturated bond-containing compound to the number of neutralized carboxyl groups is too small.

In the step (a), to what extent the carboxyl group of the polymer compound A has to be neutralized depends on what purpose the polymer compound finally obtained is used for. It may be appropriately determined within the range. For example, neutralize less than 30% of carboxyl groups,
A polymer compound obtained by adding all the remaining free carboxyl groups with a compound containing a carbon-carbon unsaturated bond is unlikely to be an aqueous solution.

In the step (a), for example, a basic compound having an unsaturated bond such as zinc mono (meth) acrylate hydroxide, magnesium mono (meth) acrylate hydroxide, and aluminum mono (meth) acrylate hydroxide. You may use together 1 type (s) or 2 or more types of a compound with a carbon-carbon unsaturated bond containing compound. By using this in combination, the storage stability of the obtained UV-curable polymer compound is lowered, but the water resistance and UV-curability of the coating film made of the compound are dramatically improved.

Next, the copolymerization step (b) will be described. The monomer having a carboxyl group in the copolymerization step (b) means a monomer having a carboxyl group and a monomer that produces a carboxyl group by polymerization,
For example, (meth) acrylic acid, alkyl (meth) acrylate (the total number of carbon atoms is 1 to 12, and the alkyl part is linear or branched; for example, methyl (meth)
Acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, etc.), crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, maleic acid, fumaric acid, itacone Examples thereof include acids, citraconic acid, β- (meth) acryloyloxyhydrogensuccinic acid, β- (meth) acryloyloxyhydrogenphthalic acid, and acrylic acid dimer. These can be used alone or in combination of two or more.

The "monomer having a carboxyl group neutralized with a base" in the copolymerization step (b) means a compound in which the carboxyl group of the "monomer having a carboxyl group" is neutralized with a base.

The copolymerization step (b) can be carried out by a conventional method. For example, in a reaction solvent in the presence of a polymerization initiator, a monomer having a carboxyl group and a monomer having a carboxyl group neutralized with a base are used. Polymerize. In particular,
For example, a monomer having a carboxyl group, a monomer having a carboxyl group neutralized with a base, and a polymerization initiator are added to a reaction solvent and stirred. In the copolymerization step (b), the reaction solvent and the polymerization initiator mentioned in the neutralization step (a) can be used, and the reaction solvent is the same as the solvent used in the next addition step. It is preferable because the solvent removal step is unnecessary.

The compounding ratio of the monomer having a carboxyl group and the monomer having a carboxyl group neutralized with a base is such that the content ratio of carboxyl group: neutralized carboxyl group in the obtained copolymer is usually 90. : 10 to 5: 9
5, preferably 90:10 to 20:80.

Next, the additional step performed after the completion of the neutralization step (a) and the copolymerization step (b) will be described. The addition step in the present invention is a step of adding a carbon-carbon unsaturated bond-containing compound to the free carboxyl group of the polymer compound obtained in the neutralization step (a) and the copolymerization step (b). . Specifically, for example, the polymer compound obtained in the neutralization step (a) or the copolymerization step (b) and the carbon-carbon unsaturated bond-containing compound are added and stirred in a reaction solvent. It is essential that the reaction solvent in the addition step is water alone, a water-soluble solvent alone, or a mixed solvent thereof.

The carbon-carbon unsaturated bond-containing compound in the addition step is not particularly limited as long as it is a compound having a carbon-carbon unsaturated bond which is cleaved by ultraviolet irradiation and a group capable of reacting with a carboxyl group. For example, a compound having an acryloyl group or a methacryloyl group as a carbon-carbon unsaturated bond which is cleaved by ultraviolet irradiation and an epoxy ring as a group capable of reacting with a carboxyl group can be mentioned. The epoxy ring as used herein means a cyclic ether in which an oxygen atom is bonded to carbons of two atoms in the same molecule, and examples thereof include oxirane, oxetane and oxolane. The carbon-carbon unsaturated bond-containing compound is
The amount used may be appropriately determined depending on how many carboxyl groups are added.

Specific examples of the compound having a (meth) acryloyl group and an epoxy ring include glycidyl (meth).
Acrylate, 2-methylglycidyl (meth) acrylate; 3,4-epoxycyclohexylethyl (meth) acrylate containing an alicyclic epoxy group, 3,4-epoxycyclohexylethyloxycarbonylpentamethyleneoxy (meth) acrylate; Examples thereof include oxetane (meth) acrylate having a 4-membered ring, and glycidyl (meth) acrylate is preferable.

When the carbon-carbon unsaturated bond-containing compound contains an epoxy ring, the addition step is preferably carried out at 80 ° C. or higher, more preferably 85 to 90 ° C., and if the temperature is lower than 80 ° C., the epoxy ring formation is more effective than the addition reaction. The hydrolysis is prioritized, the addition reaction is difficult to proceed, and a polymer compound having a smaller number of added carboxyl groups than the neutralized carboxyl groups can be obtained.

In the addition step, a catalyst is not particularly required, but an ordinary catalyst can be used, and examples thereof include alkali catalysts such as ammonia and amine, and quaternary salts such as triethylbenzylammonium chloride and triphenylphosphine. To be When using a catalyst,
0.1% or more may be added to the polymer compound.
The amount of the catalyst used is usually 1 with respect to the polymer compound.
It is 0% or less, preferably 3% or less. When it exceeds 10%, the performance of the coating film obtained from the obtained ultraviolet-curable polymer compound, such as water resistance, is deteriorated.

In addition to the above catalyst, a polymerization inhibitor may be added, and examples thereof include hydroquinone and phenothiazine, with hydroquinone being preferred. The amount of the polymerization inhibitor used is usually 0.1 to 10 relative to the polymer compound.
%, Preferably 3 to 10%. However, when hydroquinone is used, it is usually 10
~ 10,000 ppm, preferably 100-1,000
Amounts in ppm are used.

The addition reaction is carried out by the acid value (mgKO of the reaction mixture.
H / g (solid content conversion)) is 30 or less, preferably 5 to 2
It will stop when it reaches 0. The reaction can be stopped by a conventional method. If the acid value exceeds 30, the amount of unsaturated bonds introduced into the carbon-carbon unsaturated bond-containing compound will be small, and the curing rate of the resulting polymer compound by ultraviolet irradiation will be slow and the crosslinking rate will be low. Physical properties such as water resistance, alkali resistance, and acid resistance of the obtained coating film deteriorate.

By the method of the present invention described above, a water-dispersible UV-curable polymer compound containing a repeating unit having a carboxyl group, which has the following features (1) and (2), can be obtained. (1) A part of the carboxyl group is neutralized with a base. (2) A part of the carboxyl group is added with a carbon-carbon unsaturated bond-containing functional group.

In the above feature (1), preferably 1
0-95%, more preferably 10-80% carboxy
Group is neutralized with a base (synonymous with the neutralization ratio described later).
, An amine compound or an alkali
Metal compounds include NH _FourOH and KOH are preferred
Yes.

In the above feature (2), it is preferable that the carbon-carbon unsaturated bond is added with a carbon-carbon unsaturated bond-containing functional group derived from an acryloyl group or a methacryloyl group.

[0043]

[Chemical 4]

A group represented by the formula (wherein R represents a hydrogen atom or a methyl group) is preferable.

The water-dispersible UV-curable polymer compound preferably has a weight average molecular weight of 5,000 to 1,000,0.
00, more preferably 100,000 to 800,000
Is preferred. The weight average molecular weight here is G
Numerical value by PC measurement, column Shedex GP
CKF-8051 (manufactured by Showa Denko) is used, and tetrahydrofuran is used as an organic solvent, and the measurement is performed at room temperature.

The water-dispersible UV-curable polymer compound obtained in the present invention can be used in applications such as water-dispersible paints, UV-curable paints and compounded products. For example, when it is used as a water-dispersible paint, a photopolymerization initiator may be added to the water-dispersible UV-curable polymer compound of the present invention, which is applied to the surface to be coated, dried, and irradiated with ultraviolet rays. Thus, a cured coating film can be formed.

[0047]

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Further, as a method for measuring the acid value in the examples,
A sample of 0.1 to 1 mg is diluted with acetone to obtain 0.1N-
Neutralization titration is performed with an aqueous NaOH solution. Add phenolphthalein as an indicator. Example 1 A four-necked flask (5 L) was equipped with a stirrer, a thermometer, a cooling tube and a dropping funnel, and water (1800 g) and a reactive surfactant (trade name: Aqualon HS-10, 10) were used.
g) was charged, and acrylic acid (360 g, 5 mol) and ethyl acrylate (40 g) were added dropwise with a dropping funnel over 2 hours. At the same time, 10% ammonium persulfate solution (1
50 g) is added dropwise in 2 hours. The reaction temperature is from 80 to
Control to 85 ° C. Maintain at the same temperature for 8 hours,
Aging is performed to complete the decomposition reaction of the remaining initiator. Then, dimethylaminoethyl methacrylate (1
57 g, 1 mol) was added to carry out a neutralization reaction, glycidyl methacrylate (568 g, 4 mol) and hydroquinone (1 g) were added, an addition reaction was carried out at 80 to 85 ° C., and the acid value was as shown in Table 1. The reaction is stopped when it becomes.
Concentration 36.5%, viscosity (EL type viscometer) 3600 mPas
・ S / 25 ° C., weight average molecular weight (GPC measurement) 253,
000 products (hereinafter referred to as polymer A) were obtained.

Example 2 A four-necked flask (5 L) was equipped with a stirrer, a thermometer, a condenser and a dropping funnel, and water (1800 g) and a reactive surfactant (trade name: Aqualon HS-10, 10) were used.
g) was charged, and acrylic acid (360 g, 5 mol) and ethyl acrylate (4.0 g) were added dropwise with a dropping funnel over 2 hours. At the same time, 10% ammonium persulfate solution (150 g) is added dropwise in 2 hours. The reaction temperature is 8
Control to 0-85 ° C. It is maintained at the same temperature for 8 hours and aged to complete the decomposition reaction of the remaining initiator. Then potassium hydroxide (56.1 g, 1 mol)
Was added to carry out a neutralization reaction, glycidyl methacrylate (568 g, 4 mol) and hydroquinone (1 g) were added, the addition reaction was carried out at 80 to 85 ° C., and the reaction was stopped when the acid value reached the value shown in Table 1. To do. A product (hereinafter referred to as polymer B) having a concentration of 34.3%, a viscosity (EL type viscometer) of 4200 mPa · s / 25 ° C. and a weight average molecular weight (GPC measurement) of 268,000 was obtained.

Example 3 A four-necked flask (5 L) was equipped with a stirrer, a thermometer, a condenser and a dropping funnel, charged with isopropyl alcohol (1800 g), and acrylic acid (360 g, 5 mol), ethyl acrylate (4 0.0 g) and a mixed monomer of azoisobutyronitrile (4 g) are added dropwise with a dropping funnel over 4 hours. The reaction temperature is controlled at 78 to 82 ° C. It is maintained at the same temperature for 12 hours and aged to complete the decomposition reaction of the remaining initiator. Then, dimethylaminoethyl methacrylate (314 g,
2 mol) was charged and a neutralization reaction was carried out to obtain glycidyl methacrylate (471 g, 3 mol) and hydroquinone (1
g) is charged, an addition reaction is carried out at 80 to 90 ° C., and when the acid value reaches the value shown in Table 1, water (1800 g) is charged and isopropyl alcohol is removed under reduced pressure (100 mmHg). Since water is also removed at the same time, the shortage is added and the concentration is 40% and the viscosity (EL type viscometer) 1250
0 mPa · s / 25 ° C, weight average molecular weight (GPC measurement)
128,800 products (hereinafter referred to as polymer C) were obtained.

Example 4 A four-necked flask (1 L) was equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, and water (400 g) and a reactive surfactant (trade name: Aqualon HS-10, 5) were used.
g) was charged and heated to 80 ° C., 2-ethylhexyl acrylate (180 g), acrylonitrile (20 g)
And a mixed solution of acrylic acid (20 g) is added dropwise with a dropping funnel over 2 hours. Aging at the same temperature for 8 hours, 6
After cooling at 0 ° C., 25% aqueous ammonia (4 g) and water (1
50 g) was added for neutralization. Then, the temperature is raised to 80 ° C., glycidyl methacrylate (27 g) and methylhydroquinone (0.2 g) are added, and the temperature is 80 to 90 ° C.
The addition reaction was carried out. The reaction is stopped when the acid value reaches the value shown in Table 1. Neutralization rate 21.3%, concentration 32%, viscosity (EL type viscometer) 100 mPa · s / 25 ° C., reactive functional group concentration 10.9%, weight average molecular weight (GPC measurement) 3
68,000 products (hereinafter referred to as polymer D) were obtained.

In Examples 5 to 7, the amounts of 25% aqueous ammonia used were 1.9 g, 7.6 g and 15.2, respectively.
The same procedure as in Example 4 was carried out except that the amount was changed to g. The products are hereinafter referred to as polymers E to G. The following properties of the polymer compounds obtained in Examples 1 to 7 were measured. The measurement results are shown in Table 1. The neutralization rate and the addition rate in Table 1 are values calculated by the following mathematical formula. Neutralization rate (%) = (X−Y) / X Addition rate (%) = (Y−Z) / X (where X is the acid value after polymerization (mg KOH / g), Y
Represents the acid value after neutralization (mg KOH / g), and Z represents the acid value after addition (mg KOH / g). )

Water dilutability: 100 g of polymer compound at 25 ° C.
The minimum amount of water required for the white turbidity was divided by 100.
The cloudiness was visually confirmed.

Dilution viscosity (mPa · s / 25 ° C.): The viscosity of the obtained polymer compound diluted with an equal amount of water was measured.

Storage stability: The stability of a cloudy polymer compound solution was measured when it was left at 30 ° C. for 1 week. After standing for 1 week, the presence or absence of precipitation was visually confirmed.

[0055]

[Table 1]

Example a Polymer A (100 parts) was mixed with the photopolymerization initiator dulcure 11
73 (1 part) was added, and kraft paper 170 g / m ²
After coating with 5 g / m ² (solid content), it was dried at 80 ° C. for 1 minute and cured by irradiation with ultraviolet rays to obtain a cured coating film.

Example b The procedure of Example a was repeated except that the polymer A was changed to the polymer B. Example c The procedure of Example a was repeated, except that the polymer A was changed to the polymer C.

Example d Polymer A (100 parts) with a photopolymerization initiator dulcure 117
In the same manner as in Example a except that polyethylene glycol # 600 diacrylate (30 parts) was added in addition to 3 (1 part).

Example e Polymer A (100 parts) and photopolymerization initiator dulcure 117
Example 3 was repeated except that dipentaerythritol hexaacrylate (DPHA, 30 parts) was added in addition to 3 (1 part).

Example f Example f was repeated except that the polymer A was changed to the polymer B. Example g The procedure of Example d was repeated, except that the polymer A was changed to the polymer C.

Example h Polymer D (100 parts) was added to the photopolymerization initiator dulcure 11
73 (1 part) was added and the mixture was coated on a glass plate or a PC (polycarbonate plate) and then dried at 80 ° C. for 1 minute. The coating amount was 5 g / m ² (solid content). It was irradiated with ultraviolet rays and cured to obtain a cured coating film.

Example i The procedure of Example h was repeated, except that the polymer D was changed to the polymer F. Example j Example j was repeated except that the polymer D was changed to the polymer G.

Example k Polymer D (100 parts) was added to the photopolymerization initiator dulcure 117.
Example 3 was repeated except that polyethylene glycol # 600 diacrylate (30 parts) was added in addition to 3 (1 part).

Example l Polymer D (100 parts) and a photopolymerization initiator dulcure 117 were added.
Example 3 was repeated except that dipentaerythritol hexaacrylate (DPHA, 30 parts) was added in addition to 3 (1 part).

Comparative Example 1 Polyethylene glycol # 600 diacrylate (10
(0 part), the photopolymerization initiator dulcure 1173 (3 parts) and water (100 parts) were added and mixed in the same manner as in Example a.

The following measurements were carried out in order to evaluate the performance of the cured coating films obtained in Examples a to 1 and Comparative Example 1 above. The results are shown in Tables 2 and 3.

Ultraviolet curability: An ultraviolet irradiator (manufactured by Ushio Inc., product name "UVC-5034 type") was used to irradiate the coating film with a light amount of 1 pass, and the degree of curing was examined by contact. The UV curability was indicated by the integrated light quantity when completely cured.

Pencil hardness: The pencil hardness of the cured coating film is JIS-
It measured based on K-5400-6,14.

Adhesion: (1) A coating material (coating amount 5 g / m ² (solid content)) was applied to kraft paper, dried, and then irradiated with ultraviolet rays to form a cured coating film. The cured coating film was cross-cut into 2 mm × 2 mm. A test was carried out by sticking cellophane tape on the cut coating film and peeling it off. The criteria for judgment were as follows. (2) Paint on glass plate or PC plate (application amount 5 g / m ²
(Solid content)) was applied and dried, and then ultraviolet rays were irradiated to form a cured coating film. The cured coating film was cross-cut into 2 mm × 2 mm. Stick cellophane tape on the cut coating,
A test for peeling this was conducted. The criteria for judgment were as follows. ⊚: No peeling at all, ◯: Peeling off only a part, Δ: Most peeling off, ×: Peeling off the entire surface.

Water resistance: The coating film is immersed in ion-exchanged water for 20 to 25
After dipping at 6 ° C. for 6 hours, the following criteria were evaluated. ⊚: No change, ◯: Partial whitening, Δ: Full whitening, ×: Swelling.

Alkali resistance: The coating film was immersed in a 5% aqueous sodium hydroxide solution at 20 to 25 ° C. for 6 hours, and then evaluated according to the following criteria. ⊚: No change, ◯: Partial whitening, Δ: Full whitening, ×: Swelling.

Acid resistance: The coating film was immersed in 5% hydrochloric acid at 20 to 25 ° C. for 6 hours and then evaluated according to the following criteria. ⊚: No change, ◯: Partial whitening, Δ: Full whitening, ×: Swelling.

Transparency (appearance): The transparency of the coating composition was visually evaluated.

[0074]

[Table 2]

[0075]

[Table 3]

[0076]

According to the method of the present invention, in a polymer compound containing a repeating unit having a carboxyl group, a part of the carboxyl group is neutralized with a base, and a part of the carboxyl group is A water-dispersible UV-curable polymer compound characterized by being added with a carbon-carbon unsaturated bond-containing functional group can be produced.

Continued front page    F term (reference) 4J027 AA02 AJ01 CB10 CC05 CD08                 4J038 CG001 CG031 CG141 CH151                       EA011 GA01 GA03 GA07                       GA09 HA156 HA176 JA05                       JA17 JA25 JA26 JA33 JA43                       JA55 JB01 JC13 KA06 KA09                       KA16 LA01 MA04 MA08 NA11                       NA12 NA26 NA27 PA17 PB09                       PC06 PC10                 4J100 AJ02P AL03Q AL04Q BA20H                       CA31 DA01 HA11 HA31 HC39                       HC45 HE12 HE13 HE14 JA01

Claims (16)

[Claims] 1. In a polymer compound containing a repeating unit having a carboxyl group, a part of the carboxyl group is neutralized with a base, and a part of the carboxyl group is a carbon-carbon unsaturated bond. A water-dispersible UV-curable polymer compound, which is added with a functional group contained therein. 2. The polymer compound according to claim 1, wherein 10 to 95% of the carboxyl groups are neutralized. 3. The polymer compound according to claim 1, wherein the base is an amine compound or an alkali metal compound. 4. The polymer compound according to claim 1, wherein the carbon-carbon unsaturated bond is derived from an acryloyl group or a methacryloyl group. 5. A carboxyl group added with a carbon-carbon unsaturated bond-containing functional group has the formula: The polymer compound according to claim 1, which is a group represented by the formula (wherein R represents a hydrogen atom or a methyl group). 6. A weight average molecular weight of 5,000 to 1,00.
The polymer compound according to claim 1, which is 10,000. 7. The polymer compound according to claim 1, which is used for a water-dispersible coating material. 8. A polymer compound containing a repeating unit having a carboxyl group (a) after neutralizing a part of the carboxyl group with a base, or (b) neutralizing with a monomer having a carboxyl group and a base. After copolymerizing a monomer having a carboxyl group, water alone, a water-soluble solvent alone or in a mixed solvent thereof, a carbon-carbon unsaturated bond-containing compound is added to a part of the free carboxyl group, A method for producing a water-dispersible UV-curable polymer compound. 9. A free carboxyl group in water alone, a water-soluble solvent alone or a mixed solvent thereof after neutralizing a part of the carboxyl groups of a polymer compound containing a repeating unit having a carboxyl group with a base. 9. The production method according to claim 8, wherein a compound containing a carbon-carbon unsaturated bond is added to a part of the above. 10. The production method according to claim 9, wherein 10 to 95% of the carboxyl groups are neutralized. 11. The production method according to claim 9, wherein the base is an amine compound or an alkali metal compound. 12. A carbon-carbon unsaturated bond-containing compound,
The production method according to claim 9, which is glycidyl methacrylate or glycidyl acrylate. 13. After copolymerization of a monomer having a carboxyl group and a monomer having a carboxyl group neutralized with a base, carbon is added to a part of the free carboxyl group in water alone, a water-soluble solvent alone or a mixed solvent thereof. The method according to claim 8, characterized in that a compound containing a carbon unsaturated bond is added. 14. The copolymer obtained after the copolymerization has a carboxyl group: neutralized carboxyl group of 90:10.
The manufacturing method according to claim 13, which is 5:95. 15. The method according to claim 13, wherein the base is an amine compound or an alkali metal compound. 16. A carbon-carbon unsaturated bond-containing compound,
The manufacturing method according to claim 13, which is glycidyl methacrylate or glycidyl acrylate.