JP2002322206A - Active energy ray-curable resin composition, film using the same, and recording medium - Google Patents

Abstract

(57) [Problem] To provide an active energy ray-curable resin composition capable of forming a film having high water absorbency and good water resistance. SOLUTION: (A) a monomer having a polymerizable group and an acidic group polymerizable by irradiation of active energy in the molecule, and (B) a basic group and a hydrophilic group capable of forming a salt with the acidic group in the molecule. An active energy ray-curable resin composition comprising a polymer having a group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable resin composition, and a recording medium and an antifogging film produced using the same.

[0002]

2. Description of the Related Art Recording with an aqueous ink has been widely used in various fields because it has little effect on the environment and health. In particular, in recent years, the ink jet recording system has become widespread, and writing on various substrates has been studied. Here, the aqueous ink generally contains a water-soluble dye or pigment and water or a solvent containing water and a small amount of alcohol as main components. Therefore, if the printing surface is hydrophobic, the ink may be repelled without being absorbed, or the drying may be delayed, causing problems such as transfer and contamination of the surroundings. Therefore, starch, gelatin, polyvinylpyrrolidone, polyvinyl alcohol, cellulose derivatives,
It has been proposed that a hydrophilic coating film composed of a hydrophilic polymer such as sodium polyacrylate be formed on a substrate surface, or that inorganic or organic particles be mixed into the surface to be porous. . Further, since many water-soluble dyes have an anionic group such as a sulfone group, a method for preventing re-elution of ink by forming an ion complex with a cationic substance has been developed.

[0003] A coating solution for forming a hydrophilic coating film can be prepared by dissolving a hydrophilic polymer in water, but the solubility of the hydrophilic polymer in water is generally low. Therefore, it may contain a large amount of water and take time for drying. In addition, the concentration of the hydrophilic polymer in the coating liquid cannot be increased, and a coating film having a sufficient thickness may not be obtained by one coating. For this reason, coating may be repeatedly performed several times, which is an adverse effect on productivity.
Therefore, various methods for forming a hydrophilic coating film in a short time by using an active energy ray-curable resin composition have been proposed. For example, Japanese Patent Application Laid-Open No. 1-222985 proposes an ink receiving layer obtained by curing a prepolymer having photocurable groups at both ends. However, in the case of this method, if the molecular weight of the prepolymer is small, the water resistance is good but the ink absorption property cannot be maintained, while if the molecular weight of the prepolymer is large, the reaction between the ends of the high molecular weight substance is difficult. And it tends to harden. Also,
JP-A-10-67905 proposes an ink receiving layer composed of a curable composition containing a hydrophilic resin having an ethylenically unsaturated group and a hydrophilic oligomer. The method of providing groups was complicated, and the cured coating film had only a covalent bond, so the crosslinked structure was strong, and the ink absorbency and the like were still insufficient.

On the other hand, also for plastic products, various studies have been made on surface modification for imparting so-called anti-fogging property, which prevents water droplets from adhering to the plastic surface due to water vapor or steam in the air. For example, to impart hydrophilicity to the surface of the base material using a surfactant, to form a water-repellent surface using a water-repellent agent, or to form a water-absorbent surface using a hydrophilic polymer. Various surface modification methods have been proposed (JP-A-63-251401, JP-A-4-7388, JP-A-4-180986, etc.). In order to prevent condensation of minute water droplets such as steam (anti-fog), it is considered that a water-absorbing film is effective. However, a coating film having both high water absorption capacity and water resistance of the coating film itself has been developed. Has not been reached.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and is directed to an active energy ray capable of forming a film having high water absorption and good water resistance. It is an object to provide a curable resin composition. Another object of the present invention is to provide a recording medium having high absorbability for ink, particularly water-based ink, and having excellent printability. Another object of the present invention is to provide a film that can impart antifogging properties to the surface of various substrates and has excellent water resistance.

[0006]

Means for Solving the Problems The present inventor has found that when the crosslinked structure of a cured film is formed by ionic bonds, the crosslinked structure is softened and exhibits higher water absorbability. The present invention has been completed based on the findings.
That is, means for solving the above-mentioned problems are as follows. <1> (A) a monomer having a polymerizable group and an acidic group polymerizable by irradiation of active energy in the molecule;
(B) An active energy ray-curable resin composition characterized by containing a polymer having a basic group capable of forming a salt and a hydrophilic group in a molecule and a hydrophilic group. <2> The active energy ray according to <1>, wherein the acidic group in the monomer (A) is a carboxyl group, and the basic group in the polymer (B) is an amino group. It is a curable resin composition. <3> The active energy ray-curable resin composition according to <1> or <2>, wherein the monomer (A) is a monomer having at least one acryloyl group or methacryloyl group in a molecule. It is.

<4> The above-mentioned (A) monomer contains 1
A monomer having one carboxyl group and one or more acryloyl groups or methacryloyl groups, and wherein the polymer (B) is a polymer having an amino group and a hydrophilic group in the molecule. The active energy ray-curable resin composition according to <1>. <5> The active energy ray-curable resin composition according to any one of <1> to <4>, wherein the polymer (B) is a polymer having a quaternary ammonium salt. <6> The weight average molecular weight of the polymer (B) is 3,000.
<1> to <3, characterized by being 0 to 300,000.
5> The active energy ray-curable resin composition according to any one of the above.

<7> The hydrophilic group in the polymer (B) is selected from a hydroxy group, an alkoxy group, an acid amide group, an amino group, a morpholino group, an ether group, a tetrahydrofurfuryl group, a glycidyl group and a pyrrolidonyl group. <1> to <1 characterized by being at least one selected from
6> The active energy ray-curable resin composition according to any one of the above. <8> The activity according to any one of <1> to <7>, further including (C) a monomer having a polymerizable group and a hydrophilic group copolymerizable with the (A) monomer. It is an energy ray-curable resin composition. <9> The active energy ray-curable resin composition according to <8>, wherein the monomer (C) has a hydrophilic group and one or more acryloyl groups or methacryloyl groups. <10> The active energy ray-curable resin composition according to any one of <1> to <9>, further comprising a hydrophilic polymer.

<11> characterized by further containing an organic filler and / or an inorganic filler <1> to
The active energy ray-curable resin composition according to any one of <10>. <12> Based on 100 parts by weight of the polymer (B),
(A) The active energy ray-curable resin composition according to any one of <1> to <11>, which contains 1 to 250 parts by weight of a monomer.

<13> A film produced by using the active energy ray-curable resin composition according to any one of <1> to <12>. <14> A recording medium produced using the active energy ray-curable resin composition according to any one of <1> to <12>. <15> An anti-fogging film made of the active energy ray-curable resin composition according to any one of <1> to <12>.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, each component constituting the active energy ray-curable resin composition of the present invention will be described, and then adjustment of the composition and the like will be described. In this specification, “to” indicates a range including numerical values described before and after it as a minimum value and a maximum value, respectively.

First, the active energy ray-curable resin composition of the present invention contains (A) a monomer having a specific structure and (B) a polymer. (A) Monomer The (A) monomer has in its molecule a polymerizable group and an acidic group that can be polymerized by irradiation with active energy rays. (A)
The polymerizable group in the molecule of the monomer is preferably a polymerizable group containing a carbon-carbon double bond. Above all, as the monomer (A), an acrylic acid or acrylate ester-based monomer having at least one acryloyl group or methacryloyl group in a molecule (hereinafter, both are collectively referred to as “acrylate-based monomer”), or And methacrylic acid or methacrylic acid ester-based monomers (hereinafter, both are collectively referred to as “methacrylate-based monomers”). Examples of the acidic group in the molecule of the monomer (A) include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Among them, as the monomer (A), a carboxyl group is one in the molecule.
Monomers having one are preferred.

When the monomer (A) is an acrylate or methacrylate monomer having one carboxyl group in the molecule, specific examples thereof include (meth) acrylic acid and pentaerythritol triacrylate succinate monoester. , Dipentaerythritol pentaacrylate succinate monoester, pentaerythritol triacrylate maleate monoester, dipentaerythritol pentaacrylate maleate monoester, pentaerythritol triacrylate phthalate monoester, dipentaerythritol pentaacrylate phthalate monoester, penta Erythritol triacrylate tetrahydrophthalic acid monoester,
A reaction product of a hydroxyl group-containing polyfunctional acrylate such as dipentaerythritol pentaacrylate tetrahydrophthalic acid monoester and an acid anhydride is exemplified. Among them, pentaerythritol triacrylate succinate monoester is preferred. As the monomer (A), one type may be used alone, or two or more types may be used in combination.

(B) Polymer The polymer (B) has in its molecule (A) a basic group capable of forming a salt with an acidic group of a monomer, and a hydrophilic group. Examples of the basic group include an amino group, an N-substituted amino group, N,
And N-disubstituted amino groups. In particular, when the acidic group of the monomer (A) is a carboxyl group, the basic group of the polymer (B) is preferably an amino group. Less than,
The term "amino group" refers to an N-substituted amino group, N, N
-Used to include a disubstituted amino group and an unsubstituted amino group. As the hydrophilic group of the polymer (B),
Hydroxy group, alkoxy group (preferably having 1 carbon atom)
To 20 alkoxy groups), acid amide groups, amino groups, morpholino groups, ether groups, tetrahydrofurfuryl groups, glycidyl groups, amino groups and pyrrolidonyl groups. Among them, an acid amide group, a hydroxy group and an alkoxy group are more preferred.

The polymer (B) can be produced by copolymerizing a monomer (B ¹ ) having a basic group in the molecule and a monomer (B ² ) having a hydrophilic group in the molecule. it can. When the basic group is an amino group,
Examples of the monomer (B ¹ ) include (meth) acrylic acid esters of amino alcohols. Specifically, N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) Acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, N, N N-dihydroxyethylaminoethyl (meth) acrylate is exemplified. Among them, examples of the monomer (B ¹⁾ is, N, N-dimethylaminoethyl (meth) acrylate is preferably used.

The monomer having a hydrophilic group (B ² )
Has a solubility in water of preferably 1 g / 100 g (water) or more, more preferably 5 g / 100 g (water) or more, and particularly preferably 10 g / 100 g (water) or more. The monomer (B ² ) is preferably a hydrophilic (meth) acrylic monomer, and specific examples thereof include hydroxyethyl (meth) acrylate,
-Hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (Meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, diethylene glycol (meth) acrylate, triethylene glycol (meth) acrylate, polyethylene glycol (meth) A monomer having a hydroxyl group such as acrylate, dipropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, glycerin (meth) acrylate; Methyl acrylamide and the monomer having an acid amide group diethyl acrylamide; acryloyl morpholine, N- vinylpyrrolidone, 2-ethoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ethyl carbitol (meth)
Highly polar monomers such as acrylate, glycidyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate; As the monomer (B ² ), one type may be used alone, and 2
More than one type may be used in combination.

When the polymer (B) has an amino group as a hydrophilic group, the polymer (B) may be composed only of the monomer (B ¹ ) having a basic group.

It is preferable that the polymer (B) contains a quaternary ammonium salt from the viewpoint of the fixability of the aqueous ink to the recording material and the antifogging property. The quaternary ammonium salt-forming (B) polymer is obtained by copolymerizing a monomer (B ³ ) having a quaternary ammonium salt with the monomers (B ¹ ) and (B ² ). As the monomer (B ³ ) having a quaternary ammonium salt, a monomer obtained by quaternizing the (meth) acrylic acid ester of an amino alcohol exemplified as the monomer (B ¹ ) can be used.

The polymer (B) may contain another monomer (B ⁴ ) as a copolymerization component together with the monomer (B ¹ ) and the monomer (B ² ). Other monomers (B ⁴ ) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, ethylhexyl (meth) acrylate, and stearyl (meth) Alkyl (meth) acrylates such as acrylate, lauryl (meth) acrylate and tridecyl (meth) acrylate; polymerizable unsaturated group-containing compounds such as styrene and methylstyrene; and the like.

The polymer (B) can be produced by using a general radical polymerization. For example, in a solvent such as water, alcohol, ethyl acetate and methyl ethyl ketone, in the presence of a radical polymerizable initiator such as azobisisobutyronitrile, the monomer (B ¹ ) and the monomer (B ² ), and (It can be produced by copolymerizing the monomer (B ³ ) and / or the monomer (B ⁴ ).

In producing the polymer (B), the monomer (B ¹ ) and the monomer (B ² ) are mixed in a weight ratio of 1/1.
It is preferably used in a ratio of 100 to 100/1.
More preferably, it is used in a ratio of 95 to 95/5. If the amount of the monomer (B ¹ ) is too small, the crosslinked structure formed together with the monomer (A) is reduced, and the water resistance of the film tends to decrease. On the other hand, if it is too large, the crosslinked structure formed together with the monomer (A) becomes too large, and the water absorption and the like tend to decrease. Also,
When the polymer (B) contains, as a copolymerization component, the monomer (B ³ ) and / or the monomer (B ⁴ ) in addition to the monomer (B ¹ ) and the monomer (B ² ), these monomers Can be used depending on the desired effect of each addition, as long as the object and effects of the present invention are not hindered.

The molecular weight of the polymer (B) is not particularly limited, but is generally from 3,000 to 300,0.
00, preferably 5,000 to 100,000
Is more preferable. If the molecular weight is too large, the curing reaction by active energy rays tends to be difficult to proceed.

In the active energy ray-curable resin composition of the present invention, the monomer (A) is cured by irradiation with the active energy ray, and the acidic group of the monomer (A) and the polymer (B) are cured. The crosslinked structure is formed by the interaction with the basic group (salt-forming action), and the polymer (B) is incorporated into the crosslinked structure. as a result,
A film having moderately excellent film strength and high absorbency for aqueous liquids such as aqueous inks. Also,
When the film is brought into contact with a strong alkali solution or the like, the salt structure in the film is broken and eluted into the strong alkali solution. Materials can also be recycled.

In the active energy ray-curable resin composition of the present invention, the content ratio of the (A) monomer and the (B) polymer depends on the interaction between an acidic group and a basic group (salt-forming action) and (B) It can be appropriately determined in consideration of the degree of hydrophilicity of the polymer. Generally, (B) polymer 1
The amount of the monomer (A) is preferably 1 to 250 parts by weight with respect to 00 parts by weight. In particular, when used for producing a recording medium for inkjet printing, the amount of the monomer (A) is preferably from 1 to 200 parts by weight, and more preferably from 1 to 150 parts by weight, based on 100 parts by weight of the polymer (B). Is more preferred. When used for forming an anti-fogging film, the monomer (A) is used in an amount of 20 to 2 with respect to 100 parts by weight of the polymer (B).
It is preferably 50 parts by weight, more preferably 50 to 250 parts by weight.

The active energy ray-curable resin composition of the present invention may contain other components in addition to the monomer (A) and the polymer (B). Hereinafter, other components added as desired will be described.

The active energy ray-curable resin composition of the present invention may contain (C) a monomer having a polymerizable group copolymerizable with the monomer (A) and a hydrophilic group. It is preferable to contain the monomer (C) because the film strength is further improved. (C) The monomer preferably has a solubility in water of 1 g / 100 g (water) or more,
More preferably, it is 5 g / 100 g (water) or more.
It is particularly preferred that the amount is 0 g / 100 g (water) or more. As the hydrophilic group, a hydroxy group, an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms), an acid amide group, an amino group, a morpholino group, an ether group, a tetrahydrofurfuryl group, a glycidyl group and a pyrrolidonyl group are preferable. . Among them, an acid amide group, a hydroxy group and an alkoxy group are particularly preferred. As the (C) monomer,
The monomer is not particularly limited as long as it has a hydrophilic group and can be copolymerized with the monomer (A). When the monomer (A) is an acrylate or methacrylate monomer, the monomer (C) Is also preferably an acrylate-based or methacrylate-based monomer.

Specific examples of the acrylate or methacrylate monomer having a hydrophilic group that can be used as the monomer (C) include hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, and 2-hydroxy Propyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 4
-Hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, 2-hydroxy-3-
Phenoxypropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate, 2
-Hydroxy-3-methoxypropyl (meth) acrylate, diethylene glycol (meth) acrylate, triethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, dipropylene glycol (meth) acrylate, polyprorylene glycol (meth) acrylate, glycerin (Meth) acrylate, dimethylacrylamide, diethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone, 2-ethoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, glycidyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate,
Such as ethylene glycol di (meth) acrylate, propanediol di (meth) acrylate, butanediol di (meth) acrylate, pentanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate Highly polar monomers are exemplified. One of these monomers may be used alone, or two or more thereof may be used in combination.

Further, the active energy ray-curable resin composition of the present invention contains (A) a monomer and (A) to improve and adjust various physical properties such as hardness, adhesion, water resistance and moisture resistance of the obtained film. And / or (C) a monomer copolymerizable with the monomer may be contained. Examples of such a monomer include butyl acrylate, pentyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, phenoxyethyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, Examples include pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate, and oligomers such as urethane acrylate and epoxy acrylate.

The active energy ray-curable resin composition of the present invention has a hydrophilic property for improving ink absorbency and film strength in addition to the monomer (A) and the polymer (B) as long as the purpose is not impaired. It is preferable to contain a copolymer. The hydrophilic copolymer has a solubility in water of 1 g / 10
0 g (water) or more, preferably 5 g / 100 g
(Water) is more preferred. For example, polyvinylpyrrolidone, polyvinyl alcohol, hydroxyethylcellulose, hydroxypropylcellulose, polyacrylamide, a homopolymer such as polyethylene glycol, or a copolymer containing a monomer component of such a homopolymer, such as a copolymer In the case of the above, a copolymer with a non-hydrophilic monomer may be used. This hydrophilic polymer is 1
One type may be used alone, or two or more types may be used in combination.

The active energy ray-curable resin composition of the present invention may contain an organic compound for the purpose of promptly absorbing ink to promote drying, and for the purpose of improving film strength and color tone. It is preferable to include a filler and / or an inorganic filler. As the inorganic filler, for example, silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, calcium silicate, synthetic zeolite, alumina, zinc oxide, titanium oxide and the like can be used. Examples of the organic filler include polyacrylic acid ester, polymethacrylic acid ester, styrene resin, polyester resin, polycarbonate, modified melamine resin, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, polymer particles such as rubber, and crosslinked products of these polymers. Particles or powders of natural polymers such as lignin, protein, cellulose, gelatin and the like can be used. One of these inorganic fillers and organic fillers may be used alone, or two or more thereof may be used in combination.

The active energy ray-curable resin composition of the present invention can be prepared by weighing each component in a predetermined amount and mixing with stirring. In the stirring and mixing, all the components may be mixed at once. For example, when an organic filler and / or an inorganic filler are contained, (A)
After mixing and dissolving the monomer and the polymer (B),
An organic filler and / or an inorganic filler can be added and mixed by stirring. The stirring and mixing can be performed using, for example, a stirring tank, a dissolver, a ball mill, a kneader, a sand mill, a three-roll mill, an ultrasonic disperser, or the like. The mixing is preferably carried out at a temperature of normal temperature to 60 ° C. in order to prevent polymerization during the treatment.

The active energy ray-curable resin composition of the present invention can be used to form films for modifying the surface of various substrates. The film is formed by applying the active energy ray-curable resin composition to various base materials, for example, paper, glass, plastic, ceramic, metal and the like, and then irradiating the active energy ray. Can be. Coating on the surface of the base material is performed by selecting an appropriate method from various coating methods such as spray coating, dip coating, roll coater coating, flow coater coating, and spin coater coating according to the shape and material of the base material. be able to. In addition, at the time of coating, a coating solution may be prepared using a solvent, but when a solvent is used, after removing the solvent by heating and drying, irradiating with active energy rays to form a film Is preferred.

It is preferable that the active energy ray irradiated for forming the film is an ultraviolet ray, an electron beam or a radiation because a crosslinked cured film can be stably formed. Among them, from a practical point of view, a curing method by irradiating ultraviolet rays is preferable, and specifically, a method of irradiating ultraviolet rays using a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, or the like. Is preferred. The irradiation dose is generally 50 to 2000
mJ / cm ² , preferably 100-1000 m
It is more preferably J / cm ² .

The thickness of the film to be formed can be set in a preferable range by adjusting the amount of the coating. The preferred range of the film thickness varies depending on the application, but in general,
1 to 1000 μm is appropriate, and 3 to 1000 μm from the viewpoint of film physical properties.
Preferably it is 50 μm.

In the film obtained by curing the active energy ray-curable resin composition of the present invention, the crosslinked structure is formed by an ionic bond between an acidic group and a basic group. Compared to cured films, it has flexibility and high absorbency for aqueous liquids,
Also excellent in water resistance. Furthermore, since the film is polymerized and cured by irradiation with active energy rays, it has excellent film strength.

The active energy ray-curable resin composition of the present invention is preferably used for producing an aqueous ink recording medium. For example, by applying the active energy ray-curable resin composition of the present invention to the surface of a paper or plastic substrate, irradiating the active energy ray, and forming a film,
A recording medium can be manufactured. The formed film is
It can function as an ink receiving layer. The non-recording medium is preferably used as a recording medium for aqueous ink, and particularly preferably used as a recording medium for inkjet using aquatic ink.

The active energy ray-curable resin composition of the present invention is preferably used for forming a film for imparting anti-fog properties to the surface of building materials, electronic / electric devices, electronic / electric parts and the like.
For example, the active energy ray-curable resin composition of the present invention is applied to the surface of plastics, ceramics, metals, and the like, and is irradiated with active energy rays to form a film. Properties can be imparted.

[0038]

The present invention will be described more specifically with reference to the following examples. Materials, reagents, ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

[Synthesis of Polymer (B)] (Synthesis Example 1) Solmix (alcohol-based solvent, Nippon Kasei Co., Ltd.) was used as a solvent in a reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. 150 g)
Hydroxyethyl methacrylate as monomer
7.5 g, dimethylaminoethyl methacrylate 2.5 g, and azobisisobutyronitrile 0.5 g as a polymerization initiator were charged, and the system was heated to 76 ° C. under a nitrogen stream.
Temperature. After conducting a polymerization reaction at the same temperature for 2 hours, 0.05 g of azobisisobutyronitrile was added, followed by a polymerization reaction at 76 ° C. for 5 hours to obtain a weight average molecular weight (M
w) is a polymer (B-) having 30,000 (GPC measurement)
I got

(Synthesis Example 2) Synthesis was performed except that 5 g of dimethylaminoethyl methacrylate, 20 g of dimethylacrylamide, 18.75 g of methyl chloride-modified dimethylaminoethyl methacrylate (80% aqueous solution), and 10 g of benzyl methacrylate were used as monomers. Polymerization was carried out in the same manner as in Example 1, and the weight average molecular weight (Mw) was 50,0.
A polymer (B-) of 00 (GPC measurement) was obtained.

Synthesis Example 3 Polymerization was carried out in the same manner as in Synthesis Example 1 except that 35 g of methoxypolyethylene glycol methacrylate (ME40, manufactured by Toho Chemical Co., Ltd.) and 15 g of dimethylaminoethyl methacrylate were used as monomers. 40,000 weight average molecular weight (Mw)
A polymer (B-) of (GPC measurement) was obtained.

(Synthesis Example 4) In a reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 150 g of Solmix (alcohol-based solvent, manufactured by Nippon Kasei Co., Ltd.) as a solvent and methoxypolyethylene as a monomer Glycol methacrylate (ME20, manufactured by Toho Chemical Co., Ltd.)
, And 5 g of acrylic acid, and 0.5 g of azobisisobutyronitrile as a polymerization initiator.
The temperature inside the system was raised to 76 ° C. under a nitrogen stream. After conducting a polymerization reaction at the same temperature for 2 hours, 0.05 g of azobisisobutyronitrile was added, followed by a polymerization reaction at 76 ° C. for 5 hours, and a weight average molecular weight (Mw) of 32,000 (GP)
C measurement). Next, under air flow, 80
C., 9 g of glycidyl methacrylate, 0.1 g of triphenylphosphine, and 0.05 g of hydroquinone monomethyl ether were added and reacted for 20 hours.
A polymer for a comparative example having an active energy ray-curable reactive group was obtained.

[Examples 1 to 4 and Comparative Examples 1 and 2] The active energy ray-curable materials of Examples 1 to 4 and Comparative Examples 1 and 2 were prepared according to the formulations shown in Tables 1 and 2 below.

Each of the prepared active energy ray-curable materials was applied to a 100 μm-thick polyethylene terephthalate film (“T600E100”, manufactured by Diafoil Hoechst) using a bar coater to have a film thickness of 15 μm.
And dried by heating at 80 ° C. for 5 minutes. Using a high-pressure mercury lamp having an output density of 120 w / cm, ultraviolet rays of 300 mJ / cm ² were irradiated from a position separated by 15 cm under a light source to form films. With respect to the films of Examples 1 to 3 and Comparative Example 1, inkjet printability was evaluated by the following test method. The films of Example 4 and Comparative Example 2 were evaluated for antifogging properties by the following test method.
The results are shown in Tables 1 and 2.

(1) Ink-jet printability Ink absorption test An ink-jet printer (“PM900”) was prepared using a commercially available water-based ink (compatible with an inkjet printer).
C "(manufactured by EPSON), and printing was performed on the surface of the prepared film. The ink bleeding of the printed portion was visually evaluated according to the following criteria. : No bleeding was visually observed. Δ: Slight bleeding was visually observed. X: Bleeding was clearly observed visually. Water resistance test One day after printing was performed in the same manner as the ink absorption test,
Water was dropped on the printed portion, and one minute later, the water was wiped off, and the remaining state of the ink was visually evaluated according to the following criteria. : No change was visually observed in the printed portion. C: Slight discoloration of the printed portion was visually observed. ×: Significant bleaching of the printed portion was visually observed.

(2) Anti-fog property Anti-fog property test A coated PET film obtained with the film surface facing down was placed at the opening of a container containing warm water at 50 ° C., thereby sealing the container. Five minutes after sealing, the degree of cloudiness of the film was visually evaluated according to the following criteria. ：: No fogging was observed visually. Δ: Some clouding was visually observed. ×: Significant clouding was observed visually. Water resistance test The prepared coated PET film was immersed in water for 1 hour, and the degree of change of the film was visually evaluated according to the following criteria. : No change was visually observed. Δ: The film was slightly dissolved visually. ×: Dissolution of the film was clearly observed visually.

[0047]

[Table 1]

[0048]

[Table 2]

As is evident from the results shown in Table 1, the recording materials for ink-jet recording having the films based on the compositions of the present invention of Examples 1 to 3 were all satisfactory in the evaluation items of the above-mentioned ink-jet printability. Results were shown. on the other hand,
Comparison containing (B) a polymer outside the range of the polymer (a polymer having no basic group and (A) a reactive group capable of covalent bonding to a monomer) instead of the polymer. The ink-jet recording material having a film based on the composition of Example 1 had bleeding at the printed portion and poor water resistance of the ink. Further, when the film based on the composition of the present invention of Example 4 was evaluated as an antifogging film, all of the above evaluation items of the antifogging property showed good results. On the other hand, in the case of the composition outside the scope of the present invention (composition not containing the monomer (A)), no haze was observed in the film, but the film was dissolved when immersed in water.

[0050]

As described above, according to the present invention, there is provided an active energy ray-curable resin composition capable of forming a film having high water absorption and good water resistance. be able to. Further, according to the present invention, it is possible to provide a recording medium that has high absorbability to ink, particularly water-based ink, and has excellent printability. Further, according to the present invention, it is possible to provide a film which can impart anti-fogging property to the surface of various substrates and has excellent water resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/00 C09D 5/00 Z 7/12 7/12 201/02 201/02 F-term (Reference) 4J011 AA05 AC04 BA04 BB01 HA03 HB17 QA02 QA03 QA35 RA03 UA01 UA03 UA04 VA01 WA02 WA05 4J026 AA45 AA70 BA02 BA25 BA28 BA34 BB01 BB02 DB12 DB23 DB32 FA04 GA07 GA08 4J038 BA022 BA102 BA192 BA252 CA04 CC03 CC03 CC03 CC03 CC03 CE032 CH061 CH062 CH081 CH082 CH111 CH112 CH121 CH122 CH131 CH132 CH141 CH142 CH201 CH202 CH211 CH212 CH221 CH222 CK032 DA212 DD002 DE002 FA011 FA012 FA081 FA082 FA151 FA152 FA251 FA252 FA281 FA282 GA02 GA03 GA04 GA06 GA07 GA08 GA09 GA13 GA14 HA406 HA246 446 286 KA20 MA02 MA14 NA06 NA17 PA17 PB14 PC02 PC03 PC08 PC10

Claims (15)

[Claims] 1. A monomer having (A) a polymerizable group and an acidic group polymerizable by irradiation of active energy in the molecule, and (B) a basic group and a hydrophilic compound capable of forming a salt with the acidic group in the molecule. An active energy ray-curable resin composition comprising a polymer having a functional group. 2. The method according to claim 1, wherein the acidic group in the monomer (A) is a carboxyl group, and the basic group in the polymer (B) is an amino group. Active energy ray-curable resin composition. 3. The method according to claim 1, wherein the monomer (A) is a monomer having at least one acryloyl group or methacryloyl group in a molecule.
The active energy ray-curable resin composition according to the above. 4. The (A) monomer is a monomer having one carboxyl group and one or more acryloyl groups or methacryloyl groups in the molecule, and the (B) polymer is an amino group in the molecule. The active energy ray-curable resin composition according to claim 1, which is a polymer having a group and a hydrophilic group. 5. The method according to claim 1, wherein the polymer (B) is a polymer having a quaternary ammonium salt.
The active energy ray-curable resin composition according to any one of the above. 6. The active energy ray-curable resin composition according to claim 1, wherein the polymer (B) has a weight average molecular weight of 3,000 to 300,000. 7. The method according to claim 1, wherein the hydrophilic group in the polymer (B) is
Hydroxy group, alkoxy group, acid amide group, amino group,
The active energy ray-curable resin composition according to any one of claims 1 to 6, wherein the composition is at least one selected from a morpholino group, an ether group, a tetrahydrofurfuryl group, a glycidyl group, and a pyrrolidonyl group. 8. The activity according to claim 1, further comprising (C) a monomer having a polymerizable group and a hydrophilic group copolymerizable with the monomer (A). Energy ray-curable resin composition. 9. The active energy ray-curable resin composition according to claim 8, wherein the monomer (C) has a hydrophilic group and one or more acryloyl groups or methacryloyl groups. 10. The active energy ray-curable resin composition according to claim 1, further comprising a hydrophilic polymer. 11. The method according to claim 1, further comprising an organic filler and / or an inorganic filler.
The active energy ray-curable resin composition according to any one of the above. 12. The active energy ray according to claim 1, wherein the monomer (A) is contained in an amount of 1 to 250 parts by weight based on 100 parts by weight of the polymer (B). Curable resin composition. 13. A film made of the active energy ray-curable resin composition according to claim 1. Description: 14. A recording medium produced by using the active energy ray-curable resin composition according to claim 1. 15. An anti-fogging film produced by using the active energy ray-curable resin composition according to claim 1. Description: