JPH08192569A - Photosensitive resin composition and receiving material using the same - Google Patents

Abstract

PURPOSE: To provide a photosensitive resin compsn. excellent in ink drying properties, durability, feed properties or curl properties when the cured matter of the resin compsn. is used in the ink receiving layer of a receiving material of an ink jet recording system. CONSTITUTION: A photosensitive resin compsn. contains a polymer A composed of a compsn. containing a monofunctional monomer (a) containing tertiary or quaternary nitrogen and a hydrophilic monomer (b) other than the component (a), a hydrophilic monofunctional monomer (B), an ethylenically saturated group- containing compd. (C) other than the component (B) and a photopolymerization initiator (D).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition and a recording material using the same. More specifically, regarding a recording material suitably used in the inkjet recording method,
In particular, the present invention relates to a recording material having excellent ink absorbency, light resistance, and bleeding prevention under high temperature and high humidity.

[0002]

2. Description of the Related Art Ink jet recording methods include various ink (recording liquid) ejection methods, for example, an electrostatic suction method, a method in which a piezoelectric element is used to mechanically vibrate or displace ink, and ink is heated to foam. By using the pressure, etc., small droplets of ink are generated and ejected, and some or all of them are attached to a recording material such as paper for recording, but high-speed printing, multicolor printing It is attracting attention as a printing method. As a recording material suitable for full-color recording, an inkjet paper having a porous layer formed by coating a pigment such as silica on a paper surface or a resin that absorbs ink by dissolution or swelling is a plastic substrate (for example, polyester, A molded product such as polymethylmethacrylate or polycarbonate, a film, or the like, which is applied by coating or printing, has been used. For example, there is an OHP (overhead projector) film for inkjet.

[0003]

[Problems to be Solved by the Invention] OH for inkjet
P film is usually on a transparent plastic film,
An ink absorption layer made of a hydrophilic resin is provided, and the ink used for recording is absorbed by the swelling or dissolution of the resin. In this case, the printed surface is non-porous and a transparent image can be obtained. However, the absorption layer made of such a hydrophilic resin is usually soluble in water in many cases, and the image is easily destroyed when the image is exposed to water. Further, even when the ink absorbing layer itself is not dissolved in water, when the image is immersed in water, the ink absorbing layer swells, and the dye forming the image easily escapes into water, resulting in a water resistant image. There is a drawback that it is not possible to obtain sex. In order to eliminate such a defect, usually, as the dye of the inkjet ink, a direct dye or an acid dye is often used. Therefore, it is preferable to include a cationic dye fixing agent in the ink absorbing layer. Considered (JP-A-61-2610)
However, usually, the dye fixing agent that can be contained in the hydrophilic resin is often water-soluble in itself, and the portion bonded to the dye becomes water-insoluble, but the other portion. Is water-soluble, and it becomes difficult to obtain water resistance as a film of the ink absorbing layer. Further, Japanese Patent Laid-Open No. 61-10438 discloses a cation-modified polyvinyl alcohol (PV) as a water-soluble polymer in an ink absorbing layer.
It has been proposed to include A) or a crosslinked product thereof. In this case, just by adding the cation-modified PVA, the water resistance of the ink absorbing layer itself cannot be obtained as in the case of the cationic dye fixing agent. On the other hand, cation-modified PV
When A is crosslinked, although water resistance of both the ink absorption layer and the image can be obtained, cation-modified PVA must be used as the water-soluble polymer, and the material selection range is narrow and the ink absorption layer is It is difficult to increase the ratio of the cationic groups in (3), and there is a problem that sufficient water resistance cannot be obtained when the amount of dye (ink) used for recording is large. Therefore, the object of the present invention is to
It is an object of the present invention to provide a recording material which has water resistance, is excellent in ink absorption, and can obtain an image having clear and beautiful transparency or high gloss when recording by an inkjet method.

[0004]

Means for Solving the Problems That is, the present invention provides: 1) a composition containing a monofunctional monomer (a) containing a tertiary nitrogen or a quaternary nitrogen and a hydrophilic monomer (b) other than the component (a). A polymer (A), a hydrophilic monofunctional monomer (B), and an ethylenically unsaturated group-containing compound (C) other than the components (B) and a photopolymerization initiator (D). Photosensitive resin composition, 2) The hydrophilic monofunctional monomer (B) is acryloylmorpholine, N-vinylcaprolactam, 2-hydroxyethyl (meth) acrylate, dimethylamino (meth) acrylamide. 1) The photosensitive resin composition according to item 3, 3) The photosensitive resin composition according to item 1), wherein the ethylenically unsaturated group-containing compound (C) is bis (acryloxyethyl) hydroxyethyl isocyanurate, 4) Plastic A recording material having an ink receiving layer provided on a base material, wherein the material constituting the ink receiving layer is a cured product of the photosensitive resin composition described in 1), 2) and 3). Regarding materials

The polymer (A) used in the present invention contains a monofunctional monomer (a) containing a tertiary nitrogen or a quaternary nitrogen and a hydrophilic monomer (b) other than the component (a) as essential components. It is a polymer of the composition. Specific examples of the monofunctional monomer (a) containing tertiary nitrogen or quaternary nitrogen include (N, N-dimethylamino) ethyl (meth) acrylate, (N, N-diethylamino) ethyl (meth) acrylate, and the like. 3- (N, N-dimethylamino) propyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylamide, (N, N-diethylamino) ethyl vinyl ether, 4-vinylpyridine, and the like. However, a (meth) acrylamide-based monomer is preferable from the viewpoint of stability, etc.
Alternatively, two or more kinds are mixed and used.

The hydrophilic monomer (b) is, for example, hydroxy (C ₁ -C ₄ ) alkyl (meth) acrylate such as hydroxyethyl (meth) acrylate,
(Meth) acrylamide, dimethylamino (meth) acrylamide, methylamino (meth) acrylamide, etc., which may have one or two (C ₁ -C ₄ ) alkyl groups bonded thereto, vinylpyrrolidone, etc. Can be mentioned. These hydrophilic monomers may be used alone or in combination of two or more. If necessary, (a)
And a monofunctional monomer (c) other than the component (b), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid, styrene. , P-methylstyrene and the like. (A),
The mixing ratio of the components (b) and (c) is 2 for the component (a).
0 to 70% by weight, preferably 25 to 60% by weight, the component (b) is 10 to 60% by weight, preferably 20 to 50% by weight,
The component (c) is preferably 0 to 50% by weight, more preferably 0 to 40% by weight. The components (a), (b) and (c) can be polymerized by a conventionally known solution polymerization method. For example, (a),
The components (b) and (c) are mixed with a polymerization initiator (eg, azobisisobutyronitrile) in a solvent (eg, a suitable organic solvent such as methylcello rib, methyl ethyl ketone, dioxane, etc.), and a nitrogen gas stream is used. In reaction temperature 60-1
It can be obtained by reacting at 00 ° C.

Specific examples of the hydrophilic monofunctional monomer (B) used in the present invention include acryloylmorpholine, N-vinylcaprolactam, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. , Carbitol (meth) acrylate, N-vinylpyrrolidone (meth) acrylamide, dimethylamino (meth) acrylamide, 2-hydroxy-3-phenyloxypropyl (meth) acrylate,
(N, N-Dimethylamino) ethyl (meth) acrylate, (N, N-diethylamino) ethyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylamide and the like are mentioned, and particularly preferable. Examples thereof include acryloylmorpholine, N-vinylcaprolactam, 2-hydroxyethyl (meth) acrylate, dimethylamino (meth) acrylamide and the like.

Specific examples of the ethylenically unsaturated compound (C) include tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, bis (acryloxyethyl) hydroxyethyl isocyanurate, for example, Toagosei Chemical Industry. Co., Ltd., Aronix M-215), polyethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like, but preferred Examples thereof include bis (acryloxyethyl) hydroxyethyl isocyanurate and the like.

Any known photopolymerization initiator may be used as a specific example of the photopolymerization initiator (D) used in the present invention. For example, 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, benzyldimethylketal, 1
-Hydroxycyclohexyl phenyl ketone, benzophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1,2,4,6-trimethylbenzoylphenylphosphine oxide and the like can be mentioned. The photopolymerization initiator can be used in combination with an accelerator such as a tertiary amine.

The proportion of each component of the photosensitive resin composition of the present invention used is 5 to 40% by weight of the polymer (A) component.
It is particularly preferably 10 to 30% by weight. The hydrophilic monofunctional monomer (B) component is 30 to 80% by weight, particularly preferably 40 to 75% by weight. The ethylenically unsaturated group-containing compound (C) component is 5 to 60% by weight, particularly preferably 10 to 40% by weight. The photopolymerization initiator (D) component is 0.1 to 20% by weight, particularly preferably 3 to 10%.
% By weight.

The photosensitive resin composition of the present invention comprises (A),
It can be prepared by heating, dissolving and mixing the components (B), (C) and (D).

The recording material of the present invention includes various plastic substrates (for example, polyester resin, diacetate resin, triacetate resin, acrylic resin, polycarbonate resin, polyvinyl chloride resin, polyimide resin, cellophane, (Celluloid etc.) as an ink receiving layer, the photosensitive resin composition of the present invention is applied to a thickness of 1 to 100 μm and irradiated with ultraviolet rays to cure the applied photosensitive resin composition to form an ink receiving layer. Can be made.

The photosensitive resin composition of the present invention may further contain, if necessary, fillers such as silica, clay, talc, diatomaceous earth, calcium carbonate, barium sulfate, aluminum silicate, synthetic zeolite and alumina. It is also possible to add additives such as an antioxidant, an antifoaming agent, a leveling agent, a light stabilizer and a polymerization inhibitor. The photosensitive resin composition of the present invention is suitable for an ink receiving layer of a recording material for an ink jet recording system.

[0014]

The present invention will be described below in detail with reference to examples. In the text, parts and% are based on weight. (Synthesis Example of Polymer (A)) Synthesis Example 1 3- (N, N-dimethylamino) propylmethacrylamide 16 parts, dimethylacrylamide 10 parts, 2-hydroxyethyl methacrylate 10 parts, methyl acrylate 12 parts, azobisisop After 0.2 part of tyronitrile and 200 parts of methyl cellosolve were charged and nitrogen gas was passed through for 1 hour, the mixture was heated and stirred at 70 ° C. for 4 hours to carry out a polymerization reaction. After the completion, the reaction mixture was poured into a large amount of cyclohexane to precipitate the product. Next, cyclohexane containing the reaction solvent was removed by decantation, the reaction product was dried under reduced pressure, and the polymer (refractive index (25 ° C.) 1.5
10) 44 parts were obtained.

Synthesis Example 2 20 parts of 3- (N, N-dimethylamino) propylmethacrylamide, 2-hydroxyethyl methacrylate 20
Parts, 10 parts of methyl methacrylate, 0.3 parts of azobisisobutyronitrile and 200 parts of methyl cellosolve were charged, nitrogen gas was passed for 1 hour, and then heating and stirring were continued at 70 ° C. for 4 hours to carry out a polymerization reaction. After the completion, the reaction mixture was poured into a large amount of cyclohexane to precipitate the product. Next, cyclohexane containing the reaction solvent was removed by decantation, and the reaction product was dried under reduced pressure to obtain 46 parts of a polymer (refractive index (25 ° C.) 1.512).

Examples 1 to 4 and Comparative Examples 1 to 2 A photosensitive resin composition was prepared according to Table 1 and had a thickness of 10
A 0 μm polyethylene terephthalate film was coated by a bar coater method so that the film thickness after curing was 7 μm, and the coating film was cured by irradiating ultraviolet rays to prepare a recording material, and this recording material was used. Various evaluations (ink drying time, durability, transportability, absorptivity, curl property) were performed.
The ink used for recording on the recording material using the inkjet recording apparatus is yellow ink (CI Direct Yellow 8
6 2 parts, a mixture of 20 parts of diethylene glycol, 10 parts of polyethylene glycol # 200 and 70 parts of water),
Red ink (CI Acid Red 35 2 parts, diethylene glycol 20 parts, polyethylene glycol # 20
0 Mixture of 10 parts and 70 parts of water. ) Blue ink (CI Direct Blue 86 2 parts, diethylene glycol 20 parts, polyethylene glycol # 2)
Mixture of 10 parts of water and 20 parts of water) Black ink (C.
I. Food Black 2 2 parts, diethylene glycol 2
0 parts, 10 parts of polyethylene glycol # 200 and 70 parts of water).

Evaluation Method Ink Dryness: The recording material after recording was subjected to room temperature (20
When the recorded image was touched with a finger after being left at 65 ° C. (RH: 65% RH), the time until the ink dries and does not adhere to the finger was measured, and represented by ◯, Δ, and x. ○ ・ ・ ・ ・ Time to dry and no longer stick to fingers 4
It was less than a minute. △ ・ ・ ・ ・ Time until it no longer adheres to dry fingers is 4
It was between -10 minutes. × ・ ・ ・ ・ Time to dry and no longer stick to fingers 1
It was 0 minutes or more. Durability: After recording, the recording material after the ink was dried was observed for an appearance after standing for 500 hours at 80 ° C. and 80% RH. ○ ・ ・ ・ ・ There is no abnormality in the recorded image. × ... Bleeding occurred in the recorded image. Transportability: When the recording material is mounted on the printer under the condition of 35 ° C. and 85% RH, the surface of the ink receiving layer is sticky, so that it cannot be transported by the feed roller of the printer and cannot be recorded. Was marked as ○. Water absorption rate: According to Table 1, the photosensitive resin composition was applied to chin-free steel with a thickness of 200 μm using a bar coder,
The cured film was irradiated with ultraviolet rays and cured, and the cured film was immersed in water at 25 ° C. for 24 hours, taken out from the water, thoroughly wiped off the water, and the amount of water in the cured film was measured by the Karl Fischer method. Curl property: The curl state of the recording material prepared was observed. ○ ・ ・ ・ ・ No curl. △ ・ ・ ・ ・ The curl is very small. × ・ ・ ・ ・ The curl is large.

[0018]

Table 1 Examples Comparative Examples 1 2 3 4 1 2 (A) Component Polymer 20 20 20 Obtained in Synthesis Example 1 Polymer 20 20 20 (B) Component Acryloylmorpholine 120 100 60 50 140 N-Vinylcaprolactam 60 2-Hydroxyethyl methacrylate 30 30 Dimethylaminoacrylamide 50 (C) component bis (acryloxyethyl) hydroxyethyl isocyanurate 20 30 20 30 140 (D) component 1-hydroxycyclohexyl phenyl ketone 7 8 7 8 7 7 Ink drying ○ ○ ○ ○ × × ○ Durability ○ ○ ○ ○ ○ × Transportability ○ ○ ○ ○ ○ × × Water absorption rate (%) 112 86 75 90 60 130 Curling property ○ ○ ○ ○ × ○

As is clear from the evaluation results shown in Table 1, it is clear that the cured product of the photosensitive resin composition of the present invention is excellent in ink drying property, durability, transportability, curl property and the like.

[0020]

The photosensitive resin composition of the present invention, when the obtained cured product is used in the ink receiving layer of a recording material of an ink jet recording system, ink drying property, durability, transportability, curl property, etc. Is excellent.

Claims (4)

[Claims] 1. A polymer (A), which is hydrophilic and monofunctional with a composition containing a monofunctional monomer (a) containing a tertiary nitrogen or a quaternary nitrogen and a hydrophilic monomer (b) other than the component (a). A photosensitive resin composition comprising a functional monomer (B), an ethylenically unsaturated group-containing compound (C) other than the component (B), and a photopolymerization initiator (D). 2. The photosensitive resin composition according to claim 1, wherein the hydrophilic monofunctional monomer (B) is acryloylmorpholine, N-vinylcaprolactam, 2-hydroxyethyl (meth) acrylate, dimethylamino (meth) acrylamide. 3. The photosensitive resin composition according to claim 1, wherein the ethylenically unsaturated compound (C) is bis (acryloxyethyl) hydroxyethyl isocyanurate. 4. A recording material comprising an ink receiving layer provided on a plastic substrate, wherein the material constituting the ink receiving layer is a cured product of the photosensitive resin composition according to claim 1. Recording material.