JPH064801B2 - UV curable printing ink - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Object of the Invention" (Field of Industrial Application) The present invention relates to an ultraviolet curable printing ink having excellent adhesion to a substrate and curability printability.

(Prior Art) UV curable printing inks, paints, etc. have recently been attracting attention for energy saving, space saving, quick curing and pollution control, and their applications are rapidly expanding, but due to the drawback of poor adhesiveness. This is the current situation because its use in various plastics and various films is restricted. In particular, the adhesion to polyolefins, polyvinyl chloride, etc. was a problem.

Many UV-curable resins have been developed in order to improve the drawback of poor adhesiveness, but at present there are few UV-curable resins having sufficient adhesive curability.

Therefore, at present, it is general to make up for the lack of adhesive strength curability by subjecting the substrate to some treatment.

As the treatment on the base material, there are, for example, a method of directly changing the surface of the base material such as corona discharge treatment, flame treatment, and acid treatment, and a method of printing or applying an anchor coating agent.

However, the effect of corona discharge treatment is limited, and the substrates that can be treated are also limited.

The method of printing or painting the anchor coating agent on the substrate is
Adhesiveness to many types of substrates can be improved by selecting the anchor coating agent, and when combined with corona discharge treatment, the adhesiveness can be further improved. However, the method of applying the anchor coating agent to the substrate has additional steps, and has drawbacks in terms of workability and cost.

(Problems to be Solved by the Invention) The present invention has been made in consideration of such a situation.
The present invention relates to a UV-curable printing ink which has good adhesion to a film or sheet of polyolefin such as polyethylene and polypropylene, polyvinyl chloride, polyethylene terephthalate, etc. or other molded products or aluminum foil, and has excellent curability and printability. is there.

"Structure of the Invention" (Means for Solving Problems) The present invention comprises a monomer having three or more ethylenically unsaturated double bonds as a main component, and is selected from (iso) diallyl phthalate polymer and chlorinated polyethylene. The present invention relates to a UV-curable printing ink containing 1 to 10% by weight of an isocyanate compound in a composition containing a non-radical-reactive resin having no functional group that reacts with an isocyanate group as a main component.

Examples of the monomer having three or more ethylenically unsaturated double bonds used in the present invention include monomers used in general UV curable inks, that is, trimethylolpropane tri (meth) acrylate and trimethylol. (Meth) acrylate of trihydric or higher aliphatic polyhydric alcohol such as ethanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, or three or more (meth) acryloyl groups in one molecule It is possible to use a urethane-modified polyvalent acrylate or epoxy acrylate having Many of these monomers are usually liquid at room temperature.

In the present invention, a monomer having 3 or more ethylenically unsaturated double bonds is mainly used, but a monomer having 2 or less ethylenically unsaturated double bonds, that is, a (meth) acrylic acid ester, is mainly used for viscosity adjustment. , For example, ethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, 1,4 butanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) Aliphatic (meth) acrylates such as acrylate, dipropylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate, or their halogen-substituted or hydroxyl-substituted compounds can be used.

As the non-radical reactive resin having no functional group which reacts with the isocyanate group used in the present invention, (iso) diallyl phthalate polymer, chlorinated polyethylene and the like are used.

The isocyanate compound used in the present invention includes 2
・ 4-Tolylene diisocyanate, 2,6-Tolylene diisocyanate, Xylylene diisocyanate, Hexamethylene diisocyanate, Isophorone diisocyanate, Diphenylmethane-4.4 diisocyanate, Coronate L, Millionate MR, Coronate EH, Coronate HL (all four points above) It is possible to use a compound containing a terminal isocyanate group obtained by reacting an isocyanate compound with various polyether polyols, polyester polyols, polyamides, etc. manufactured by Nippon Polyurethane Industry Co., Ltd.

The pigments used in the present invention are azo pigments (Hanser Yellow, Benzidine Yellow, Laked C,
Carmine 6B, Permanent Red 2B, etc.), phthalocyanine-based pigments (phthalocyanine blue, phthalocyanine green, etc.), quinacridone-based pigments, isoindolinone-based, quinophthalone-based organic pigments, titanium white, carbon black, red iron oxide, alumina Inorganic pigments such as silica, talc, zinc white, and calcium carbonate can be used.

Examples of the photopolymerization initiator used as an additive in the present invention include benzoin ether types such as isobutyl benzoin ether, isopropyl benzoin ether, benzoin ethyl ether, and benzoin methyl ether, benzyl,
Benzyl ketal type compounds such as 2,2-dimethoxy-2-phenylacetophenone and hydroxycyclohexyl phenyl ketone, acetophenone derivatives such as diethoxyacetophenone and 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone and chlorothioxanthone. , 2-chlorothioxanthone, isopropylthioxane, etc., and a tertiary amine as a photosensitizer for promoting photopolymerization may be used in combination therewith.

Further, a thermal polymerization inhibitor such as hydroquinone, p-benzoquinone, phenothiazine or t-butylcatechol may be added to prevent gelation due to a dark reaction during production or storage.

Furthermore, metal compounds such as various activators, leveling agents, waxes, silicones, aluminum chelates, silane coupling agents, etc. in consideration of wetting with the base material as pigments and additives, leveling, improvement of film physical properties, misting, etc. Depending on the case, a small amount of organic solvent or the like can be added.

The composition of the UV-curable printing ink of the present invention comprises 20 to 90 monomers having 3 or more ethylenically unsaturated double bonds.
% By weight, 0 to 30% by weight of a monomer having 2 or less ethylenically unsaturated double bonds, 1 to 20% by weight of a non-radical reactive resin having no functional group which reacts with an isocyanate group, and 0 to 50% by weight of a pigment. , 1% to 30% by weight of an additive, and 1% to 10% by weight of an isocyanate compound, particularly 1% by weight of an isocyanate compound.
When it is less than 1, the adhesiveness to the substrate, particularly the adhesiveness at the time of storage or at high temperature and high humidity is deteriorated, which is not preferable. Further, even if it exceeds 10% by weight, the improvement of the adhesiveness reaches the limit, and gelation may occur during printing, which is not preferable. The isocyanate compound is usually mixed with the UV-curable component immediately before it is applied to the substrate (two-component type), but in some cases, it can be mixed with the UV-curable component at the same time.

Further, the above resin is mainly intended to improve printability, but if it exceeds 20% by weight, the viscosity becomes high and it is not suitable for printing. In addition, if a resin having reactivity with an isocyanate group such as an alkyd resin or an epoxy resin is used, the viscosity after the compound of the isocyanate compound increases remarkably and is not suitable for practical use.

From the viewpoint of storage stability, the isocyanate compound used in the present invention should be mixed as soon as possible before use. Furthermore, since the isocyanate compound has reactivity with water, dry offset or waterless offset printing is preferable. .

By using the ultraviolet curable printing ink of the present invention,
The following advantages occur.

1) Anchor coat becomes unnecessary and cost and productivity are improved.

2) It has a wide range of uses due to its excellent adhesion and curability.

3) Since it is a solvent-free type, it has little adverse effect on the base material, and because it is an ultraviolet curing type, there is no concern about deformation of the base material due to heat.

In the present invention, the ultraviolet curable printing ink of the present invention is printed on a substrate which is a polyolefin, polyvinyl chloride, polyester, aluminum foil, or a composite material thereof by a method such as a dry offset or a waterless offset, and a film is irradiated by ultraviolet rays. Cure.

Next, examples will be shown below in order to more specifically describe the present invention. In the examples, “part” means part by weight.

Production Example 1 Super Clone 507 (manufactured by Sanyo Kokusaku Pulp, chlorinated polyolefin) 25 parts, dipentaerythritol triacrylate propionate 70 parts, and hydroquinone 0.1 part were heated and dissolved while agitating to 100 ° C. while blowing air little by little, A viscous resin composition (I) having a viscosity of 4000 poise at 25 ° C. was obtained.

Production Example 2 Daiso Dup (Osaka Soda, diallyl phthalate polymer) 30 parts, dipentaerythritol triacrylate propionate 70 parts, and hydroquinone 0.1 part were heated and dissolved with stirring to 100 ° C. while blowing air little by little, and 25 ° C. To obtain a viscous resin composition (II) having a viscosity of 4000 poise.

Production Example 3 40 parts of Super Clone 507, A-BP manufactured by Shin Nakamura Chemical
60 parts of E-4 and 0.1 parts of hydroquinone were dissolved by heating while blowing air little by little to 100 ° C. with stirring to obtain a viscous resin composition (III) having a viscosity of 4000 poise at 25 ° C.

Production Example 4 Lipoxy SP-1509 (Showa High Polymer, epoxy acrylate prepolymer) 65 parts, dipentaerythritol triacrylate propionate 35 parts, and hydroquinone 0.1 part were heated and dissolved while blowing air at 25 ° C.
Viscous resin composition having a viscosity of 4000 poise (IV)
Got

Example 1 25 parts of the resin composition (I) obtained in Production Example 1, 20 parts of dipentaerythritol triacrylate propionate, 5 parts of benzyl, 50 parts of TYPAKE R-670 (manufactured by Ishihara Sangyo, titanium oxide), 3 parts An ink was formed using a roll, and 5 parts of Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd., an isocyanate compound) was blended to obtain an ultraviolet curable ink composition.

Using a RI tester, add this to a polyvinyl chloride sheet (thickness
0.3 mm) was developed, and ultraviolet rays were cured under the conditions of 80 w / cm two air-cooled mercury lamps and a passing speed of 30 m / min to obtain a printed matter.

Example 2 40 parts of the resin composition (I) obtained in Synthesis Example 1, 30 parts of dipentaerythritol triacrylate propionate, 4,
4-bis (diethylamino) benzophenone 5 parts, benzophenone 5 parts, Fines Red F2B (red pigment made by Toyo Ink Co., Ltd.) 20 parts were made into an ink using a three-roll mill,
5 parts of Coronate L was blended to obtain an ultraviolet curable ink composition.

This was color-developed in the same manner as in Example 1 to obtain a printed matter.

Example 3 The resin composition (II) obtained in Production Example 2 was used to form an ink in the same manner as in Example 2, and 7 parts of Coronate HL (manufactured by Nippon Polyurethane Industry Co., Ltd., an isocyanate compound) was blended to prepare an ultraviolet curable ink. A composition was obtained.

This was color-developed in the same manner as in Example 1 to obtain a printed matter.

Comparative Example 1 A printed matter was obtained in the same manner as in Example 1 except that 20 parts of Coronate L was added.

Comparative Example 2 A printed matter was obtained in the same manner as in Example 1 except that Coronate L was not blended.

Comparative Example 3 50 parts of the resin composition (III) obtained in Production Example 3, 20 parts of A-BPE-4 manufactured by Shin-Nakamura Chemical, 5 parts of 4,4-bis (diethylamino) benzophenone, 5 parts of benzophenone, Fines Red F2B20. Parts were made into an ink with three rolls, and 5 parts of Coronate L were blended to obtain an ultraviolet curable ink.

This was color-developed in the same manner as in Example 1 to obtain a printed matter.

Comparative Example 4 40 parts of the resin composition (IV) obtained in Production Example 4, 30 parts of dipentaerythritol triacrylate propionate, 4,
4-bis (diethylamino) benzophenone 5 parts, benzophenone 5 parts, Fines Red F2B 20 parts 3 parts
This roll was used to make an ink, and 5 parts of Coronate L was blended to obtain an ultraviolet curable ink composition.

This was color-developed in the same manner as in Example 1 to obtain a printed matter.

Comparative Example 5 70 parts of dipentaerythritol triacrylate propionate, 5 parts of 4,4-bis (diethylamino) benzophenone, 5 parts of benzophenone, Fines Red F2B
20 parts was made into an ink using a triple roll and 5 parts of Coronate L was blended to obtain an ultraviolet curable ink.

This was color-developed in the same manner as in Example 1 to obtain a printed matter.

The performance of the above inks and printed materials is shown below.

Claims (2)

[Claims] 1. A non-radical reactive resin having no functional group that reacts with an isocyanate group selected from a monomer having three or more ethylenically unsaturated double bonds, (iso) diallyl phthalate polymer, and chlorinated polyethylene. 1 to 1 of the isocyanate compound with respect to the composition as the component
An ultraviolet-curable printing ink, characterized by containing 10% by weight. 2. 20 to 90% by weight of a monomer having 3 or more ethylenically unsaturated double bonds, 0 to 30% by weight of a monomer having 2 or less ethylenically unsaturated double bonds, and (iso) diallyl phthalate. Polymer, non-radical reactive resin having no functional group reacting with isocyanate group selected from chlorinated polyethylene 1 to 20% by weight, pigment 0 to 5
The ultraviolet-curable printing ink according to claim 1, wherein an isocyanate compound is mixed in an amount of 1 to 10% by weight with respect to a composition of 0% by weight and an additive of 1 to 30% by weight.