JPH01123875A - Photocurable coating agent - Google Patents

Abstract

PURPOSE:To obtain the above highly brilliant one-pack coating agent excellent in storage stability, by adding a photocuring metallic pigment composition prepared by adding a coupling agent to a mixture of a specified metallic pigment (paste) with an ethylenically unsaturated compound. CONSTITUTION:A photocuring metallic pigment composition is obtained by adding a coupling agent (B) such as a silane, titanate, aluminum or zirconium coupling agent to a mixture (A) of a metallic pigment (paste) (a) obtained by treating a metallic pigment such as an Al powder or a copper-zinc powder with a higher fatty acid such as stearic acid with a compound (b), preferably, of a low viscosity, such as p-alkylphenol acrylate (ethylene oxide adduct). This composition is mixed with a binder such as an alkyd acrylate, a petroleum resin and, optionally, a photoreaction initiator, a sensitizer, a viscosity modifier, a flow improver, etc., to obtain the title coating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a photocurable coating containing a metal pigment that can be cured when irradiated with ultraviolet rays, electron beams, or the like.

(Prior art) Conventionally, in order to obtain printed matter with a metallic luster, one method is to print with an ink called metalworking ink that has adhesive properties on three surfaces, and then sprinkle gold powder on top of it.
Alternatively, many printing shops have used a method of mixing metal powder or metal pigment paste with a vehicle and printing as ink immediately before printing. However, these methods had problems in terms of work efficiency and environmental hygiene.

Since then, methods have been developed to prevent metal powder from turning black, improving storage stability, and a printing ink, generally called a one-component type, has been developed. For example, in JP-A-51-115105, a phenol-modified xylene resin obtained by reacting a xylene resin with a bifunctional p-alkylphenol and a tetrafunctional phenol is used. A gold ink for printing is prepared by dispersing a resin composition containing a group amine and a metal powder treated with stearic acid, and a gold ink for a heat-set rotary offset press is disclosed in JP-A-54-152503. ing.

However, there are ultraviolet curing inks (UV inks) and electron beam curing inks (EB inks) that are cured by ultraviolet rays or electron beams.
Ink), the vehicle used.

One-component gold ink is extremely prone to dark reactions.

It can be said that it is difficult to obtain silver ink, and furthermore, there is no silver ink that is satisfactory in terms of hue change over time.

(Problems to be Solved by the Invention) The present invention is characterized by treating a composition obtained by premixing a metal pigment or metal pigment paste with a prepolymer or monomer having an ethylenically unsaturated bond with a coupling agent. It was discovered that it exhibits good storage stability, leading to the present invention. - In liquid form.

Moreover, the present invention provides a photocurable coating material that achieves high brightness.

[Structure of the invention]

SUMMARY OF THE INVENTION The present invention provides a premixed mixture of metal pigments or metal pigment pastes treated with higher fatty acids and compounds that form ethylenically unsaturated double bonds.

The present invention is a photocurable coating material containing a photocurable metal pigment composition to which a bling agent is added.

The present invention is a photocurable coating material in which the coupling agent is at least one coupling agent selected from silane, titanate, aluminum, and zirconium.

Any metal pigment can be used as the metal pigment according to the present invention, and examples include aluminum powder and copper-zinc (brass) powder, which are the most commonly used. Metal pigments that are treated with higher fatty acids such as stearic acid and oleic acid can be used as the metal pigment. Furthermore, there are pastes that use a high boiling point solvent such as mineral spirit for this metal powder to improve handling and scattering properties.

Further, any prepolymer or monomer used to premix these gold powders and pastes may be used, and although not particularly limited, those with low viscosity are preferred from the viewpoint of good workability. For example, p
- Alkylphenol acrylates and acrylates of aliphatic polyhydric alcohols, as well as acrylates of aliphatic polyhydric alcohols.

Ethylene oxide (EO), propylene oxide (
These include those added with P O), those modified with fatty acids, and prepolymers diluted with these monomers.

The coupling agent used in the present invention is a silane-based, titanate-based, aluminum-based, or zirconium-based coupling agent. Preferably.

A silane-based or titanate-based coupling agent.

An example of these coupling agents will be given below.

Vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane.

N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-r-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ- Mercaptopropyltrimethoxysilane, vinyltrichlorosilane, T-chloropropylmethyldichlorosilane, γ-chloropropylmethyldimethoxysilane, T-chlorobutylmethyljethoxysilane, T-
Glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, T-ureidopropyltriethoxysilane, isopropyltriisostearoyltitanate, isopropyltridecylbenzenesulfonyltitanate, isopropyltris(
Dioctylpyrophosphate) titanate.

Tetraisopropyl bis(dioctyl phosphite) titanate Tetra octyl bis(ditridecyl phosphite) titanate Tetra(2,2-diallyloxymethyl-1-butyl) bis(di-tridecyl) phosphite titanate, tris(dioctyl pyrophosphate) ethyl Titanates, alkyl acetoacetates, aluminum diisopropylates, etc.

Inks, paints, etc. that are photocurable coating materials according to the present invention are inks, paints, etc. that are cured by irradiation with active energy rays such as ultraviolet rays and electron beams, and include prepolymers having ethylenically unsaturated double bonds, An ink mainly composed of oligomers and/or monomers, an ink mainly composed of a resin having no polymerizable unsaturated double bonds, and a monomer having polymerizable unsaturated double bonds.

Examples include inks mainly composed of prepolymers having polymerizable unsaturated double bonds.

In coating materials, alkyd acrylates, epoxy acrylates, urethane acrylates, diallyl phthalate prepolymers, phenyl novolanc-based polyfunctional allyl ethers, etc. are used as binders, but other materials such as petroleum resins, rosin-modified phenolic resins, etc. that do not have photocurability are used. There are some things. Furthermore, various photoreaction initiators and sensitizers can be mixed when curing using ultraviolet rays. Also organic to slightly change the hue.

Inorganic pigments can also be added. Other monomers or organic solvents may be mixed for viscosity adjustment. Furthermore, additives for improving fluidity and other physical properties may be mixed, and such additives include the various coupling agents described above.

The present invention will be explained below with reference to examples.

Example 1 A treated paste was prepared with the following weight ratios. In addition.

Gold powder and monomer were premixed in advance.

Gold powder 75 Nanatsuma-23 Coupling agent 2 The gold powder, monomer, and coupling agent in this formulation are as follows.

[Gold powder]

G1 Beer Gold 5550 (manufactured by Fukuda Kinzoku ■, No. 5 color gold powder) G2 #3000 Super Lynch Gold (manufactured by West German Ekal Co., Ltd., No. 7 color gold powder) [Monomer] Ml Aronifukus M-117 (manufactured by Toagosei ■).

Nanatsuma) M2 5R-355 (manufactured by American Sartomer).

monomer) M3 KAYARAD R-604 (Nippon Kayaku e
(manufactured by Nippon Unica, monomer) M4 NK ester A-BPE-4 (manufactured by Shin-Nakamura Chemical, monomer) [Coupling agent] CI Silicon A-1120 (manufactured by Nippon Unica, silane coupling agent) C02 Silicon KBM503 (manufactured by Shin-Etsu Chemical) ■Made by.

Silane coupling agent) C3 Silicon A-172 (manufactured by Nippon Unicar, silane coupling agent) C4TPT (manufactured by Mitsubishi Gas Chemical ■, titanium coupling agent) C5 Orgatysox ZA60 (manufactured by Matsumoto Pharmaceutical Co., Ltd., zirconium coupling agent) C6 aluminum chelate M (manufactured by Yoken Fine Chemical ■, aluminum coupling agent) [Prescription table] The treated paste thus obtained was mixed with the following medium to form an ink.

However, in Comparative Example 1-1, monomer M1 was added during ink formation, and in 1-7, monomer was added during ink formation, and C1 was added after ink formation. There is no difference in prescription.

[Mixing medium prescription]

KAYARAD DPHA (manufactured by Nippon Kayaku ■, monomer RIPOXY1519X2 (manufactured by Showa Kobunshi Kagaku ■).

Epoxy acrylate) 27 Irgacure 907 (manufactured by Ciba Geigy, photoreaction initiator) 3, ZZO 7
．． Non-2 This medium was obtained by kneading with three rolls, and by mixing it with the previously treated paste at a ratio of 1:1, a one-component all-ink was obtained.

The gold ink obtained in this way was checked for gelation after being left for a long time, and 0.4 cc of the ink was spread on coated cardboard using an R1 tester made by Mei Seisakusho. The results are shown below, where the cured type was rubbed off with the tip of a finger, and the brightness was measured using a gloss meter manufactured by Murakami Color Research Institute.

Also, products using metal pigment paste instead of gold powder also had excellent storage stability.

Example 2 A treated paste was prepared in the following proportions. Note that the aluminum paste and monomer were premixed in advance.

Aluminum paste 0231M (Aluminum paste manufactured by Toyo Aluminum ■) 50 monomers 48 coupling agents 2 The monomers and coupling agents in this recipe are as follows.

Similar to monomer example 1, M1 to M4. Further, the coupling agents were also 01 to C5, which were the same as in Example 1.

[Prescription table]

The treated paste thus obtained was mixed with the following medium to form an ink. However, in Comparative Example 2-1.

Coupling agent (C1) is added after ink formation, 2-2~
In No. 2-6, the monomer (Ml) was added at the time of ink formation, so that there was no difference in formulation between the example and the comparative example.

[Mixing medium prescription]

KAYARAD DPHA 20EBEC
RYL DEC657 (Belgium UCB company prepolymer) 35 Irgaki Yua 9
07 3benzophenone
2 This medium was obtained by kneading with three rolls, and a one-component silver ink was obtained by mixing this medium with the treated paste in a ratio of 6/4.

These were tested as in Example 1.

Also, products using aluminum powder instead of aluminum paste had excellent storage stability.

Claims (1)

[Claims] 1. A photocurable metal pigment composition obtained by adding a coupling agent to a mixture of a metal pigment or metal pigment paste treated with a higher fatty acid and a compound having an ethylenically unsaturated double bond. A photocurable coating material characterized by containing a substance. 2. The photocurable coating material according to claim 1, wherein the coupling agent is at least one coupling agent selected from silane, titanate, aluminum, and zirconium.