JPH0489872A - Photo-setting covering material - Google Patents

Abstract

PURPOSE:To form a photo-setting covering material excellent in printability, gloss, cleanability, etc., by using a monomer obtained by reacting a butylene oxide adduct of a hydroxylated aliphatic compound with (meth)acrylic acid. CONSTITUTION:A photo-setting covering material containing a monomer obtained by reacting a butylene oxide adduct of a hydroxylated aliphatic compound with (meth)acrylic acid. Examples of the hydroxylated aliphatic compound include monohydric and polyhydric alcohols, such as methanol, hexanediol, glycerin, pentaerithritol, and sorbitol. In addition to the monomer, a prepolymer having photo-setting double bonds and/or a resin having no photo-setting double bonds can be used in combination in the above-mentioned covering material.

Description

[Detailed Description of the Invention] [Objective of the Invention] (Industrial Application Field) The present invention is a photocurable material that cures when irradiated with ultraviolet rays or electron beams, and has excellent printability, gloss, and washability. The present invention relates to a coating material.

(Prior art) In recent years, research into curable coatings using activated Z-rays has been actively conducted, and practical applications are progressing in the fields of printing ink clear varnishes, paints, adhesives, photoresists, etc. ing. These are radically polymerizable monomers,
It consists of a prepolymer and, if necessary, a radical polymerization initiator and a pigment.The prepolymer includes alkyd acrylate, polyester acrylate, epoxy acrylate, urethane-modified acrylate, etc., and the monomer includes ethylene glycol diacrylate and triethylene glycol. Acrylic esters of glycols such as diacrylate and tripropylene glycol diacrylate, or acrylic esters of polyhydric alcohols such as glycerin, trimethylolprohane, and pentaerythritol, such as glycerin diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, penta Examples include erythritol tetraacrylate.

There are also acrylates in which ethylene oxide or propylene oxide is introduced in order to impart flexibility after one polymerization.

For example, JP-A-53-11925 discloses a (meth)acrylate motsumer obtained by adding ethylene oxide or propylene oxide to pentaerythritol. Other (meth)acrylate monomers introduced into alkylene oxide include
Publication No. 22333 describes the addition of ethylene oxide or propylene oxide to a mononuclear polyhydric phenol (meth).
Acrylate monomers are disclosed. Furthermore, Japanese Patent Publication No. 60-28288 discloses a (meth)acrylate monomer of an alkylene oxide adduct to a phenol derivative substituted with a monovalent hydrocarbon group having an aromatic group.

Further, JP-A-57-51768 discloses a composition in which a (meth)acrylate monomer in which an alkylene oxide is added to a phenol novolac is used in combination.

Recent physical properties required of active energy ray-curable coating materials include printability, gloss, and washability (easy to wash with white kerosene), which are at a level close to that of oil-based inks.

However, the conventional monomer composition cannot satisfy the above-mentioned level, and the actual situation is that the scope of application of the curable coating material is narrowed.

(Problems to be Solved by the Invention) The present invention provides a photocurable coating material that is excellent in printability, gloss, washability, etc.

[Structure of the Invention] (Means for Solving the Problems) The present invention provides a photocurable coating material containing a 7-mer, which is obtained by reacting a butylene oxide adduct of a hydroxyl group-containing aliphatic compound with acrylic acid or methacrylic acid. and a photocurable coating further comprising a prepolymer having a photocurable double bond and/or a resin having no photocurable double bond.

The hydroxyl group-containing aliphatic compound according to the present invention includes:

Monohydric or higher alcohols, such as aliphatic monohydric alcohols such as methanol, hexanol, and lauryl alcohol; aliphatic 2 alcohols such as hexanediol and neopentyl glycol;
Trihydric alcohol, trimethylolpropane 5 Trihydric alcohol such as glycerin, tetrahydric alcohol such as pentaerythritol, ditrimethylolpropane, sorbitol,
Examples include alcohols having a valence of 6 or more, such as dipentaerythritol.

More specifically, in the addition of butylene oxide, the reaction temperature is 180° under an alkali catalyst such as sodium hydroxide.
It is added between C-160°C.

In the acrylic esterification reaction, any of sulfuric acid, paratoluenesulfonic acid, etc. may be used as a catalyst.

Further, as a polymerization inhibitor, hydroquinone, hydroquinone 7-methyl ether, etc. can be used.

The reaction is carried out while blowing air at a temperature below the temperature at which acrylic acid is not thermally polymerized in the presence of the catalyst (1) and the polymerization inhibitor (2), usually in the range of 80 to 110°C. The azeotropic solvent used at this time may be organic solvents that form azeotropic compounds with water, such as benzene, toluene, xylene, n-hexane, methyl isobutyl ketone, etc., and are substantially immiscible with water, either alone or in mixtures. obtain.

The number of moles of butylene oxide added is preferably 1 to 10 moles, particularly preferably 1.5 to 3 moles, per one hydroxyl group of the hydroxyl group-containing aliphatic compound.

If the amount is less than this, the lipophilicity is low, and if it is more than this, the lipophilicity is low.
Curability deteriorates.

The reaction amount of acrylic acid or methacrylic acid is (meth)
The carboxyl group of acrylic acid/hydroxyl group of the butylene oxide adduct is about -1.1 to 0.9.

Applications include, for example, clear coatings for various raw materials, coatings that do not contain pigments such as overprint faces, and furthermore, for example, offset inks.

It can be used in photocurable coatings such as color coatings containing pigments such as silk screen inks.

The photocurable coating material of the present invention includes a compound having a photocurable double bond, that is, a prepolymer,
Other nanatsumers can be used in combination.

As a prepolymer, 9 e.g. epoxy acrylate
Examples include urethane acrylate alkyd acrylate, diallyl phthalate prepolymer, and phenyl novolak-based polyfunctional allyl ether. In addition, when curing with ultraviolet rays, a photoreaction initiator and a sensitizer can be mixed. In addition, organic solvents, additives, and various non-photocurable resins may be used in combination as necessary.

Examples of resins that do not have photocurable double bonds are 1. Usually solid, 5. Petroleum resins, and rosin-modified phenolic resins.

These include Epon ester resin, acrylic resin, diallyl phthalate resin, etc.

(Examples) The present invention will be explained below with reference to synthesis examples and examples. Example: Middle part means parts by weight, and 2% means percent by weight.

Synthesis Example 1 In a small autoclave equipped with a thermometer, a nitrogen introduction device/butylene oxide introduction device, and a stirring device.

134 parts of trimethylolpropane, 2 parts of sodium hydroxide
and 296 parts of butylene oxide, and while stirring, purged the system with nitrogen, and heated to 160'C, 5kg/afl.
The reaction is carried out gradually as follows. Gauge pressure after reaction completion: 0.1
Continue stirring until the concentration is below 30 kg/d for one reaction.
It took minutes.

430 parts of the obtained adduct, 195 parts of acrylic acid, 0.6 parts of hydroquinone, 6 parts of p-toluenesulfonic acid, and 60 parts of cyclohexane were reacted at 100°C for 15 hours while blowing air in a four-bottle flask equipped with a stirrer, and the acid When the value reached 5.7, the solvent was removed and pumped out. The obtained monomer is designated as A.

Synthesis Example 2 254 parts of dipentaerythritol, 2 parts of sodium hydroxide, and 370 parts of butylene oxide were charged into the apparatus of Synthesis Example 1 and reacted in the same manner as in Synthesis Example 1.

624 parts of the obtained adduct, 390 parts of acrylic acid, 0.9 parts of hydroquinone, 9 parts of P-toluenesulfonic acid, and 90 parts of cyclohexane were reacted in the same manner as in Synthesis Example 1. Obtained acid value 6. Let B be the monomer of O.

Synthesis Example 3 In the apparatus of Synthesis Example 1, 110 parts of resorcin, 2 parts of sodium hydroxide, and 176 parts of ethylene oxide were charged and reacted in the same manner as in Synthesis Example 1.

286 parts of the obtained adduct, 130 parts of acrylic acid, 0.6 parts of hydroquinone, 6 parts of p-toluenesulfonic acid, and 60 parts of cyclohexane were reacted in the same manner as in Synthesis Example 1. Obtained acid value5. Let C be the monomer of O.

Synthesis Example 4 134 parts of trimethylolpropane, 2 parts of sodium hydroxide, and 232 parts of propylene oxide were charged into the apparatus of Synthesis Example 1 and reacted in the same manner as in Synthesis Example 1.

366 parts of the obtained adduct, 195 parts of acrylic acid, 0.5 parts of hydroquinone, 5 parts of p-toluenesulfonic acid, and 50 parts of cyclohexane were reacted in the same manner as in Synthesis Example 1. The obtained monomer having an acid value of 5.1 is designated as D.

Synthesis Example 5 31.6 parts of trimethylolpropane, / 2) L43
3.5 parts of xylene and 5 parts of xylene were placed in four flasks and reacted under a nitrogen gas stream at 200°C until the acid value reached 5. When the acid value reached 1.0, the solvent was removed. , and then cooled to 100°C (this is referred to as intermediate M).

Furthermore, 5 parts of cyclohexane, 0.1 part of hydroquinone p
-) 1 part of luenesulfonic acid was charged, and while blowing air, 15.3 parts of acrylic acid was added to the chemical IPF using a dropping funnel, and after 15 hours at 100"C, the acid value was 5.5.
So, remove the solvent and then pump it out.

This will be referred to as prepolymer E.

Synthesis Example 6 Epicoat 1004 (epoxy resin manufactured by Shell Chemical Co., Ltd.)
58.8 parts 2 41.2 parts of oleic acid, 0.1 part of triethylenediamine, and 5 parts of xylene were charged into a four-loaf flask equipped with a stirrer, and reacted at 150°C for 11 hours under a nitrogen gas stream, and further heated at 200°C, 4 parts. Let time react.

It was pumped out when the acid value reached 5.5. The obtained non-radically polymerizable resin is designated as F.

Using the prepolymer resin obtained in Synthesis Example 1 below, photocurable coatings having the compositions shown in the table below were prepared.

The sample was irradiated at a distance of 10 cm under a high-pressure mercury lamp I lamp with an intensity of /cm at a conhair speed of 100 w+/min. Also, Example 3. For Comparative Example 8, irradiation was performed at 10 Mrad using a curtain beam type electron beam irradiation device.
hardened. Thereafter, the gloss value was measured using a Murakami Color Gloss Needle 60-60. Additionally, after printing, the cleaning performance of the printing press with white kerosene was tested.

Also, Example 4. Comparative Example 9 was coated with a test coater to a film thickness of 5 μm on Maricoat paper (manufactured by Hokuetsu Paper Co., Ltd.), irradiated with the above-mentioned high-pressure mercury lamp at a speed of 50 m/min, and the gloss was measured. Furthermore, the washability with a coater was tested.

The results are shown in Table-2.

Coating Examples 1 to 3 shown in Table-1. KO Comparative Examples 5 to 8
Printing was performed using an RD Heidelberg printing machine, and the number of sheets with stains on non-image areas during printing was measured.

Furthermore, Examples 1-2. 120 oath for Comparative Examples 5 to 7 [
Effects of the Invention] The photocurable coating material of the present invention has excellent printability, gloss, and washability, and can expand its range of application.

Claims (1)

[Scope of Claims] 1. A photocurable coating material containing a monomer obtained by reacting a butylene oxide adduct of a hydroxyl group-containing aliphatic compound with acrylic acid or methacrylic acid. 2. The photocurable coating material according to claim 1, further comprising a prepolymer having a photocurable double bond and/or a resin having no photocurable double bond.