JPH0493367A - Photocurable coating material - Google Patents

Abstract

PURPOSE:To obtain the title material curable by exposure to ultraviolet rays or electron beams and excellent in printability, gloss, washability, etc., by using a monomer obtd. by reacting a butylene oxide adduct of a monocyclic phenol or an alicyclic hydroxy compd. with (meth)acrylic acid. CONSTITUTION:A monomer obtd. by reacting a butylene oxide adduct of a monocyclic phenol (e.g. phenol, cresol, t-butylphenol, catechol, or resorcinol) or an alicyclic hydroxyl compd. (e.g. tricyclodecane-mono-or dimethylol) with (meth)acrylic acid is used to prepare a photocurable coating material, which is curable by irradiating with to ultraviolet rays or electron beams and excellent in printability, gloss, washability, etc.

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 sexual coating agent.

(Prior Art) In recent years, research has been actively conducted on coating materials that can be cured by active energy rays, and among them, printing inks.

Practical applications are progressing in fields such as clear faces, paints, adhesives, and photoresists. These consist of a radically polymerizable monomer, a prepolymer, and 2 radical polymerization initiators and pigments as necessary.The prepolymers include alkyd acrylate and polyester acrylate.
Epoxy acrylate, urethane-modified acrylate, and other monomers.

Ethylene glycol diacrylate Acrylic acid esters of glycols such as triethylene glycol diacrylate and tripropylene glycol diacrylate,
Alternatively, there are acrylic acid esters of polyhydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol, such as glycerin diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and pentaerythritol 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. The publication discloses a composition in which a (meth)acrylate monomer in which an alkylene oxide is added to a phenol novolac is used in combination.

The physical properties required of recent active energy ray-curable coatings are 2. Printability, gloss, and washability (washed with white kerosene, 5.
There has been a demand for a level similar 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 monomer obtained by reacting a mononuclear phenol or a butylene oxide adduct of a hydroxyl group-containing alicyclic compound with acrylic acid or methacrylic acid. It is a photocurable coating material which further includes a prepolymer having a photocurable double bond and/or a resin having no photocurable double bond.

The mononuclear phenol according to the present invention is, for example, a compound represented by the following general formula.

R-P h-(OH), -3 (In the formula, R represents CP, H2,1I (n is 0 to 9), and Ph represents a phenyl group.) For example, phenol, alkyl (having 1 to 1 carbon atoms) 9) Phenols, such as cresol, t-butylphenol, octylphenol, nonylphenol, catechol, t-
Examples include butylcatechol, resorcinol, hydroquinone, and pyrogallol.

Further, examples of the hydroxyl group-containing alicyclic compound include a water-added compound of mononuclear phenol, tricyclodecane mono- or di-methylol, tricyclodecane mono- or di-alcohol, and the like.

More specifically, in the addition of butylene oxide, the reaction temperature is 180" under an alkali catalyst such as sodium hydroxide.
The addition is carried out between C and 160C.

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.

In the presence of these catalytic double polymerization inhibitors, the reaction is carried out while blowing air at a temperature below the temperature at which acrylic acid does not undergo thermal polymerization, 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 hydroxyl group of the mononuclear phenol or hydroxyl group-containing alicyclic compound. When the amount is less than this, the lipophilicity is low, and when it is more than this, the curability is deteriorated.

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

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

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

In addition to the monomer, the photocurable coating material of the present invention includes a compound having a photocurable double bond, that is, a prepolymer,
Other monomers can be used in combination.

Examples of prepolymers include epoxy acrylate,
Urethane acrylates include alkyd acrylates, diallyl phthalate prepolymers, and phenyl novolak-based polyfunctional allyl ethers. 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 include petroleum resins and rosin-modified phenolic resins, which are usually solid.

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 Resorcinol 1 was placed in a small autoclave equipped with a thermometer, nitrogen introduction device/butylene oxide introduction device, and stirring device.
10 parts, 2 parts of sodium hydroxide, 2 parts of butylene oxide
Charge 20 parts, replace the system with nitrogen while stirring, and bring to 160
The reaction is carried out gradually at °C and 5 kg/cij or less. After the reaction was completed, stirring was continued until the gauge pressure became 0.1 kg/cd or less, and 30 minutes were required for the two reactions.

330 parts of the obtained adduct and 144 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 fourth flask equipped with a stirrer, and the solvent was removed when the acid value reached 5.7. , pumped out. The obtained monomer is designated as A.

Synthesis Example 2 Add 200 g of tricyclodecane dimethylol to the apparatus of Synthesis Example 1.
parts, sodium hydroxide 2 parts, butylene oxide 220 parts
1 part was charged and reacted in the same manner as in Synthesis Example 1.

420 parts of the obtained adduct and 144 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. The obtained monomer having an acid value of 6.0 is designated as B.

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

286 parts of the obtained adduct and 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. The obtained monomer having an acid value of 5.0 is designated as C.

Synthesis Example 4 Add 200% tricyclodecane dimethylol to the apparatus of Synthesis Example 1.
1 part, 2 parts of sodium hydroxide, 174 parts of propylene oxide
5 parts were charged and reacted in the same manner as in Synthesis Example 1.

374 parts of the obtained adduct and 144 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, 33.5 parts of nonylic acid
1 part and 5 parts of xylene were placed in a four-round flask, 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 100
It was cooled to °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 over 1 hour using a dropping funnel. After 15 hours at 100°C, the acid value became 5.5. Desolvent and then pump.

This will be referred to as prepolymer E.

Synthesis Example 6 Ebicoat 1004 (epoxy resin manufactured by Shell Chemical Co., Ltd.)
58.8 parts of oleic acid, 41.2 parts of triethylenediamine, and 5 parts of xylene were placed in a four-loaf flask equipped with a stirrer, and reacted at 150°C for 71 hours under a nitrogen gas stream, and further at 200°C for 4 hours. 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 monomers and prepolymer resins obtained in the following two synthesis examples, a photocurable coating having the composition shown in the table below was prepared.

Table 1 A 10 cm area was irradiated under a single high pressure mercury lamp with an intensity of 7 cm at a conveyor speed of 100 ta/min. Also, Example 3. For Comparative Example 7, 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. For Comparative Example 8, a test coater was used to coat Maricoat paper (manufactured by Hokuetsu Paper Co., Ltd.) to a film thickness of 5 μm, and the gloss was measured by irradiating with the above-mentioned high-pressure mercury lamp at a conveyor speed of 50 m/min. Furthermore, the washability with a coater was tested.

The results are shown in Table-2.

Printing was performed using a WORD Heidelberg printing machine, and the number of sheets with stains on non-image areas during printing was measured.

Furthermore, Examples 1-2. 120 Effects of the Invention for Comparative Examples 5 and 6] 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] A photocurable coating material comprising a monomer obtained by reacting a mononuclear phenol or a butylene oxide adduct of a hydroxyl group-containing alicyclic 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.