JPH02150465A - Coating agent and printing ink curable with actinic energy radiation - Google Patents

Abstract

PURPOSE:To obtain the subject coating agent having excellent printability, adhesivity, etc., by reacting a univalent carboxylic acid anhydride with a (hydroxyl-containing) ester of (meth)acrylic acid, removing by-produced univalent carboxylic acid and using the product as a component. CONSTITUTION:The objective coating agent contains a substance produced by reacting (A) a hydroxyl-containing ester derived from (meth)acrylic acid and a compound capable of forming an ester with (meth)acrylic acid with (B) a univalent carboxylic acid anhydride and removing the by-produced univalent carboxylic acid from the reaction product. Preferably, the above product is added with a monomer having radically polymerizable double bond and, as necessary, further with a radical polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION Object of the Invention (Field of Industrial Application) The present invention relates to an active energy ray-curable coating and a printing ink. Moreover, the present invention relates to active energy ray-curable coatings and printing inks that have excellent printability, adhesion to substrates, and the like.

(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 are composed of a radically polymerizable resin and monomer, and if necessary, a radical polymerization initiator and an R material.

Examples of resins with radical polymerizability include alkyd (meth)acrylate, polyester (meth)acrylate,
Epoxy (meth)acrylate, urethane modified (meth)
Acrylate, etc., and monomers include bisphenol A alkylene oxide adduct di(meth)acrylate, neopentyl glycol di(meth)acrylate,
trimethylolpropane tri(meth)acrylate,
tetramethylolmethanetetra(meth)acrylate,
dipentaerythritol hexa(meth)acrylate,
Alkylphenol alkylene oxide adduct mono
(Meth)acrylate etc. were used. Note that in this specification, (meth)acrylate refers to acrylate and/or methacrylate, and (meth)acrylic acid refers to acrylic acid and/or methacrylic acid.

Recently, there has been a desire for faster printing and painting, and in order to meet these demands, active energy ray-curable coatings often use radically polymerizable resins or acrylic esters, which cure rapidly as monomers. . However, these acrylic esters have residual hydroxyl groups, and when used as a curable coating material, for example in an offset printing ink that uses dampening water, the ink tends to emulsify, resulting in staining.

Floating stains often occur, and adhesion to treated or untreated various metals, plastics, and other substrates is poor, and improvements are desired.

(Problems to be Solved by the Invention) The present invention provides an active energy ray-curable coating and a printing ink that solve the above-mentioned stains during printing, poor transfer, and adhesion to substrates. be.

"Structure of the Invention" (Means for Solving the Problems) The present invention has been made as a result of intensive research to improve these drawbacks.
We have discovered active energy ray-curable coatings and printing inks that have excellent printability and adhesion to substrates.

That is, the present invention involves reacting a compound that undergoes an esterification reaction with acrylic acid and/or methacrylic acid (hereinafter referred to as (meth)acrylic acid) and an esterified product of (meth)acrylic acid with a monohydric carboxylic anhydride. , an active energy ray-curable coating material containing a product obtained by removing by-produced monovalent carboxylic acids, and an active energy ray-curable coating material further containing a monomer having a radically polymerizable double bond and, if necessary, a radical polymerization initiator. Line-curable coatings and products thereof.

The present invention relates to an active energy ray-curable printing ink containing a monomer having a radically polymerizable double bond, a pigment, and optionally a radical polymerization initiator.

The active energy ray-curable coating material in the present invention is as follows.

It is a substance that can be a trivalent polymer, an oligomer, or a prepolymer, and is a monovalent carboxylic acid by-produced by reacting an esterified product of (meth)acrylic acid and a compound that undergoes an esterification reaction with a monovalent carboxylic acid anhydride. obtained by removing.

The compound that undergoes an esterification reaction with (meth)acrylic acid is an alcohol having a negative value or higher. In addition, when obtaining a prepolymer as an active energy ray-curable coating material, 5
For example, it is a product obtained by crosslinking an alcohol having a value of - or more with a polybasic acid and esterifying the remaining hydroxyl groups with (meth)acrylic acid. In addition, in these reactions, monovalent carboxylic acid may be used in combination.

Examples of alcohols having a value greater than or equal to - are aliphatic alcohols having 1 to 18 carbon atoms, benzyl alcohol, and alkylene oxide adducts of (alkyl)phenol.

etc.

Methyl alcohol is a monohydric alcohol.

Ethyl alcohol, propyl alcohol, allyl alcohol, butyl alcohol, amyl alcohol.

Hexyl alcohol, octyl alcohol, caprylic alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol.

Aliphatic alcohols such as stearyl alcohol, aromatic alcohols such as benzyl alcohol, phenol, alkylene oxide adduct 1 of alkylphenol, cyclohexanol, rosin alcohol.

Examples include water-added rosin alcohol. Moreover, the esterified product with one alcoholic hydroxyl group remaining is an esterified product with a monohydric carboxylic acid.

Examples of dihydric or higher alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol,
Dipropylene glycol 2 Tripropylene glycol, polypropylene glycol, butylene gelicol, pentyl glycol, neopentyl glycol, hexanediol, glycerin.

Jig Vaseline. Trimethylolpropane, ditrimethylolpropane, trimethylolethane, ditrimethylolethane, tetramethylolmethane, dipentaerythritol, polycyclopentadiene diallyl alcohol copolymer, spiroglycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, Bisphenol F ethylene oxide adduct, bisphenol F propylene oxide adduct (
The number of moles of alkylene oxide added is usually 1 to 2 moles per hydroxyl group of bisphenol. ), water-added bisphenol A, water-added bisphenol F, etc.

To add alkylene oxide to bisphenols, add bisphenols and about 0.5% by weight of sodium hydroxide as a catalyst (based on the total amount charged including alkylene oxide) in an autoclave, and
The reaction was carried out at 60°C and below 5Kg/cm'', and the gauge pressure was 0.
The end point is 1Kg/cm" or less.

In addition, polybasic acids or polycarboxylic acids, that is, organic compounds having two or more carboxyl groups, include oxalic acid,
Malonic acid, succinic acid, alkyl succinic acid.

Glutaric acid, maleic acid or their acid anhydrides.

fumaric acid, adipic acid, pimelic acid, speric acid.

Azelaic acid, sebacic acid, 0SK-DASL-12,
03K-DASL-20,03K-DASB-12,0
3K-DASB-20,03K-DAUL-20,03
K-DAUB-20 (O3K series is intermediary oil manufacturing (II
aliphatic dicarboxylic acids such as long-chain dibasic acids), dimer acids such as linseed oil fatty acids and tung oil fatty acids.

O-phthalic acid, water-added O-phthalic acid, Himic acid.

Methylhimic acid, diphenic acid, trimellitic acid.

Pyromellitic acid, naphthalic acid, benzophenonetetracarboxylic acid and their acid anhydrides, isophthalic acid, terephthalic acid, hemimellitic acid, trimesic acid.

Brenidic acid, merophanic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid, homophthalic acid.

o, m, p-phenyleneacetic acid, 0-phenyleneacetic acid-β-
Examples include aromatic polycarboxylic acids such as propionic acid, rosin dimer acid, and the like.

Other single carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, and trimethylacetic acid.

Aliphatic carboxylic acids such as caproic acid, n-mebutanoic acid, caprylic acid, pelargonic acid, methoxyacetic acid, coconut oil fatty acid, palmitic acid, stearic acid, oleic acid, linoleic acid, luronic acid, benzoic acid, alkylbenzoic acid, alkyl Aminobenzoic acid, phenylacetic acid.

halogenated benzoic acid, anisic acid, benzoylbenzoic acid,
Examples include aromatic carboxylic acids such as naphthoic acid, rosin, and water-added rosin. Further, there is an esterified product of the above-mentioned dihydric carboxylic acid, a monohydric alcohol or one alcoholic water Hg, and a monohydric alcohol or an esterified product in which one alcoholic hydroxyl group remains.

The other carboxylic acid was used to shorten the reaction time.

In many cases, esterification reaction is performed before (meth)acrylic acid.

The esterification reaction is carried out at a temperature at which thermal polymerization of (meth)acrylic acid does not occur, 130°C or lower, preferably 120°C or lower. That is, it is carried out by a conventionally known method while blowing air at a temperature of 70 to 130° C., preferably 80 to 120° C., in a PJl, four-roof flask equipped with a stirrer. Further, if necessary, as a reaction catalyst, an acidic catalyst such as sulfuric acid or p-toluenesulfonic acid, or hydroquinone, which is a polymerization inhibitor, is used.

However, for one or more esterification reactions, OR/Co□II
Ratio 0°8~1.2. Preferably it is carried out between 0.9 and 1.1.

However, hydroxyl groups remain due to secondary hydroxyl groups, steric hindrance, etc., and when used in printing ink, the ink emulsifies, causing ink stains and deterioration of adhesive properties.

Usually, 5 to 30% of hydroxyl groups remain after esterification with respect to hydroxyl groups before (meth)acrylic esterification.

Therefore, in the present invention, in order to esterify the remaining hydroxyl groups, a monovalent carboxylic acid anhydride is reacted.

The reaction between the esterified product containing a hydroxyl group and the monocarboxylic acid anhydride is carried out at a temperature at which the system does not undergo gelation, i.e. 70/130°C, preferably 90-120°C, for 1 to 4 hours while blowing air. It is done on condition. The ratio during the reaction is 1 carboxylic acid anhydride per hydroxyl group and 0.
1 to 1 mol, and 0.8 mol or more when used as an offset printing ink.

In some cases, it is also effective to use an excess of 1 mole or more of monocarboxylic acid anhydride. In this case, excess acid anhydride is removed together with one carboxylic acid by-produced after hydrolysis by distillation under reduced pressure or by washing with water.

Examples of monovalent carboxylic anhydrides include acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, trimethylacetic anhydride,
Caproic anhydride, hebutanoic anhydride, caprylic anhydride, pelargonic anhydride, methoxyacetic anhydride.

Examples include nonyl acid anhydride, coconut oil fatty acid anhydride, palmitic anhydride, stearic anhydride, oleic anhydride, linoleic anhydride, lyllic anhydride, benzoic anhydride, alkylbenzoic anhydride, cinnamic anhydride, and acrylic anhydride.

The reaction between these monovalent carboxylic acid anhydrides and hydroxyl groups produces monovalent carboxylic acids as by-products, and if these monovalent carboxylic acids remain in the system, they cause stains during printing and corrosion of printing machines and ink filling cans. Therefore, it is undesirable. Therefore, the remaining monovalent carboxylic acid is removed by an appropriate method such as distillation under reduced pressure or washing with water. The temperature of vacuum distillation is set to a temperature at which gelation does not occur in the system, that is, 120° C. or lower. An effective distillation pressure is 2QmmlLg or less. Therefore, when removing by vacuum distillation, carboxylic acids 9 that can be removed under such conditions, such as acetic anhydride, propionic anhydride, acrylic anhydride, methacrylic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, isoanhydride Contains valeric acid and caproic anhydride. However, to make this vacuum distillation more effective, it is preferable to select from acetic anhydride, propionic anhydride, acrylic anhydride, methacrylic anhydride, butyric anhydride, and isobutyric anhydride. In yet another embodiment, it is also preferable to add water during vacuum distillation to perform azeotropic distillation.

If the by-produced monovalent carboxylic acid has a high boiling point and is difficult to remove by distillation under reduced pressure, it can also be removed by washing with water. When washing with water, an amine, ammonia, or an alkali can be added as necessary, and washing with water is performed two to three times or more.

The active energy ray-curable coating material thus obtained is used as a monomer, oligomer or prepolymer. In other words, the active energy ray-curable coating material is
It is used as an active energy ray-curable coating composition or printing ink by mixing with a monomer pigment having radical polymerizability and, if necessary, a radical polymerization initiator.

Furthermore, a resin that does not have radical polymerizability can also be used in combination. For example, alkyd resin, Epon ester resin, etc. Further, prepolymers having radical polymerizability other than the active energy ray-curable coating material of the present invention may be used in combination. Examples include alkyd acrylate, epoxy acrylate, urethane acrylate, petroleum resin acrylate, and the like.

Examples of radically polymerizable monomers other than the active energy ray-curable coating material of the present invention include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, allyl (meth)acrylate, and butyl (meth)acrylate. .

Amyl (meth)acrylate, Hexyl (meth)acrylate, Octyl (meth)acrylate, Capryl (meth)acrylate, Decyl (meth)acrylate, Lauryl (meth)acrylate, Myristyl (meth)acrylate, Cetyl (meth)acrylate , stearyl (
meth)acrylate, benzyl(meth)acrylate,
Alkylene oidide adducts of alkylphenols (
Meta) acrylate.

Examples include monofunctional monomers such as cyclohexyl (meth)acrylate. Furthermore, ethylene glycol di(meth)acrylate is used as a monomer with more than two functionalities.

Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate propylene glycol di(meth)acrylate dipropylene glycol di(meth)acrylate tripropylene glycol di(meth)acrylate, tripropylene glycol Ji(
Meta) acrylate.

butylene glycol di(meth)acrylate pentyl glycol (meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxybiparyl hydroxypipalate di(meth)acrylate hexanediol di(meth)acrylate.

(di)glycerin poly (meth)acrylate, (di)glycerin alkylene oxide poly (meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane alkylene oxide tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate , ditrimethylolpropane alkylene oxide tetra(meth)acrylate, trimethylolethane tri(meth)acrylate
ditrimethylolethanetetra(meth)acrylate,
Trimethylolethane alkylene oxide tri(meth)acrylate.

Ditrimethylolethane alkylene oxide tetra (
meth)acrylate tetramethylolmethanetetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate bisphenol A alkylene oxybi di(meth)acrylate.

Bisphenol F alkylene oxide di(meth)acrylate, dihydroxybenzene alkylene oxide di(meth)acrylate, trihydroxybenzene alkylene oxide di(meth)acrylate, water-added bisphenol A di(meth)acrylate, water-added bisphenol F di(meth)acrylate, Water-added bisphenol A alkylene oxide adduct di(meth)acrylate, water-added bisphenol F alkylene oxide adduct di(meth)acrylate, and the like. In addition, monomers of lactone adducts may be mentioned. Namely.

Polyethylene glycol polylactonate di(meth)acrylate polypropylene glycol polylactonate di(meth)acrylate, alkylene glycol polylactonate di(meth)acrylate, glycerin polylactonate tri(meth)acrylate, digvaseline polylactonate tetra(meth)acrylate ) acrylate, trimethylolpropane polylactonate tri(meth)acrylate, ditrimethylolpropane polylactonate tetra(meth)acrylate, pentaerythritol polylactonate tetra(meth)acrylate, dipentaerythritol polylactonate hexaacrylate, etc. Polyol lactonate polyacrylate.

In addition, the lactone of the above monomer is T-butyrolactone-
It is a compound containing an ester functional group -CO-O- in the ring, such as 8-valerolactone and ε-caprolactone. This radically polymerizable hexamer is used in an amount of 10 to 1,000 parts by weight, usually 1 part to 200 parts by weight, per 100 parts by weight of the active energy ray-curable resin.

In the coating composition of the present invention, when the active energy ray is ultraviolet rays, it is necessary to add a photosensitizer, that is, a radical polymerization initiator, and benzoin.

Benzoin sensitizers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-acrylic benzoin, benzophenone, p-
Aryl ketone sensitizers such as methylbenzophenone, p-chlorobenzophenone, tetrachlorobenzophenone, methyl O-benzoylbenzoate, acetophenone, etc., 4
．． Dialkylaminoarylketone sensitizers such as 4-bisdiethylaminobenzophenone, isoamyl p-dimethylaminobenzoate, p-dimethylaminoacetophenone, polycyclic carbonyl sensitizers such as thioxanthone 1-alkylxanthone and its halogen substituted product, Irgacure 907 (photosensitizer manufactured by Ciba Geigy).

These may be used alone or in appropriate combinations. These photosensitizers are present in the composition in an amount of 1 to 30% by weight.
It can be used in a range of 2 to 15% by weight, but preferably in a range of 2 to 15% by weight. If the active energy ray is stronger than ultraviolet rays, for example an electron beam, it is not necessary to add a radical polymerization initiator.

Further, in addition to the organic pigment and the inorganic pigment-1 extender pigment, a plasticizer, a surfactant, a thermal polymerization inhibitor, etc. can be added as necessary.

To prepare an active energy ray-curable printing ink composition,
Furthermore, the pigment is usually dispersed, but this method is not particularly limited, and can be carried out by a conventional dispersion method such as a three-roll mill or a ball mill. In addition to organic pigments and inorganic pigments, various additives such as plasticizers, surfactants, and thermal polymerization inhibitors can be added as necessary. Of course, an ink composition that does not use a pigment may also be used. The amount of pigment to be used may be appropriately determined by those skilled in the art depending on the purpose. Furthermore, it is also possible to use other resins in combination within a range that does not impede the effects of the present invention.

The present invention will be explained below using specific examples. All parts in the examples indicate parts by weight.

Production Example 1 136 parts of dipentaerythritol, 432 parts of acrylic acid, 0.6 parts of hydroquinone, 6 parts of p-toluenesulfonic acid
4 parts, 30 parts of benzene/toluene (1/1) with a stirrer
Pour into a two-ringed flask and blow in air until it reaches 90~1.
React at 15°C for 40 hours. Since the acid value stopped at 50, washing with water was repeated three times.

The acid value at this time was 2.6. Also, the hydroxyl value is 4
It was 7.4. This will be referred to as monomer a.

Production example 2 136 parts of dipentaerythritol, 200 parts of coconut oil fatty acid
1 part and 20 parts of toluene were placed in 4 flasks equipped with a stirrer, and the temperature was gradually increased under a nitrogen stream until the acid value reached 2 at 220°C.
．． 5, so remove the solvent under reduced pressure.

After further cooling, 0.8 parts of hydroquinone, 430 parts of methacrylic acid, benzene/
40 parts of toluene (1/1) was charged and reacted at 90 to 115°C. Since the acid value stopped at 48 after 38 hours, washing with water was repeated three times. The acid value at this time was 2.6.

Moreover, the hydroxyl value was 46.8.

This will be referred to as monomer b.

Production Example 3 268 parts of trimethylolpropane, 148 parts of phthalic anhydride
1 part, and 20 parts of toluene were charged into 4 flasks equipped with a stirrer, heated under a nitrogen stream, and reacted at 150°C for 1 hour.

The temperature was further gradually raised, and when the acid value reached 2.5 at 220°C, the solvent was removed under reduced pressure. After further cooling, while blowing air at 90°C, 0.7 parts of hydroquinone, 288 parts of acrylic acid, and 30 parts of benzene/toluene (1/1) were charged and reacted at 90 to 115°C. After 40 hours, the acid value stopped at 50, so washing with water was repeated three times. The acid value at this time was 2.2. Moreover, the hydroxyl value was 48.0. This is designated as prepolymer 〇.

Production Example 4 272 parts of pentaerythritol, 152 parts of tetrahydrophthalic anhydride, 280 parts of oleic acid, and 20 parts of toluene are placed in a four-bottle flask equipped with a stirrer, heated under a nitrogen stream, and reacted at 150° C. for 1 hour. The temperature further increases gradually,
Since the acid value reached 2.3 at 220°C, the solvent was removed under reduced pressure. After further cooling, while blowing air at 90"C, 0.7 parts of hydroquinone, 9420 parts of methacryl, and 50 parts of benzene/toluene (1/1) were added.
The reaction was carried out at ℃. After 43 hours, the acid value stopped at 51, so washing with water was repeated three times. The acid value at this time was 2.2. Moreover, the hydroxyl value was 50.0. This is referred to as prepolymer d.

Manufacturing example 1 530 parts of monomer a of Production Example 1, 80 parts of butyric anhydride.

0.2 part of hydroquinone was placed in a four-bottle flask with a stirrer, and heated to 90 to 115°C while blowing air.

Let react for 2 hours. Thereafter, the pressure was reduced to 120"C to remove the generated butyric acid. The monovalent hydroxyl value of monomer a-1 was 1.
It was 1.

Production Example 2 530 parts of monomer a of Production Example 1, 280 parts of oleic anhydride
1 part, and 0.2 part of hydroquinone were placed in 4 flasks equipped with a stirrer, and heated at 90 to 115°C, 2 parts while blowing air.
Allow time to react. Thereafter, it was cooled and the produced oleic acid was removed by washing with water. The hydroxyl value of this monomer a-'l is 1.0
Met.

Hereinafter, an active energy ray-curable coating material was obtained according to Production Example 1.2. They are shown in Table 11 and Table 2, respectively.

(Margin below) Table 1 (according to Manufacturing Example 1) (Margin below) Table 2 (according to Manufacturing Example 2) (Margin below) The photosensitizers and pigments in Table 3 are as follows.

Photosensitizer A: 4,4'-bis(diethylamino)bensif, enone/benzophenone = 21 Pigment: Fines Red F2 BW: Red pigment manufactured by Toyo Ink Manufacturing Co., Ltd. (Printing test) Coating composition shown in Table 3 (printing ink).That is, Comparative Example Samples 1, 3, and Example Samples 1, 2, 5, and 6 were printed on a WORD Heidelberg printing machine, and the stains on the non-image areas during printing were investigated. The number of sheets generated and the amount in water (Note-1) were measured, and the results are shown in Table 4.

l) In water: Measurement was carried out by installing a device to control the amount of dampening water in the printing press. The lower limit number indicates the amount of water that causes stains when the amount of water is decreased, and the upper limit number indicates that when the amount of water is increased, the ink emulsifies and transfers poorly. Represents the amount of water consumed. The numbers are scales that represent the amount of dampening water, and there is no specific unit.

Table 4 Example Number of sheets with stains Underwater comparative example 1 2.000 (sheets > 12-18 Example 1 15.000 10-20〃2
20,000 8-22 Comparative Example 3 5.0
00 12-20 Example 5 20,000
8～22〃6 20,000
8-22 Next, 30a+g of the coating composition shown in Table 3 was applied to a TFS board coated with alkynd resin, epoxy phenol resin (E/P), and acrylic resin using an R1 tester.
Printing was carried out to give a dry coverage of /100 cd.

Comparative example 2. Examples 3 and 4 were coated with Bar Coater #5. Comparative Examples 1.2 in Table 3. Regarding Examples 1 to 4,
The material was irradiated and cured by placing it on a conveyor belt 10 cm below two high-pressure mercury lamps having an intensity of 80 W/cm.

Also, Comparative Example 3. Examples 5 and 6 were cured by irradiating at 10 Mrad using a curtain beam type electron beam irradiation device. Table 5 shows the results regarding the adhesion of each coating film.

The adhesion value indicates the residual rate of the coating film in the cellophane tape peeling test.

Table 5 Excellent, the range of application of active energy ray-curable coating compositions can be expanded.

Claims (1)

[Scope of Claims] 1. A by-product obtained by reacting a monohydric carboxylic anhydride with a compound that undergoes an esterification reaction with acrylic acid and/or methacrylic acid, and a hydroxyl group-containing esterified product using acrylic acid and/or methacrylic acid. An active energy ray-curable coating comprising a product obtained by removing a monovalent carboxylic acid. 2. An active energy ray-curable coating material comprising the product according to claim 1, a monomer having a radically polymerizable double bond, and, if necessary, a radical polymerization initiator. 3. An active energy ray-curable printing ink comprising the product according to claim 1, a monomer having a radically polymerizable double bond, a pigment, and, if necessary, a radical polymerization initiator.