JPH0333117A - Actinic radiation-curable resin composition and printing ink composition - Google Patents

Abstract

PURPOSE:To obtain an actinic radiation-curable resin composition useful as an ink vehicle which does not cause staining and poor transfer during printing by reacting an ester compound obtained from a specified acid component and a polyalcohol with (meth)acrylic acid. CONSTITUTION:Alloocimene or terpinene and maleic acid (anhydride) are subjected to an addition reaction to obtain a product comprising a polybasic acid (anhydride) of any one of formulas I-III. An acid component comprising said product and optionally another polycarboxylic acid (anhydride) is reacted with a polyalcohol in an amount to give OH groups in excess of the acid component at 80-300 deg.C in an inert gas to obtain an ester compound. This compound is reacted with (meth)acrylic acid at 80-120 deg.C in the presence of a polymerization inhibitor and an acid catalyst.

Description

Detailed Description of the Invention [Objective of the Invention] (Industrial Field of Application) The present invention relates to active energy ray-curable resin compositions, and particularly to coating compositions and printing inks that are cured by irradiation with ultraviolet rays or electron beams. The present invention relates to resin compositions useful in compositions.

(Prior art) In recent years, research has been actively conducted on coating compositions that can be cured by active energy rays, and practical applications are progressing in the fields of printing inks, clear varnishes, paints, adhesives, photoresists, etc. These are composed of radically polymerizable resins and monomers, as well as radical polymerization initiators and pigments if necessary.The radically polymerizable resins include alkyd (meth)acrylate and polyester (meth)acrylate. 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, etc. Acrylate, tetramethylolmethanetetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, alkylphenol alkylene oxide adduct mono(meth)acrylate, etc. were used.

In this specification, (meth)acrylate refers to acrylate and/or methacrylate, and (meth)acrylic acid refers to acrylic acid and/or methacrylic acid.

However, when curable coating compositions using these compounds are used, for example, in printing inks, they often cause poor transfer due to stains during printing or emulsification of the ink. The reality is that the scope has been narrowed.

In order to solve this problem, some attempts have been made to improve the printability by using a vehicle in which Epon ester or diallyl phthalate polymer, which is solid at room temperature, is dissolved in a monomer or prepolymer having a radical double bond. W still needs to be resolved in the stain of time
There are i issues.

(Problem B to be Solved by the Invention) The present invention provides an active energy ray-curable resin composition and a printing ink composition using the same, which solves the problem of staining and poor transfer during printing as described above. It is something.

"Structure of the Invention" (Means for Solving the Problems) The present invention provides a method for combining one or more acid components of a product (A) obtained by addition-reacting alloocimene with maleic acid or its anhydride, and a polyhydric acid component. To provide an active energy ray-curable resin &Il curable resin, which is obtained by reacting an esterified product (B) with an excess of OH groups with acrylic acid or methacrylic acid.

The above product (A) is prepared by a conventional method.
, 6-dimethyl-2,4,6-octatriene) to 1 to 2 moles of maleic acid or its anhydride, and has the following structural formula [l], (n
) and (III) or anhydrides thereof are obtained.

It contains a polyhydric alcohol and further undergoes an esterification reaction with a polyhydric carboxylic acid as a crosslinking agent and some carboxylic acid as a modifier with an excess of OH groups, and as part or all of this polyhydric carboxylic acid. Product (A) is used. This ester compound (B) is further imparted with crosslinkability by irradiation with active energy rays by subjecting acrylic acid or methacrylic acid to an esterification reaction.

Other polyhydric carboxylic acids or anhydrides thereof that can be used in combination with the above product (A) include, for example, oxalic acid, malonic acid, succinic acid, dodecenyl succinic acid, pentadecenyl succinic anhydride, glutaric acid, and maleic acid. Acids or their acid anhydrides, fumaric acid, adipic acid, pimelic acid, superic acid, azelaic acid, sebacic acid, 05K
-DASL-12,03K-DASL-20,05K-
DASB-12,0SK-DASB-20,05K-D
AUL-20, 03K = DAUB-20 (O3K series is a long chain dibasic acid manufactured by Seiza Seishin Co., Ltd.), aliphatic dicarboxylic acids such as dimer acids such as linseed oil fatty acids and tung oil sac fatty acids,
0-7 talic acid, water-added □o-phthalic acid, methylated hydrogenated high-main tsutaic acid, methyl-high methacic acid, diphenic acid, trimellitic acid, pyromellitic acid, naphthalic acid, benzophenonetetracarboxylic acid and their acid anhydrides isophthalic acid, terephthalic acid, hemellitic acid, trimesic acid, brenidic acid, merophanic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid, homophthalic acid, o, m
, p-phenylenediacetic acid, aromatic polycarboxylic acids such as 0-phenyleneacetic acid-β-propionic acid, rosin dimer acid, and the like.

The weight ratio of the product (A) in the polyhydric carboxylic acid and the other polyhydric carboxylic acid or its anhydride is 10010 to 100.
10/90, preferably 100/l O to 50,150. When the ratio of the compound (A) used in the polyhydric carboxylic acid increases, the solubility in the monomer (B) having the radically polymerizable double bond tends to be insufficient. In addition, if the amount is too small, the lipophilicity will be insufficient and the improvement in the printing effect, which is an effect of the present invention, cannot be expected.

-valent carboxylic acids include formic acid, acetic acid, propionic acid,
butyric acid, valeric acid, trimethylacetic acid, caproic acid, n
- aliphatic carboxylic acids such as hebutanoic acid, caprylic acid, pelargonic acid, methoxyacetic acid, coconut oil fatty acid, palmitic acid, stearic acid, oleic acid, linoleic acid, lilunic acid, etc.
Examples include aromatic carboxylic acids such as benzoic acid, alkylbenzoic acid, alkylaminobenzoic acid, phenylacetic acid, halogenated benzoic acid, anisic acid, benzoylbenzoic acid, and naphthoic acid, rosin, and water-added rosin.

Furthermore, there are esterified products of the above-mentioned dihydric carboxylic acids and -valent alcohols or esterified products in which one alcoholic hydroxyl group remains. In selecting this -valent carboxylic acid, short chain fatty acids such as formic acid, acetic acid, and propionic acid, benzoic acid, hydrogenated rosin, etc. are used in order to obtain the alxodo resin composition (A) that is solid at room temperature. It is preferable to do so. These -valent carboxylic acids are appropriately used for the purpose of raising the gel point.

Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and propylene glycol.

Dipropylene glycol, dipropylene glycol polypropylene glycol, butylene glycol, pentyl glycol, neopentyl glycol, hexanediol, glycerin, diglycerin, 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, and suphenol F propylene oxide adduct (the number of moles of alkylene oxide added is The amount is usually 1 to 2 mol per hydroxyl group of bisphenol.), hydrated bisphenol A1, hydrated bisphenol F, etc.

Next, a reaction method for the ester compound (A) will be described.

Add the acid component (a) and alcohol component (b) to a flask with four stirrers at a functional group ratio (OH/C0OH group ratio) of 1.05 to
1.80°C, add an inert reaction solvent as necessary, and while blowing inert gas such as nitrogen or carbon dioxide, the reaction temperature is 80 to 300°C, preferably 15°C.
A zero reaction in which 90% or more of the theoretical amount is reacted at 0 to 260°C is preferably followed by checking the acid value, which is 1O or less, preferably 3 or less.

The composition according to the present invention includes the above ester compound (A),
Esterification reaction of acrylic acid or methacrylic acid. The reaction is carried out at a temperature of 80-120 °C in the presence of air or inert gas, using a polymerization inhibitor such as hydroquinone, mass production, and an acidic catalyst such as P-)luenesulfonic acid.The M value is below 20. .

In the composition according to the present invention, in addition to the active energy striped curable resin composition, monomers having a radically polymerizable double bond, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl ( meth)acrylate, allyl(meth)acrylate, butyl(meth)acrylate, amyl(meth)acrylate, hexyl(meth)acrylate, octyl(meth)acrylate, caprylic(meth)acrylate, decyl(meth)acrylate,
meth)acrylate, lauryl(meth)acrylate,
ξ Monofunctional monomers such as listyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylate of an alkylene oxide adduct of alkylphenol, and cyclohexyl (meth)acrylate can be mentioned. . In addition, monomers with more than two functionalities include ethylene glycol di(meth)acrylate, diprolene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, positive ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and diethylene glycol di(meth)acrylate. (meth)acrylate, l-lipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, pentyl glycol (meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxy Piparyl hydroxybiparate di(meth)acrylate, hexanediol di(meth)acrylate, (di)glycerin tri(meth)acrylate, diglycerin alkylene oxide tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylol Propane alkylene oxide tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ditrimethylolpropane alkylene oxide tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, ditrimethylolethane tri(meth)acrylate, trimethylolethane Alkylene oxide tri(meth)acrylate, ditrimethylolethane alkylene oxide tetro(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dibenquerythritol hexa(meth)acrylate, bisphenol A alkylene oxide tri(meth)acrylate, bisphenol F alkylene Oxybi di(meth)acrylate, dihydroxybenzene alkylene oxide di(meth)acrylate, trihydroxybenzene alkylene oxide di(meth)acrylate, hydrated bisphenol A di(meth)acrylate
Examples include acrylate, water-added bisphenol F di(meth)acrylate, water-added bisphenol A alkylene oxide adduct di(meth)acrylate, and water-added bisphenol F alkylene oxide adduct di(meth)acrylate. In addition, monomers of lactone adducts may be mentioned. Namely, polyethylene glycol polylactonate di(meth)acrylate, polypropylene glycol borylactonate di(meth)acrylate, alkylene glycol borylactonate di(meth)
Acrylate, glycerin polylactonate tri(meth)acrylate, diglycerin polylactonate tri(meth)acrylate, trimethylolpropane polylactonate tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol polylactonate Each polyol lactonate polyacrylate such as tetra(meth)acrylate, dipentaerythritol polylactonate hexaacrylate. In addition, the above monomer lactone can be used in combination with a compound contained in the functional group -co-o-4N of the ester such as T-butyrolactone, 8-valerolactone, and ε-caprolactone, and the proportion of the combined use depends on the purpose. Tei! Generally, the proportion of the active energy ray-curable resin composition according to the present invention is 20% by weight.
Below this, the effect of the present invention decreases.

Furthermore, when the active energy ray is ultraviolet rays, it is necessary to add a radical polymerization initiator, such as benzoin-based sensitizers such as benzoin, henzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and α-acrylic benzoin. agent, benzophenone,
Aryl ketone sensitizers such as p-methylbenzophenone, p-chlorobenzophenone, tetrachlorobenzophenone, methyl 〇-benzoylbenzoate, acetophenone, 4,4-bisdiethylaminobenzophenone, p-dimethylaminobenzoic acid isoal, p -Dialkylaminoarylketone sensitizers such as dimethylaminoacetophenone, polycyclic carbonyl sensitizers such as thioxanthone, xanthone and their halogen-substituted products, Irgacure 9
07 (sensitizer manufactured by Ciba Geigy, trade name), etc., and these can be used alone or in an appropriate combination.

In the present invention, the pigment is dispersed in the resin composition to obtain the printing ink m acid, but this method is not particularly limited and may be carried out by a conventional dispersion method such as a three-roll mill or a ball mill. I can do it. In addition to organic and inorganic pigments and extender pigments, plasticizers, surfactants, thermal polymerization inhibitors, and the like can be added as necessary. Of course, there may be ink compositions that do not use pigments.

Furthermore, it is also possible to use other resins in combination within a range that does not impede the effects of the present invention.

Hereinafter, the present invention will be explained with reference to specific examples. All parts in the examples indicate parts by weight.

Production side-1 (comparative example) Pyromellitic acid 269 parts Glycerin 202 parts Toluene
35 parts were placed in a flask equipped with 4 stirrs and reacted at 200°C for 12 hours under a stream of nitrogen gas. When the acid value reached 3.5, the solvent was removed, and then 8
Cool to 0'C and at this temperature add 50 parts of benzene, 1 part of hydroquinone, p-toluenesulfone 6M108B and 134% of methacrylic acid under an equal atmosphere of nitrogen gas/air.
The temperature was gradually raised to react in the range of 90 to 115°C, and when the acid value became 20 or less, the solvent was removed. This will be referred to as resin a. The weight average molecular weight of this resin a was 12,000.

Production Example-2 (Example) Compound of formula (III) 390 parts Glycerin 202 parts Toluene 35 parts was added to the stirrer 4
11 at 200℃ under nitrogen gas flow.
React for a period of time, remove the solvent when the acid value reaches 3.0,
Next, it was cooled to 80°C, and at this temperature, 50 parts of benzene, 1 part of hydroquinone, p-
10 parts of toluenesulfonic acid and 134 parts of methacrylic acid were charged, and the temperature was gradually raised to react in the range of 90 to 115°C. When the acid value became 20 or less, the solvent was removed. Let's call this a resin. The weight average molecular weight of this resin was 11,500.

Production Example 3 (Comparative Example) Tetrahydrophthalic anhydride 288 parts Trimethylolpropane 294 parts O-benzoylbenzoic acid 147 parts Toluene
50 parts were placed in a fourth flask equipped with a stirrer and reacted at 200°C for 13 hours under a stream of nitrogen gas. When the acid value reached 3.1, the solvent was removed, and then 80
At this temperature, 50 parts of benzene, 1 part of hydroquinone, 10 parts of p-toluenesulfonic acid, and 72 parts of acrylic acid were charged under a uniform flow of nitrogen gas/air, and the temperature was gradually raised to 90-115°C. The acid value is 20.
When the amount was below, the solvent was removed. This will be referred to as resin C. The weight average molecular weight of this resin C was 11,500.

Production Example-4 (Example) Compound of formula [1] 446 parts Trimethylolpropane 294 parts 0-benzoylbenzoic acid 147 parts Toluene
60 parts were placed in a fourth flask equipped with a stirrer and reacted under a stream of nitrogen gas for 11 hours at 1°C. When the acid value reached 3.0, the solvent was removed, and then the mixture was cooled to 80°C and at this temperature. Under an equal flow of nitrogen gas/air, 50 parts of benzene, 1 part of hydroquinone, 10 parts of p-toluenesulfonic acid and 72 parts of acrylic acid were charged and the temperature was gradually raised to react in the range of 90 to 115°C until the acid value reached 20. When the temperature was below, the solvent was removed using a desolvation mechanism.This was designated as resin d.The softening point of this resin d was 81°C, and the weight average molecular weight was 11,000.

Production Example-5 (Comparative Example) Tetrahydrophthalic anhydride 292 parts Pentaerythritol 300 parts Propionic acid 74 parts Toluene 50 parts were placed in a flask equipped with four stirrers and heated at 200'C for 12 hours under a nitrogen gas stream.
After reacting for an hour and reaching an acid value of 3.3, the solvent was removed, and then cooled to 80°C. At this temperature, under an equal atmosphere of nitrogen gas/air, 50 parts of benzene, 1 part of hydroquinone, and 110 parts of p-toluenesulfone ff were added. Then, 245 parts of acrylic acid was charged, and the temperature was gradually raised to react in the range of 90 to 115° C. When the acid value became 20 Dl or less, the medium was discharged. This will be referred to as resin e. The weight average molecular weight of this resin e was 1050'0.

Production Example-6 (Example) Compound of formula (n) 450 parts Pentaerythritol 300 parts Propionic acid 74 parts Toluene 60 parts were charged into a flask equipped with 4 stirrs and reacted at 200°C for 11 hours under a nitrogen gas stream to give an acid value of 2. , 8, the solvent was removed, then cooled to 80°C, and at this temperature, 5 opB of benzene, 1 part of hydroquinone, p-
10 parts of toluenesulfonic acid and 245 parts of acrylic acid were charged, and the temperature was gradually raised to react in the range of 90 to 115°C. When the acid value became 20 or less, the solvent was removed.

This will be referred to as resin r. The weight average molecular weight of this resin f is 1
It was 1000.

Next, an active energy ray-curable coated Mikaimono was prepared using the above-mentioned resin and a heptanomer.

Table 1 below shows the weight average molecular weight and the formulation of the composition.

Margin below (Note-1) Abbreviations in Table-1 are as follows.

ABPE-4: Bisphenol A mole ethylene oxide adduct diacrylate TMPTA: ) Limethylolpropane triacrylate TMPEOA: ) Trimethylolpropane 3-addition ethylene oxide adduct triacrylate Photosensitizer: 4.4-bis(diethylamino)benzophenone /benzophenone-215 Pigment: Fines Red F2BW: Toyo Ink Manufacturing Red Pigment Examples 1 to 4 and Comparative Examples 1 to 4 Coating composition (printing ink) shown in Table 1, that is, Comparative Example Samples 1 to 4 , KORD example sample l-4
Printed in Heidelberg, stains on non-embroidered areas during printing,
In water (Note-2) was measured and shown in Table-2.

Margin Table 2 (Note 2) Underwater: The printing machine was equipped with a device to control the amount of warm water and was measured. The numbers are scales that represent the amount of dampening water, and there is no specific unit.

The lower limit number in the table represents the amount of water in which stains were generated when the amount of water was decreased. Further, the upper limit number represents the amount of water at which the ink becomes emulsified and poor transfer occurs when the amount of water is increased.

Example-J The coating compositions printed in the above Examples and Comparative Examples were heated to 80 W for Comparative Example Samples 1 to 3 and Example Samples 1 to 3.
A portion 10 cm below the two high-pressure mercury lamps having an intensity of /as was placed on a conveyor and irradiated at Loom/min. Further, Comparative Example Sample 4 and Example Sample 4 were irradiated at 3 Mr ad using a curtain beam type electron beam irradiation device. Both were hardened.

〔Effect of the invention〕

As shown in Examples and Comparative Examples, the active energy ray-curable coating composition of the present invention has a better printing effect than conventional coating materials, and is widely used as an active energy ray-curable coating composition. The range can be expanded.

Claims (1)

[Claims] 1. One or more acid components of the product (A), which is an addition reaction of alloocimene and maleic acid or its anhydride, are reacted with a polyhydric alcohol with an excess of OH groups. An active energy ray-curable resin composition prepared by reacting an esterified product (B) with acrylic acid or methacrylic acid. 2. The product (A) obtained by addition reaction of alloocimene and maleic acid or its anhydride has the following structural formula [I]
, [II] and [III], or an anhydride thereof. ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I]▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[III] 3. Resin composition according to claim 1 or 2 An active energy ray-curable printing ink composition containing an active energy ray-curable printing ink composition as a vehicle component.