JPH01115918A - Coating composition curable with actinic energy radiation - Google Patents

Abstract

PURPOSE:To provide the subject composition containing a specific alkyd resin, a monomer containing radically polymerizable double bond, etc., curable by irradiation of ultraviolet ray, electron ray, etc., and having excellent printability, etc. CONSTITUTION:The objective composition contains (A) an alkyd resin produced by using pentadecenylsuccinic acid or its anhydride, (B) a monomer having radically polymerizable double bond (e.g., trimethylolpropane triacrylate) and, as necessary, (C) a radical polymerization initiator (e.g., 4,4-bisdiethylamino benzophenone).

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 composition, and more specifically, it is cured by irradiation with ultraviolet rays or electron beams, and furthermore, The present invention relates to an active energy ray-curable coating composition that has excellent printability and the like.

(Prior Art) In recent years, research on coating compositions curable with active energy rays has been actively conducted, and among them, printing inks,
Practical applications are progressing in fields such as clear varnishes, paints, adhesives, and photoresists. These are radically polymerizable monomers and prepolymers that have radical polymerizability, and if necessary, a radical polymerization initiator.

The prepolymer includes alkyd acrylate, polyester acrylate, epoxy acrylate, urethane-modified acrylate, etc., and the monomer includes bisphenol A alkylene oxide adduct diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate,
Tetramethylolmethanetetraacrylate, dipentaerythritol hexaacrylate.

Alkylphenol alkylene oxide adduct monoacrylate and the like have been used.

However, curable coating compositions using these compounds, for example, when used in printing inks, may cause stains during printing.

Emulsification of ink often causes poor transfer. Therefore, the actual situation is that the scope of application of these curable coating materials has been narrowed.

"Structure of the Invention" (Means for Solving Problems) The present invention has been developed as a result of intensive research to improve these drawbacks.
Excellent printability. This led to the invention of an active energy ray-curable coating composition. Namely.

(A) Alkyd resin obtained using pentadecenylsuccinic acid or its anhydride.

(B) A monomer containing a radically polymerizable double bond.

(C) A radical polymerization initiator if necessary.

The present invention relates to an active energy ray-curable coating composition comprising:

To explain the present invention in detail, alkyd resin is generally produced by esterifying a polyhydric alcohol with a polyhydric carboxylic acid as a crosslinking agent and a monobasic acid as a modifier. It uses pentadecenyl succinic anhydride.

1 as a polyhydric alcohol, for example, ethylene glycol,
Diethylene glycol, triethylene glycol.

Polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol.

Polypropylene glycol, butylene glycol, pentyl glycol, neopentyl glycol, hexanediol, glycerin, diglycerin 1, 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 1 hydroxyl group of bisphenol), water-added bisphenol A, water-added bisphenol F, etc. be.

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.
Gradually add alkylene oxide, 160℃, 5k
g/cj or less, with a gauge pressure of 0.1 kg/
The end point is below cnt.

In addition, when used in combination with pentadecenylsuccinic acid or its anhydride as a polybasic acid, the polycarboxylic acid used in combination, that is, an organic compound having two or more carboxyl groups, is oxalic acid, malonic acid, or succinic acid. , dodecenylsuccinic acid, glutaric acid, maleic acid or their acid anhydrides,
Fumaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, 03K-DASL-12,03
K-DASL-20,03K-DASB-12,03K
-DASB-20,03K-DAUL-20,03K-
Aliphatic dicarboxylic acids such as DAUB-20 (O3K series is a long-chain dibasic acid manufactured by Intermediate Oil Co., Ltd.), dimer acids such as linseed oil fatty acids and tung oil fatty acids.

0-phthalic acid, water-added 0-phthalic acid, Himic acid.

Methylhimic acid, diphenic acid, trimellitic acid.

Pyromellitic acid, naphthalic acid, benzophenonetetracarboxylic acid and their acid anhydrides, isophthalic acid.

Aromatic polyesters such as terephthalic acid, hemimellitic acid, trimesic acid, brenidic acid, merophanic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid, homophthalic acid, o, m, p phenylene acetic acid, 0-phenylene acetic acid-β-propionic acid, etc. Examples include carboxylic acids, rosin dimer acids, and the like.

Single 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, valmitic 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, the above-mentioned dihydric carboxylic acid and a -hydric alcohol or an esterified product with one alcoholic hydroxyl group remaining,
There are esterified products of

In addition, the -valent alcohol is methyl alcohol.

Aliphatic alcohols such as ethyl alcohol, propyl alcohol, allyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, octyl alcohol, caprylic alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, benzyl alcohol, phenol, alkyl phenol Examples include aromatic alcohols such as alkylene oxide adduct 1, cyclohexanol, rosin alcohol, and water-added rosin alcohol.

Furthermore, the esterified product with one alcoholic hydroxyl group remaining is the esterified product with the above-mentioned carboxylic acid.

Next, the reaction method will be described.

Polyhydric alcohol and polybasic acid in a 4-roof flask with a stirrer.

-valent carboxylic acid at a functional group ratio (OH/C0OH group ratio) between 0°5 and 2.0, and if necessary, add an inert reaction solvent and blow inert gas such as nitrogen or carbon dioxide gas. while the reaction temperature is 80 to 300°C, preferably 15°C.
90% or more of the theoretical amount is reacted at 0 to 260°C.

It is best to follow the reaction using the acid value.

In addition, - the basic acid has radical double bond properties - the basic acid 2
For example (meth)acrylic acid, sorbic acid, cinnamic acid.

When vinyl acetic acid and crotonic acid are reacted, the reaction is carried out at 80 to 120° C. with the residual OH compound resulting from the esterification reaction of polyhydric alcohol, polycarboxylic acid, and -carboxylic acid.

Hydrochloric acid, sulfuric acid, P-
A reaction catalyst such as toluenesulfonic acid and a polymerization inhibitor such as hydroquinone are used.

The coating composition of the present invention contains, in addition to the resin (A), one or more other prepolymers or monomers (B) having radically polymerizable double bonds as necessary. Examples include 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, lauryl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate,
Benzyl (meth)acrylate (meth)acrylate of alkylene oidide adduct of alkylphenol,
Examples include monofunctional monomers such as cyclohexyl (meth)acrylate. Furthermore, as heptadons with more than two functional groups, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, brobylene glycol di(meth)acrylate, dipropylene Glycoldi (meth)
Acrylate, tripropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, pentyl glycol (meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypiparyl hydroxypiparate di(meth)acrylate,
Hexanediol di(meth)acrylate (di)glycerin tri(meth)acrylate, diglycerin alkylene oxide tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane alkylene oxide tri(meth)acrylate, ditrimethylolpropane Tetra (meta)
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, tetramethylolmethanetetra(
meth)acrylate, dipentaerythritol hexa(
meth)acrylate, bisphenol A alkylene oxide dra(meth)acrylate Bisphenol F alkylene oxide dra(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-h, water-added Examples include bisphenol F alkylene oxide adduct di(meth)acrylate. In addition, lactone adducts such as lactones 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.
Diglycerin polylactonate tetra(meth)acrylate Trimethylolpropane polylactonate tri
(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol polylactonate tetra(meth)acrylate, dipentaerythritol polylactonate hexaacrylate, and other polyol lactonate polyacrylates. The lactone monomer is a compound containing an ester functional group -CO-O- in the ring, such as γ-butyrolactone, 8-valerolactone, and ε-caprolactone.

When using the coating material 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 (also a radical polymerization accelerator) (C), and benzoin, benzoin Methyl ether, benzoin ethyl ecotyl. Benzoin-based sensitizers such as benzoin isopropyl ether and α-acrylic benzoin,
Benzophenone, p-methylbenzophenone, p-chlorobenzophenone, tetrachlorobenzophenone, 0-
Aryl ketone sensitizers such as methyl benzoylbenzoate and acetophenone, 4,4-bisdiethylaminobenzophenone, isoamyl p-dimethylaminobenzoate, p
-Dialkylaminoarylketone sensitizers such as dimethylaminoacetophenone.

Examples include polycyclic carbonyl sensitizers such as thioxanthone, xanthone, and halogen-substituted products thereof, and these can be used alone or in appropriate combinations.

These photosensitizers can be used in the composition in an amount of 1 to 30% by weight, preferably in a range of 0 to 15% by weight.

In addition, the resin of the present invention (A), drying oil, and paraffin.

It can also be used for thermal polymerization and oxidative polymerization in combination with olefins, aromatic solvents, etc.

To prepare an active energy ray-curable ink composition, pigments are usually dispersed in the above-mentioned diluted varnish, 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. can. Also.

In addition to organic and inorganic basic pigments, plasticizers are used as needed.

Surfactants, thermal polymerization inhibitors, etc. can be added.

Of course, there may be ink compositions that do not use the R material. 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-1 268 parts of trimethylolpropane 148 parts of phthalic anhydride 20 parts of toluene were added to the stirrer 4
The mixture was charged into a double-bottomed flask and reacted at 200°C for 5 hours under a stream of nitrogen gas until the acid value reached 4.8. After cooling, 0.6 parts of hydroquinone and 6 parts of p-toluenesulfonic acid were added and 260 parts of acrylic acid was added while blowing air. Prepare 100
After 10 hours at °C, the acid value reached 9°9, so the solvent was removed.
I pumped it out.

This will be referred to as resin a.

Production Example-2 268 parts of trimethylolpropane 310 parts of pentadecenyl succinic anhydride 25 parts of toluene were stirred into a fourth flask and reacted at 200°C for 5 hours under a stream of nitrogen gas. When the acid value reached 4.9, the mixture was cooled. , 0.7 parts of hydroquinone and 7 parts of p-1-luenesulfonic acid were charged, and while blowing air, 260 parts of acrylic acid was added.
After 10 hours at 00°C, the acid value reached 9.8, so the solvent was removed and pumped out.

Let's call this a resin.

Production Example-3 Glycerin 148 parts Succinic acid 118 parts 0-benzoylbenzoic acid 813 parts Toluene
75 parts were placed in a flask equipped with four stirrers and reacted at 200°C for 11 hours under a stream of nitrogen gas. When the acid value reached 4.7, the solvent was removed and pumped out.

This will be referred to as resin C.

Production Example-4 Glycerin 184 parts Pentadecenyl succinic acid 328 parts O-benzoylbenzoic acid 813 parts Toluene 75 parts were placed in a flask equipped with four stirrers and heated at 200°C under a nitrogen gas stream.
After reacting for 1 hour, the acid value reached 4.8, so the solvent was removed and pumped out.

This will be referred to as resin d.

Production example-5 Pentaerythritol 272 parts Isophthalic acid 166 parts Water-added rosin 990 parts Toluene
70 parts were placed in a flask equipped with four stirrers and reacted at 200°C for 10 hours under a stream of nitrogen gas until the acid value reached 4.0. After cooling, 1.3 parts of hydroquinone and 13 parts of P-toluenesulfonic acid were added and air was introduced. While blowing, add 194 parts of acrylic acid to 100 parts.
After 9 hours at °C, the acid acetic acid value reached 9.8, so the solvent was removed and the mixture was pumped out.

This will be referred to as resin e.

Production Example-5 Pentaerythritol 272 parts Isophthalic acid 166 parts Water-added rosin 990 parts Toluene 70 parts were placed in a flask with four stirrers and reacted at 200°C for 10 hours under a stream of nitrogen gas. When the acid value reached 4.0, the mixture was cooled. , 1.3 parts of hydroquinone and 13 parts of p-toluenesulfonic acid were charged, and 194 parts of acrylic acid was charged while blowing air.
After 9 hours at 100°C, the acid acetic acid value reached 9.8, so the solvent was removed and pumped out.

This will be referred to as resin e.

Production Example-6 Pentaerythritol 272 parts Pentadecenyl succinic anhydride 310 parts Water-added rosin 990 parts Toluene
75 parts were placed in a flask equipped with four stirrers and reacted at 200°C for 10 hours under a stream of nitrogen gas. When the acid value became 4.5 or less, the mixture was cooled, and 1.6 parts of hydroquinone and 16 parts of P-toluenesulfonic acid were placed in the air. Add 194 parts of acrylic acid while blowing in 1
00. After 9 hours at °C, the acid acetic acid value reached 9.7, so the solvent was removed and the mixture was pumped out.

This is referred to as resin f.

Next, an active energy ray-curable coating composition was prepared using the above resin, monomer, etc.

The weight average molecular weight and the formulation of the composition are shown in the table below.

(Note-1) Monomer ABPE-47 bisphenol A mole ethylene oxide adduct diacrylate TMPTA: Trimethylolpropane triacrylate TMPEOA: Trimethylolpropane 3 mole ethylene oxide adduct triacrylate Photosensitizer: 4,4-bis (Diethylamino)benzophenone/benzophenone-215 Pigment: Fines Red F2BW: Red pigment manufactured by Toyo Ink Manufacturing Company Example 1 The coating composition (printing ink) shown in Table 1, that is, Comparative Example Samples 1 to 4. KORD example samples 5 to 8
Printed with Heidelberg, stains on non-printing areas during printing,
In water (Note-2) was measured (Table-2).

Table 2 (Note 2) Underwater: Measured by installing a device to control the amount of dampening water in the printing press. 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-2 The coating composition printed in Example-1 was used as comparative sample 1 to
3. Example samples 5/7 were placed on a conveyor and irradiated at a distance of 10 cm from two high-pressure mercury lamps having an intensity of 80 W/mouth at a rate of 100 m/min. Comparative example sample 4.
Example sample 8 was irradiated at 3 Mr ad using a curtain beam type electron beam irradiation device. Both were hardened.

〔Effect of the invention〕

The active energy ray-curable coating composition of the present invention was compared with the conventionally known coating composition in Example 1. As shown in Example 2, the printing effect is good and the range of application of the active energy ray effective coating composition can be expanded.

Procedural amendment (spontaneous) Showa year 1 > month] 7th 1, case description 1988 Patent Application No. 273359 2
, Title of the invention Active energy ray curable coating composition 3,
Relationship with the case of the person making the amendment Patent applicant address: 2-3-13-4 Kyobashi, Chuo-ku, Tokyo, “Detailed description of the invention” column (1) of the specification to be amended, page 2, number 17 of the specification Correct the line "Coating agent" to "Coating composition".

(2) "-Basic acid" on page 3, line 11 of the specification is corrected to "-valent carboxylic acid."

(3) "Polybasic acid" on page 4, line 18 of the specification is corrected to "polycarboxylic acid."

(4) "-Basic acid" on page 7, line 10 of the specification is corrected to "-valent carboxylic acid."

(5) “-Basic acid” on page 7, lines 10-11 of the specification is replaced with “
-Corrected to "carboxylic acid".

(6) "Production Example-5..." on page 15, lines 5 to 16 of the specification.
...This is referred to as resin e. ” to be deleted.

(7) In Table 2 on page 19 of the specification, the column ``Number of sheets where stains start to occur'' for Example Sample 7 indicates that stains occur at 20,000 sheets, but no stains occur at 20,000 sheets.''
Correct to.

(8) In Table 2 on page 19 of the specification, the column ``Number of sheets where stains start to occur'' for example sample 8 indicates that stains occur at r20,000 sheets, but no stains occur at r20,000 sheets.''
Correct to.

(9) r5/7J on page 20, line 8 of the specification is “5-7”
Correct to.

Claims (1)

[Claims] 1. (A) an alkyd resin obtained using pentadecenylsuccinic acid or its anhydride, (B) a monomer having a radically polymerizable double bond, (C) as necessary. An active energy ray-curable coating composition comprising: a radical polymerization initiator;