JPS63117023A - Resin composition and printing ink composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having good stability and a high curing rate and being low in coloration of a cured product, by mixing polyurethane (meth)acrylate with acryloylmorpholine. CONSTITUTION:A resin composition containing polyurethane (meth)acrylate and acryloylmorpholine. Examples of desirable polyurethane (meth)acrylates include polyether polyurethane acrylate, polyester polyurethane acrylate, etc. The amount of the polyurethane (meth)acrylate used is preferably 10-80wt% based on the resin composition. Acryloylmorpholine is easily available from the market, and its amount of use is preferably 5-60wt% based on the resin composition. This resin composition can be cured, for example, by ultraviolet rays and is suitable for use in, especially, a UV-curing screen printing ink.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a resin composition, and particularly to a resin composition suitable for an ultraviolet curable screen printing ink (composition for printing ink).

(Prior art) Examples of photocurable compositions containing polyurethane acrylate include JP-A-48-25095 and JP-A-49-133.
491, No. 57-83562, and the like. Moreover, the proportion of these materials used in printing inks and coating agents is increasing.

(Problems to be Solved by the Invention) Since polyurethane acrylate has a high viscosity, it is necessary to dilute it with a low-viscosity monomer before use. Currently, N-vinyl pyrrolidone is often used due to the problem of adhesion to various base materials (eg, polyvinyl chloride, polycarbonate, polymethacrylic resin, etc.). By using N-vinyl pyrrolidone,
Although it is possible to make inks, coatings, etc. with excellent curability and adhesion, compositions containing N-vinyl pyrrolidone tend to thicken, gel, or become colored over time. Moreover, the cured product becomes colored, which is a problem especially in the case of a composition containing a white pigment (titanium oxide, etc.).

(Means for Solving the Problems) In order to solve the above problems, the present inventors have conducted intensive research and found that a resin with good stability of the liquid composition, fast curing speed, and little coloring of the cured product The present invention has been completed by successfully providing a composition.

That is, the present invention provides (1) a resin composition characterized by containing polyurethane (meth)acrylate and acryloylmorpholine, and (2) a resin composition characterized by containing polyurethane (meth)acrylate and acryloylmorpholine. The present invention relates to a composition for printing ink.

In the present invention, polyurethane (meth)acrylate is used. Polyurethane (meth)acrylate is obtained by reacting a polyol compound, an organic diisocyanate, and a (meth)acrylic acid ester having a hydroxyl group to the extent that the polyurethane (meth)acrylate contains substantially no NCO groups. Representative polyol compounds include ethylene glycol, propylene glycol, 1.3-7'' ethylene glycol, neopentyl glycol, cyclohexa/dimetatool, and tricyclodecane dimethylol.

1,4-butanediol, 1,6-hexenediol,
Polyols such as trimethylolpropane Polyether polyols such as polypropylene glycol, polyethylene glycol, polytetramethylene glycol, glopylene glycol-modified polytetramethylene glycol, trimethylolpropane polyethoxy, and trimethylolpropane polyethoxy.

The above-mentioned polyol or polyether polyol, or a compound in which ε-caprolactone or valerolactone is added to the above-mentioned polyol is used as the alcohol component, and one of the acid components is adipic acid, cepacic acid, azelaic acid, dodecanedicarboxylic acid, phthalic acid. , polyester polyols made of dibasic acids such as tetraphthalic acid, hexahydrophthalic acid, and their anhydrides, and polycarbonate polyols made of the above polyols, polyether polyols, and polyester polyols as alcohol components.

Typical organic diincyanates include aromatic diisocyanates such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate, alicyclic diisocyanates such as inphorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate, and hexyl diisocyanates. There are aliphatic diincyanates such as chimetele diincyanate and 2,2'-)limethylhexamethylene diincyanate. The ratio of the polyol compound and the organic diisocyanate used in the urethanization reaction is preferably 1.1 to 2.0 chemical equivalents of the NCO group of the organic diisocyanate per 1 chemical equivalent of the OH group of the polyol compound. Particularly preferably, the chemical weight is 1.5 to 2.0. This urethanization reaction can be carried out in procedures known to those skilled in the art. The reaction temperature of this urethanization reaction is from room temperature to 1
00°C, preferably 50-80°C.

Then, in the (meth)acrylation reaction,
0.9 to 1.5 chemical equivalents of the OH group of the (meth)acrylic ester having a hydroxyl group per 1 chemical equivalent of the NCO group of the compound having a terminal incyanate group obtained by the urethanization reaction, Preferably 1.0 to 1.
1 chemical equivalent is used. Typical examples of methane acrylic acid esters having a hydroxyl group include β-hydroxyethyl (meth)acrylate, β-hydroxyglobil (meth)acrylate, ε-caprolactone-β-hydroxyethyl (meth)acrylate, and pentaerythritoltri acrylate, dipe/taerythritol bentaacrylate, etc.In this reaction, 50 to 2000 ppm of hydroquinone, hydroquinone monomethyl ether, P-methoxy It is preferable to add a heavy metal collector such as phenol or P-benzoquino/etc. Also, the reaction temperature of this acrylation reaction is room temperature to 100°C, preferably 50 to 80°C. The reaction between the
Conventional catalysts such as organometallic compounds such as dibutyltin silaurylate, dibutyltin diacetate, or tin chlorides may also be used.

Further, the NC of the reaction product with 0.5 chemical equivalent of the OH group of the (meth)acrylic acid ester having the hydroxyl group per 1 chemical equivalent of the NCO group of the organic diincyanate.
For one chemical equivalent of O group, O of the polyol compound
Polyurethane (meth)acrylates formed by reacting with 0.5 to 1 chemical equivalent of H groups can also be used. Preferred polyurethane (meth)acrylates include polyether polyurethane acrylate and polyester polyurethane acrylate. The amount of polyurethane (meth)acrylate used is 10 to 8 of the resin composition (or printing ink composition excluding pigments and fillers).
0% by weight is preferred, particularly preferably 20-70% by weight. In the present invention, acryloylmorpholine is used. Acryloylmorpholine is easily available on the market. For example, they are made by Kenjin ■, ACMO, etc. The amount of acryloylmorpholine used is 5 to 60% of the resin composition (or printing ink composition excluding pigments and fillers).
% by weight is preferred, particularly preferably 10-50% by weight. In the resin composition or printing ink composition of the present invention, various known ethylenically unsaturated compounds can be used as components other than polyurethane (meth)acrylate and acryloylmorpholine. Typical examples of ethylenically unsaturated compounds include tetrahydrofurfuryl acrylate, carpitol acrylate, phenoxyethyl acrylate, inbornyl acrylate, and hydrogenated dicyclopentadiene acrylate (manufactured by Hitachi Chemical, FA-513).
A), tricyclodecane dimethylol diacrylate,
Hydroxypivalate neopentyl glycol diacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, phenyl glycidyl ether acrylate, 1,6-hexanediol diacrylate, glycerin monoacrylate, epoxy acrylate, such as acrylate of epoxy resin of bisphenol A, Bisphenol F epoxy resin acrylate, bisphenol A urethane modified epoxy resin acrylate, polyester acrylate, etc.
For example, ethylene glycol, propylene glycol,
Diethylene glycol, cyclopyrene glycol, 1.
Acrylate of a polyester diol consisting of a diol component such as 5-bentanediol or 1,6-hexanediol and a dibasic acid such as succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid or tetrahydrophthalic acid, the above diol component and 2 Examples include acrylates of lactone-modified polyester diols consisting of a basic acid and ε-caprolactone or valerolactone, polycarbonate acrylates, such as acrylates of polycarbonate diols containing 1,6-hexanediol as a diol component.

Particularly preferred ethylenically unsaturated compounds include, for example, phenylglycidyl ether acrylate, phenoxytamide acrylate, hydrogenated dicyclopentadiene acrylate, and tetrahydrofurfuryl acrylate. The above-mentioned ethylenically unsaturated compounds may be used alone or in combination of two or more Fi compounds in any ratio, if necessary. The amount of the ethylenically unsaturated compound used is preferably 0 to 50% by weight, and 20 to 40% by weight in the resin composition (or printing ink composition excluding pigments and fillers).
% by weight is particularly preferred.

These ethylenically unsaturated compounds can be easily obtained manually from the market. The resin composition or printing ink composition of the present invention can be cured by a known method. For example, it can be cured by ultraviolet light. In the case of curing by ultraviolet light,
It is necessary to use a photoinitiator. As the photopolymerization initiator, any known photopolymerization initiator may be used, but it is required to have good storage stability after blending. Examples of such photopolymerization initiators include benzoin alkyl ethers such as benzoin ethyl ether, benzoin isobutyl ether, and benzoin isopropyl ether;
Acetophenone series such as 2,2-jetoxyacetophenone, 4'-phenoxy-2,2-dichloroacetophenone, 2-hydroxy-2-methylpropiophenone,
4'-isopropyl-2-hydroxy-2-methylpropiophenone, 4'-dodecyl-2-hydroxy-2-
Propiophenones such as methylpropiophenone, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone (manufactured by Chipa Geigy ■).

Irgacure 84) and anthraquinones such as 2-ethylanthraquinone and 2-chloroanthraquinone,
Other examples include thioxanthone-based photopolymerization initiators. Particularly preferred are benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone,
Examples include diethyl thioxanthone. These photopolymerization initiators may be used alone or in a mixture of two or more in any proportion. The amount used is usually 0.1 of the resin composition (or printing ink composition excluding pigments and fillers).
-10% by weight, preferably 3-7% by weight.

The resin composition or printing ink composition of the present invention may optionally contain non-reactive resins, pigments, and various other additives, and the non-reactive resin is polyester resin.

Examples include alkyd resins, phenolic resins, polyurethanes, polybutadiene, polyethers, epoxy resins, and styrene-containing polymers. In addition, the above additives include silicon compounds, Modaflow (leveling agent),
Examples include polymerization inhibitors and others.

When the resin composition of the present invention is used as an ultraviolet ray curable screen printing ink, a screen printing method is suitable as the printing method.

It is printed on a substrate (eg, polycarbonate, polyvinyl chloride, etc.) to a thickness of 10 to 30 microns by screen printing, and then cured by UV irradiation.

(Example) The present invention will be specifically explained below using an example. In addition,
Parts in the examples are parts by weight.

[Polyurethane (meth)acrylate] Synthesis Example 1 Into a 21 reactor equipped with a stirrer, temperature control device, thermometer, and condenser, 230 parts of polyester diol (polyester diol with a molecular weight of 480 consisting of neopentyl glycol and adipic acid), Polytetramethylene glycol (manufactured by Odugaya Chemical, PTG-500p, molecular weight approximately 2000
244.8 parts of 2-hydroxyethyl acrylate and 200 parts of inphorone diincyanate were charged, and after raising the temperature, the reaction was carried out at 75°C for 10 hours.Then, the reaction solution was cooled to 60°C, and 68.7 parts of 2-hydroxyethyl acrylate and 0.0 parts of methoquinone were added. 37 parts and 0.114 parts of di-n-butyltin laurate were charged, and after raising the temperature, 75
The reaction was carried out at ~80°C. The reaction was continued until completion as indicated by about 0.1 or less free incyanate groups.

The product has the following properties.

Viscosity 1510 pojse (60'C) Synthesis Example 2
゜The same reactor K as in Synthesis Example 1, 430.9 parts of polypropylene glycol (manufactured by Sanyo Kasei ■, Sannix [) p-2000, molecular weight 2000), 427 parts of polytetramethylene glycol (molecular weight 2000), tricyclodecanediol 187.7 parts of methylol and 620.4 parts of inphorone diincyanate were charged, and after raising the temperature, the reaction was carried out at 80'C for 10 hours.Then, the reaction solution was cooled to 60°C, and 334 parts of 2-hydroxyethyl acrylate and 1.4 parts of methoquinone were charged. 0 copies,
0.4 part of di-n-butyltin laurate was charged, and after raising the temperature, the reaction was carried out at 75 to 80°C. The reaction was continued until completion as indicated by about 0.1 or less free incyanate groups. The product has the following properties.

Viscosity (60°C) 6600 poise Synthesis Example 3゜In the same reactor as Synthesis Example 1, polyester diol (consisting of neopentyl glycol and adipic acid with a molecular weight of 48
0 polyester diol) 384 parts, 7"ropylene glycol modified polytetramethylene glycol (manufactured by Odugaya Chemical, PPTG-2000, molecular weight 2000) 40
0 parts and Coronate 2094 (diisocyanate compound manufactured by Nippon Polyurethane ■, reaction product of 1 mole of hydrogenated bisphenol A and 2 moles of hexamethylene diisocyanate,
N00% is.

14.6%) 864 parts and heated to 10% in SO'C.
After reacting for an hour, the reaction solution was cooled to 60°C, and 176.4 parts of 2-hydroxyethyl acrylate and 0 parts of methoquinone were added.
．． After charging 9 parts and raising the temperature, the reaction was carried out at 75 to 80°C. The reaction was continued until completion as indicated by about 0.1 or less free incyanate groups. The product has the following properties.

Viscosity (60'C) 6800 poise [Resin composition (printing ink composition)] Example 1゜28 parts of polyurethane acrylate obtained in Synthesis Example 1, 28 parts of acryloylmorpholine, 14 parts of phenylglycisin ether acrylate, Irgacure 184 (Chibaφ
Geigy ■, photopolymerization initiator) 2 parts, diethylthioxanthone (Nippon Kayaku ■, KAYACURE, DET)
X, photopolymerization initiator) 1 part, N,N-dimethylbenzoic acid ethyl ester (manufactured by Nippon Kayaku ■, KAYACURE EP
A. Photopolymerization accelerator) 2 parts, methoquinone (polymerization inhibitor)
A resin composition (printing ink composition) A was prepared by mixing 0.035 parts and 30 parts of titanium dioxide (white pigment) and kneading with a three-roll mill. Table 1 shows the properties of the liquid composition and cured product.

Example 2゜35 parts of polyurethane acrylate obtained in Synthesis Example 2, 35 parts of acryloylmorpholine, 184.2 parts of Irgacure
1 part of diethylthioxanthone, 2 parts of N,N-dimethylbenzoic acid ethyl ester, methquinone (polymerization inhibitor)
Mix 0.035 parts and 30 parts of titanium dioxide.

Knead with three rolls to form resin composition (printing ink composition)
B was prepared. Table 1 shows the properties of the liquid composition and cured product.

Example 3゜28 parts of polyurethane acrylate obtained in Synthesis Example 3, 21 parts of acryloylmorpholine, 7 parts of tetrahydrofurfuryl acrylate, 14 parts of hydrogenated dicyclopentadiene acrylate (Hitachi Kasei, FA-513A), Irgacure 184 2 parts, 1 part of diethylthioxatone, N,
2 parts of N-dimethylbenzoic acid ethyl ester, 0.035 parts of methoquinone (polymerization inhibitor), and 30 parts of titanium dioxide were mixed and kneaded using three rolls to prepare a resin composition (printing ink composition) C. Table 1 shows the properties of the liquid composition and cured product.

Example 4゜21 parts of polyurethane acrylate obtained in Synthesis Example 1, 21 parts of acryloylmorpholine, 14 parts of phenyl glycidyl ether acrylate, 14 parts of phenoxyethyl acrylate, 184.2 parts of Irgacure, 1 part of diethylthioxanthone, N,N-dimethyl Mix 2 parts of benzoic acid ethyl ester, methoquinone (0.035 parts of polymerization inhibitor) and 30 parts of titanium dioxide.

Knead with three rolls to form resin composition (printing ink composition)
D was prepared. Table 1 shows the properties of the liquid composition and cured product.

Comparative Example 1 A resin composition (printing ink composition) E was prepared in the same manner as in Example 1, except that N-vinylpyrrolidone was used in place of acryloylmorpholine.

Table 1 shows the properties of the liquid composition and cured product.

Comparative Example 2 A resin composition (printing ink composition) F was prepared in the same manner as in Example 2, except that N-vinylpyrrolidone was used in place of the acryloylmorpholine.

imAqq &;Qi and ntz at ”f, 1
ni+=*z.

In Table 1 above, curable compositions of A, B, C, D, E and F were applied to a thickness of 1 m.
It was printed using a screen (thickness: 15 μm) on a polycarbonate resin of 100 m, and then irradiated with a high-pressure mercury lamp (lamp output: 2 kW) at a position of 8 cr IL under a light source arranged in parallel (conveyor speed: 5 m/min).
hardened.

The irradiation amount (mj/crd) until curing was determined.

Colorability: The degree of coloration on the printed surface was observed after the printed matter cured by the above method was left at 90°C for 24 hours.

○... has almost no discoloration.

△...Slightly discolored.

X: Significant discoloration.

Adhesion: Printed matter cured using the above method.

Crosscut - Sellotape peel test Do the following.

○: No peeling or cracking occurs at all.

△... Some cracks in the eyes are observed.

x: Peeling and chipping occurred.

Stability of liquid: 100 g of compositions A, B, C, D, E, and F were placed in a brown 100 ml polybottle and left at 70°C. After 30 days, the presence or absence of gelation was observed.

(Effects of the Invention) The resin composition (composition for printing ink) of the present invention has good liquid composition stability, fast curing speed, and little coloring of the cured product, and is particularly useful for ultraviolet curable screen printing inks. Suitable.

Claims (2)

[Claims] (1) A resin composition characterized by containing polyurethane (meth)acrylate and acryloylmorpholine. (2) A printing ink composition containing polyurethane (meth)acrylate and acryloylmorpholine.