JPS609045B2 - UV-curable resin composition with excellent pigment dispersibility and adhesive properties - Google Patents

Description

[Detailed description of the invention] The present invention relates to an ultraviolet curable resin composition.

An object of the present invention is to provide an ultraviolet curable resin composition that has excellent maneuverability, adhesiveness, processability, and good pigment dispersibility. In recent years, in response to social demands such as resource saving, non-pollution, and safety, the development of ultraviolet curable resins, which are so-called solvent-free resins, has been actively promoted.

Examples of binders for UV-curable inks, paints and coatings include epoxy acrylate,
Various resins such as urethane-modified acrylate and oligoester acrylate have been proposed (for example, Japanese Patent Publication No. 53-37902, Japanese Patent Publication No. 54-15691, Japanese Patent Publication No. 54-15473, etc.), but paper, At present, it has only been put into practical use in some areas, such as in the woodworking field. Although UV-curable inks, paints, and coatings have many advantages such as being non-polluting, fast-curing, and resource-saving, the main reason for their sluggish growth is that they have poor adhesive properties compared to conventional products. , it is significantly inferior in terms of flexibility and workability.

Therefore, in order to expand the field of application of ultraviolet curable resins, it is necessary to improve their adhesion to metals, various plastics, various films, coated metal plates, etc., as well as their flexibility and processability. However, as there are currently no UV-curable resins with good adhesion, flexibility, and processability that can be used in these fields of application, special and complicated treatments are applied to the substrate to achieve twilling. At present, the performance has been improved (for example, Japanese Patent Application Laid-open No. 150504/1983).

). Needless to say, such treatment of the adherend substrate not only complicates the process but also increases production costs. As described above, currently no UV-curable resin with excellent adhesiveness, flexibility, or processability has been developed, and the industry is strongly demanding the development of a resin that meets these performance requirements. be. The present inventors used a saturated copolymerized polyester that is soluble in polymerizable compounds in order to obtain an ultraviolet curable resin with excellent adhesion, miscibility, and processability. We have discovered that it is possible to obtain a composition that has excellent adhesion to various films, coated metal plates, etc., and has practical adhesion, camouflage properties, processability, etc. without the need for the above-mentioned complicated treatments. I have already proposed it (Tokukoshi Sho 54-171820).

However, although this ultraviolet curable resin composition was revolutionary in that it had extremely good adhesion to untreated composite substrates, the dispersibility of pigments was not necessarily sufficient. There wasn't.

The present inventors conducted further intensive research to improve this point, and found that by using a saturated copolymerized polyester containing a sulfonic acid metal base, the pigment dispersibility was excellent, and metal
The inventors have discovered that a composition with further improved adhesion to glass and the like can be obtained, and have thus arrived at the present invention. That is, the present invention uses a polymerizable compound (b) with a soluble molecular weight of 1000 to 150.
00 saturated copolymerized polyester (1), polymerizable compound (
b) and a photosensitizer (m), and the saturated polycarboxylic component of the saturated copolymerized polyester (1) is 'a} 0 to 80 mol% of aliphatic or alicyclic dicarboxylic acid, 'b}
Aromatic dicarboxylic acids containing no sulfonic acid metal bases 9
9.5 to 19.5 mol%, and {c-sulfonic acid metal base-containing aromatic dicarboxylic acid 0.5 to 20 mol%, and at least one portion of the polymerizable compound (b) has two molecules in the molecule. The present invention is an ultraviolet curable resin composition having excellent pigment dispersibility and adhesive properties, and is characterized by being a compound having the above polymerizable double bond.

In the present invention, by containing a sulfonic acid metal base-containing aromatic dicarboxylic acid as the saturated polycarboxylic brewing component of the saturated copolymerized polyester, an ultraviolet curable resin composition with very good pigment dispersibility can be obtained.

This composition also has excellent adhesion, flexibility and processability. The saturated copolymerized polyester (1) having a molecular weight of 1,000 to 15,000 and soluble in the polymerizable compound used in the present invention is a polyester produced from a saturated polycarboxylic acid, a derivative thereof, and a polyhydric alcohol, The saturated polycarboxylic brewing component is ta) 0 to 80 mol% of aliphatic or alicyclic dicarboxylic acid, tb) 99.5% of aromatic dicarboxylic acid containing no sulfonic acid metal base.
It is a saturated copolymerized polyester consisting of ~19.5 mol% and (c) 0.5 to 20 mol% of an aromatic dicarbonate brewing component containing a sulfonic acid metal group. The saturated copolymerized polyester is a saturated copolymerized polyester that dissolves in a polymerizable compound, particularly acrylic acid esters, at least 2% by weight or more and provides a uniform and transparent solution at room temperature.

Aliphatic or alicyclic dicarboxylic acid of the present invention {a' includes succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid,
Examples include chlorendic acid, and the amount is 0 to 80 mol%, preferably 0 to 60 mol% of the saturated polycarboxylic brewing component.

If it exceeds 80 mol%, a composition with good water resistance, adhesion, coating strength, etc. cannot be obtained. Examples of aromatic dicarboxylic acids 'b} that do not contain sulfosometallic bases include terephthalic acid, isophthalic acid, orthophthalic acid, 2.6
Examples include mono-naphthalenedicarbosic acid.

Particularly preferred are terephthalic acid and/or isophthalic acid. These aromatic dicarboxylic acids that do not contain sulfonic acid metal bases contain 99.5 to 19
．． 5 mol%, preferably 99.5 to 39.5 mol%. Sulfonic acid metal base-containing aromatic dicarboxylic acid 'c}
Examples include sulfoterephthalic acid, 5-sulfisophthalic acid, 4-sulfophthalic acid, and 4-sulfonaphthalene-2.
Examples include metal salts of 7-dicarboxylic acid, 5-[4-sulfophenoxy]isophthalic acid, and the like.

Metal salts include Li, Na, K, Mg, Ca, CuFe
Salts such as Particularly preferred is 5-sodium sulfisophthalic acid. These sulfonic acid metal group-containing aromatic dicarboxylic acids are 0.5 to 20 mol%, preferably 1.0 to 10% by mole of the saturated polycarboxylic brewing ingredients.
It is mole%. If the amount of the aromatic dicarboxylic acid containing a sulfonic acid metal group exceeds 20 mol %, water resistance will be impaired and solubility in polymerizable compounds will also be reduced, which is not preferable. As the saturated polycarboxylic brewing component, in addition to the above compounds, it is also possible to use trifunctional or higher functional polycarboxylic acids such as trimellitic acid and pyromellitic acid, in which case the amount is 10 mol% or less. This is desirable.

Examples of polyhydric alcohol components include ethylene glycol, propylene glycol, 1,4-phthanediol,
Alkylene glycols such as 1,6-hexanediol, 1,5-pentanediol, neobentyl glycol,
Polyoxyalkylene glycols such as diethylene glycol, triethylene glycol, tetra or more polyethylene glycol, dipropylene glycol, tri or more polypropylene glycol, polytetramethylene glycol, halogenated alkylene glycols such as dibromoneobentyl glycol, 1・4-Cyclohexanediol, ethylene oxide of bisphenol A or/
and propylene oxide adducts, hydrogenated bispheno-
Examples include ethylene oxide and/or propylene oxide adducts of Formula A, 1,4-cyclohexanedimethanol, and the like.

These polyhydric glycol components may be used alone or in combination. As the polyhydric alcohol component, in addition to the above-mentioned glycols, it is also possible to use trihydric or higher polyhydric alcohols such as trimethylolpropane, trimethylolethane, bentaerythritol in an amount of 10 mol % or less.

If necessary, a small amount of monohydric carboxylic acid or monohydric alcohol may be used in combination. These saturated copolymerized polyesters may be used alone or in combination of two or more. The method for producing the saturated copolymerized polyester (1) of the present invention is not particularly limited, and methods such as transesterification and direct esterification are used, and if necessary, tetra-n-butyl titanate,
Known catalysts such as stannous oxalate, zinc acetate and antimony trioxide are used.

The saturated copolymerized polyester (1) of the present invention has a molecular weight of 1000 to 1
6000 and must be soluble in the polymerizable compound (b) described below.

Examples of preferred components of the saturated copolymerized polyester (1) that satisfy solubility in the polymerizable compound (0) include, for example, 5-sodium sulfisophthalic acid as an essential component, terephthalic acid and isophthalic acid three-component system of acids,
There are four-component systems of terephthalic acid, isophthalic acid and adipic acid, three-component systems of terephthalic acid and adipic acid, four-component systems of terephthalic acid, isophthalic acid and sebacic acid, and polyhydric alcohol components include ethylene glycol and Examples include a two-component system of propylene glycol, a two-component system of ethylene glycol and 1,6-hexanediol, and a one-component system of ethylene glycol and neobentyl glycol, but are not limited to these. The solubility of the saturated copolymerized polyester (1) in the polymerizable compound (b) is greatly affected by the acid value and molecular weight of the saturated copolymerized polyester (1), so the molecular weight is 1000.
It is necessary that the acid value is in the range of ~15,000, and the acid value is 5.
It is preferably 0 or less.

The polymerizable compound (b) used in the present invention is in the molecule]
It is a photopolymerizable compound having two or more polymerizable double bonds, and at least part of the polymerizable compound (0) is a compound having two or more polymerizable double bonds in the molecule.

Examples of photopolymerizable compounds having one polymerizable double bond in the molecule include (i) styrene compounds such as styrene, b-methylstyrene, and chlorostyrene;
i} Methyl (meth)acrylate (meaning methyl acrylate and methyl methacrylate. The same abbreviation hereinafter), ethyl (meth)acrylate, n- and i-propyl (meth)acrylate, n-, sec and t
-butyl (meth)acrylate, 2-ethylhexyl (
meth)acrylate, lauryl(meth)acrylate,
Alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and stearyl (meth)acrylate, or alkyl (meth)acrylates such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and butoxyethyl (meth)acrylate. Alkyl (meth)acrylate, allyloxyalkyl (meth)acrylate such as phenoxyethyl (meth)acrylate, hydroxyalkyl (such as hydroxyethyl (meth)acrylate)
meth)acrylate, halogen-substituted alkyl methacrylate, or polyethylene glycol mono(meth)
Acrylate, polypropylene glycol mono(meth)
Examples include polyoxyalkylene glycol mono(meth)acrylate such as acrylate and substituted alkyl mono(meth)acrylate such as alkoxypolyoxyalkylene glycol. Also, 0ii) Mono(meth)acrylates of alkylene oxide adducts of bisphenol A, such as ethylene oxide or/and propylene oxide adducts of bisphenol A, or hydrogenated bisphenol A, such as ethylene oxide and/or propylene oxide adducts. Bisphenol A
These include mono(meth)acrylates with alkylene oxide adducts. Furthermore, GV] one in the molecule obtained by reacting a terminal isocyanate group-containing compound obtained by reacting a diisocyanate compound and two or more alcoholic hydroxyl group-containing compounds in advance with an alcoholic hydroxyl group-containing (meth)acrylate. Urethane-modified mono(meth)acrylate having a (meth)acryloyloxy group, or epoxy mono(meth)acrylate obtained by reacting acrylic acid or methacrylic acid with a compound having one or more epoxy groups in the M molecule Alternatively, there may be acrylic acid or methacrylic acid as a skin carboxylic acid component, and oligoester mono(meth)acrylate obtained by reacting a polyhydric carboxylic acid with two or more polyhydric alcohols as an alcohol component. Photopolymerizable compounds having two polymerization double bonds in the molecule include:
For example, (i) ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1
・Alkylene glycol di(meth)acrylates such as 4-butanediol di(meth)acrylate, neobentyl glycol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, tri- Ethylene glycol di(meth)acrylate, dipropylene glycol di(
meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate
Polyoxyalkylene glycol di(meth)acrylates such as acrylates, substituted alkylene glycol di(meth)acrylates such as halogen-substituted alkylene glycol di(meth)acrylates, hydroxyl-substituted alkylene glycol di(meth)acrylates, ( ii) Di(meth)acrylates of alkylene oxide adducts of pisphenol A, such as ethylene oxide or/and propylene oxide adducts of bisphenol A; Alkylene oxide adduct di(meth)acrylate, (i
il) Two (2) ( Epoxy di(meth)acrylate obtained by reacting acrylic acid or methacrylic acid with a molecular weight having two or more epoxy groups in the molecule of G, a urethane-modified di(meth)acrylate having a meth)acryloyloxy group, M Typical examples include acrylic acid or methacrylic acid as the carboxyl-brewing component, and oligoester di(meth)acrylate obtained by reacting a polyhydric carboxylic acid with a polyhydric alcohol of dihydric or higher valence as the alcohol component.

Examples of photopolymerizable compounds having three or more polymerizable double bonds in the molecule include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(
Polyhydric (meth)acrylate of trivalent or higher aliphatic polyhydric alcohol such as meth)acrylate, bentaerythritol tetra(meth)acrylate, or polyhydric (meth)acrylate of trivalent or higher hydroxyl-substituted aliphatic polyhydric alcohol, (ii) Three or more terminal isocyanate group-containing compounds obtained by reacting a diisocyanate compound and two or more alcoholic hydroxyl group-containing compounds in advance with an alcoholic hydroxyl group-containing (meth)acrylate in the molecule. Examples include urethane-modified (meth)acrylates having (meth)acryloyloxy groups.
These polymerizable compounds (0) are used alone or in combination.

However, the polymerizable compound used in the present invention (
At least a portion of (b) needs to be a compound having two or more polymerizable double bonds in the molecule.
The amount is 1 to 100% by weight, preferably 5 to 90% by weight of the compound (b) having two or more polymerizable double bonds in the molecule. In particular, when a compound having one polymerizable double bond in the molecule and a compound having 2, 3 or 4 polymerizable double bonds in the molecule are used together, two or more polymerizable double bonds in the molecule Compounds having a double bond are polymerizable compounds (b) 5-
Preferably, it is 8% by weight.

Furthermore, when a compound having two polymerizable double bonds in the molecule and a compound having three or four polymerizable double bonds in the molecule are used together, two polymerizable double bonds in the molecule The compound having 85 to 95% by weight of the polymerizable compound (D)
It is preferable that If only a compound having one polymerizable double bond in the molecule is used, the so-called curing reaction cannot occur, so the object of the present invention cannot be achieved. The blending ratio of the soluble saturated copolymerized polyester (1) and the polymerizable compound (b) is saturated copolymerized polyester (1):polymerizable compound (0) in a weight ratio of 10:90 to 80:20, Preferably 30
:70 to 70:30. Saturated copolymerized polyester (
If the blending ratio of 1) is less than 1% by weight, a product with excellent adhesiveness and flexibility cannot be obtained, and if it exceeds 8% by weight, the viscosity becomes too high to be practical. The photosensitizer (m) used in the present invention is the polymerizable compound (0)
Compounds that promote the photopolymerization reaction of, and are not particularly limited to, for example, penzoins such as penzoin methyl ether, benzoin ethyl ether, penzoin-i-propyl ether, benzoin, Q-methylbenzoin, etc.
10-anthraquinone, 1-chloroanthraquinone, 2
- anthraquinones such as chloroanthraquinone, penzophenones such as benzophenone, p-chlorobenzophenone and p-dimethylaminobenzophenone, sulfur-containing compounds such as diphenyl disulfide and tetramethylthiuram disulfide, methylene blue, Eosin,
Dyes such as fluorescein may be used alone or in combination of two or more.

The amount of the photosensitizer (m) is 0.05 based on the total amount of the saturated copolymerized polyester (1) and the polymerizable compound (b).
-2% by weight, especially 0.5-1% by weight are preferred.

In addition, in order to increase the photopolymerization reaction promoting effect of photosensitizers, amines such as triethanolamine, triethylamine, N-N-diethylaminoethyl (meth)acrylate, and phosphorus such as triphenylphosphine are used as photosensitizers. It is also possible to use compounds in combination.

The ultraviolet curable resin composition of the present invention has thermal and heavy E at the time of manufacture.
In order to prevent reactions during synthesis and storage, known thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethylenal, t-butylcatechol, p-benzoquinone, 2,5-t-butyl-hydroquinone, and phenothiadiso are added. is desirable.

The blending amount is 0.0001 per polymerizable compound (day)
-0.1% by weight, preferably 0.001-0.05% by weight. The ultraviolet curable resin wire composition of the present invention has uses,
Depending on the purpose, for example, white pigments such as titanium dioxide and zinc white, black pigments such as carbon black, pine smoke, and graphite, yellow pigments such as yellow lead, light yellow lead, red zinc, and zinc yellow, vermilion, red iron, etc. red pigments, blue pigments such as navy blue, cobalt blue,
Green pigments such as chrome green and green earth; iron oxide pigments such as iron oxide yellow, iron oxide black, and mars yellow; extender pigments such as calcium carbonate, barium sulfate, clay, alumina, and talc; Azo organic pigments such as Phthalocyanine Flu B, Phthalocyanine organic pigments such as Phthalocyanine Glyrin, Quinacryzone organic pigments such as Quinacryzone Red, Metal powder pigments such as silver powder, copper powder, gold powder, glass beads, glass powder, glass flakes, etc. can be blended.

In addition to the above-mentioned pigment additives, the ultraviolet curable resin composition of the present invention may contain acrylic additives known as surface smoothing agents, such as Modaflow (manufactured by Monsanto Chemicals) and Polyflow S (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.). ) etc. and silicone additives, such as Vynro)/OL (manufactured by Bayer AG), Y
F-3818 (manufactured by Toshiba Silicon ■) etc. can be added.

The ultraviolet curable resin composition of the present invention may include synthetic resins other than saturated copolymer polyester/l-ray, such as melamine resins, epoxy resins, phenoxy resins, polyurethane resins, polystyrene, Polybutadiene, polyvinyl chloride, polyethylene, polypropylene, polyvinyl acetate, ethylene monopynylacetate copolymer, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, styrene- It is also possible to blend a maleic anhydride copolymer, a butadiene m maleic anhydride copolymer, and the like. The ultraviolet curable resin composition of the present invention is coated or printed on an adherend substrate using a conventional coating method or printing method, and then irradiated with ultraviolet rays to induce a photopolymerization reaction and to be cured.

As a light source used for irradiating this ultraviolet ray, sunlight, a chemical lamp, a low pressure mercury lamp, a high pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, etc. are used. Of course, the ultraviolet curable resin composition of the present invention can also be applied to curing methods by thermal polymerization using organic peroxides instead of ultraviolet rays, and electron beam curing methods in which curing is performed by irradiating electron beams. does not necessarily require a photosensitizer.

The ultraviolet curable resin composition of the present invention has adhesive properties, malleability,
Not only does it have processability that conventional ultraviolet curable resins cannot achieve, but by using a saturated copolymer polyester containing sulfonic acid metal bases,
The dispersibility of the pigment is very good, and it must be said that the industrial significance of the present invention is extremely large.The ultraviolet curable resin composition of the present invention takes advantage of the above characteristics to be used in glass, ceramics, metals, various plastics, Used as a binder for inks, paints, and coatings for various films, ceramic plates, painted metal plates, etc.

EXAMPLES Examples are given below to explain the present invention more specifically, but the present invention is of course not limited by the Examples.

In Examples and Synthesis Examples, parts indicate parts by weight.

The mol% of each component in the polyester was determined by NM old analysis (solvent:
CDC13). Moreover, the molecular weight was measured by the vapor pressure drop method. The viscosity in the examples is a value measured at 25 qo using a B-type rotational viscometer.

Further, the pencil hardness of the cured film was measured according to JIS K5400, and the adhesiveness was measured by peeling from a goblin-cellotape. Synthesis Example 1 In a stainless steel autoclave equipped with a rope machine, a thermometer, and a partial reflux condenser, 19 parts of dimethyl terephthalate, 188 parts of dimethyl isophthalate, 191 parts of ethylene glycol, and 15 parts of 1,6-hexanediol were added.
6 parts and 0.25 part of tetra-n-butyl titanate were added, and the temperature was gradually raised until the reaction temperature reached 220 qo, and the reaction was carried out at 220 qo for 2 hours.

Next, 13.4 parts of 5-sodium sulfoisophthalic acid was added and reacted for 1 hour at 220 qo to 260 oz, and then reacted for 1 hour at a temperature of 260 oz under a reduced pressure of 1 tung Hg to form a saturated copolymerized polyester sail. Obtained. The molecular weight of the obtained saturated copolyester polyester (2) was 3,500. NMR
The composition measured by the method was as follows. Polyvalent carboxylic acid brewing ingredients: Terephthalic acid 49.0 mol% Isophthalic acid 48.5 mol% 5-sodium sulfoisophthalic acid 2.5 mol% Polyhydric alcohol ingredient: Ethylene glycol 40 mol%
1,6-hexanediol 60 mol%.

Various saturated copolymerized polyesters 'B} to [E} shown in Table 1 were produced in a similar manner.

Table 1 Synthesis Example 2 Add dimethyl terephthalate 19 to the same reaction vessel as Synthesis Example 1.
Add 19 parts of dimethyl isophthalate, 142 parts of ethylene glycol, 22 parts of neobentyl glycol, 0.2 parts of zinc acetate, and 0.2 parts of antimony trioxide, and heat the ester at 140°C to 220q○ for 3 hours. An exchange reaction was performed.

Next, 11 parts of 5-sodium sulfisophthalic acid was added and the esterification reaction was carried out at 220°C to 260°C for 1 hour.
The reaction was carried out for 2 hours under a reduced pressure of ~0.2 skin Hg to obtain a saturated copolymerized polyester {F}. The molecular weight of the obtained saturated copolymerized polyester was 19,500. The composition determined by NMR was as follows. Polyhydric carboxylic acid brewing components: Terephthalic acid 49 mol% Isophthalic acid 49 mol% 5-sodium sulfisophthalic acid 2 mol Polyhydric alcohol components: Ethylene glycol 40 mol Neobentyl glycol 60 mol% Synthesis example 3 Same as synthesis example 1 194 parts of dimethyl terephthalate in the reaction vessel,
Dimethyl isophthalate, 191 parts of ethylene glycol,
156 parts of 1,6-hexanediol and 0.25 parts of tetra-n-butyl titanate were added, the temperature was gradually raised until the reaction temperature reached 220 qo, and the reaction was carried out at 220 qo for 2 hours, and then the pressure was gradually reduced. IQ Misaki Hg under reduced pressure 260
The saturated copolymerized polyester (
G) was obtained.

The molecular weight of the obtained saturated copolymerized polyester (G) is 39
It was 00. The composition measured by NM old was as follows. Polyhydric carbon brewing ingredients: Terephthalic acid 50 mol% Isophthalic acid 50 mol% Polyhydric alcohol ingredient: Ethylene glycol 40 mol%1
-6-hexanediol 60 mol%.

Example 1 50 parts of the saturated copolymerized polyester obtained in Synthesis Example 1, 25 parts of tetrahydrofurfuryl acrylate, 25 parts of 1,6-hexanediol diacrylate, 3 parts of penzoethyl ether as a photosensitizer, and 0.01 part of hydroquinone as a heat build-up inhibitor was mixed and dissolved under heating at 80°C to obtain an ultraviolet curable resin composition '1- of the present invention.

The obtained resin composition was a transparent and uniform solution. Various ultraviolet curable resin compositions {11 to (11
) was prepared.

Next, the obtained composition was coated on an untreated polyethylene terephthalate film (thickness: 12 mm) using a bar coater #20.
5r) and after applying to untreated mild steel plate 5. A transparent cured film was obtained by irradiating ultraviolet rays with a high-pressure mercury lamp at a distance of 15 skins for 3 times. Table 2 shows the results of measuring the performance of the cured film. Table 2 Example 2 and Comparative Example 1 45 parts of the saturated copolymerized polyester wind obtained in Synthesis Example 1 was added to 80 parts of
With addition of salt, 3 parts of tetrahydrofurfuryl acrylate, 3 parts of diacrylate of 4 moles of ethylene oxide adduct of bisphenol A, 5 parts of 1,6-hexanediol diacrylate, and 0.02 part of hydroquinone monomethyl ether. The ultraviolet curable resin composition (12) of the present invention was obtained by dissolving 7 parts of penzoin ethyl ether in a mixed solution of the above.

85 parts of the obtained composition, 13 parts of titanium dioxide, and 2 parts of an acrylic surface smoothing agent were thoroughly kneaded using three rolls to prepare an ultraviolet curable ink [a}. An ultraviolet curing* ink (b) was prepared in exactly the same manner as described above, except that the saturated copolymer polyester (G) obtained in Synthesis Example 3 was used instead of 45 parts of the saturated copolymer polyester. Using these inks {a} and {b}, print on various substrates using a 300-mesh screen printing plate, and 5. irradiate the printed film with ultraviolet rays for 19 seconds at a distance of 12 skins under a Fox W high-pressure mercury lamp. The performance of these inks was measured in glass bottles (
It was put into a volume (100 cc), sealed tightly, and stored in a 2,500-meter container to measure storage stability. These results are shown in the third
Shown in the table. Comparative Example 2 50 parts of the saturated copolymerized polyester Tsukuda obtained in Synthesis Example 2, 25 parts of tetrahydrofurfuryl acrylate, 25 parts of neobentyl glycol diacrylate, 0 parts of hydroquinone
．． 01 part was mixed under 80 ml of salt, but the solubility was extremely poor and it was difficult to form a uniform solution.

Table 3

Claims (1)

[Claims] 1 Molecular weight soluble in polymerizable compound (II) 1000-15
000 saturated copolymerized polyester (I), a polymerizable compound (II) and a photosensitizer (III), and the saturated polycarboxylic acid component of the saturated copolymerized polyester (I) is (a)
Aliphatic or cycloaliphatic dicarboxylic acid 0 to 80 mol%, (b
) 99.5 to 19.5 mol % of an aromatic dicarboxylic acid not containing a sulfonic acid metal group and (c) 0.5 to 20 mol % of an aromatic dicarboxylic acid containing a sulfonic acid metal group, and the polymerizable compound ( An ultraviolet curable resin composition having excellent pigment dispersibility and adhesiveness, characterized in that at least a portion of II) is a compound having two or more polymerizable double bonds in the molecule.