JP3428145B2 - Active energy ray-curable resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which can be cured by irradiating an active energy ray such as an electron beam or an ultraviolet ray. More specifically, the present invention relates to a resin composition containing, as an essential component, an alkylene oxide-modified di (meth) acrylate of 1,4-cyclohexanedimethanol which is liquid at ordinary temperature. The resin composition of the present invention is expected to be applied to various uses such as active energy ray-curable coatings, printing inks and adhesives. [0002] Conventionally, thermosetting resin compositions have been used as resin compositions used for inks, paints, adhesives and the like. In recent years, however, energy saving, short curing treatment, and production of products have been used. Many inks, paints, adhesives, and the like using the active energy ray-curable resin composition have been developed and spread from the viewpoint of space saving by shortening the process line. Specifically, active energy ray-curable resin compositions containing various kinds of acrylates as main components are used. [0003] Above all, an active energy ray-curable resin composition containing a low-viscosity di (meth) acrylate as a main component is fast-curing and has good adhesion to a substrate.
It plays an important role in the surface hardening of the base material and in imparting functionality to inks and adhesives. [0004] In recent years, as a novel functional di (meth) acrylate, 1,4-
Cyclohexane di (meth) acrylate was reported.
Although the resin composition containing the compound is excellent in adhesion to a substrate, when the compound is used as a resin composition because it is a solid at room temperature, it must be dissolved in a solvent to form a liquid. The workability at the time of preparation and coating is poor, and the compound precipitates as crystals after the preparation of the resin composition, or the compatibility with other components is poor, and the cured product becomes cloudy. Had issues. The present inventors have made intensive studies on the above-mentioned problems, and as a result, modified 1,4-cyclohexanedimethanol with an alkylene oxide and then (meth) acrylated. In addition, by using a resin composition containing di (meth) acrylate which is liquid at ordinary temperature as an essential component, it can have low viscosity and low skin irritation, and has excellent curability and adhesion to a substrate. It has been found that an active energy ray-curable resin composition can be obtained, and the present invention has been completed. That is, the present invention provides the following (A) component:
Di (meth) acrylate of a diol represented by the general formula (I), wherein 1 to 8 mol of an alkylene oxide having 2 to 3 carbon atoms is added to 1 mol of 1,4-cyclohexanedimethanol.
5 to 90 parts by weight, and the number of functional groups is 3 or more as the component (B),
Polyfunctional (meth) acrylate having a molecular weight of 2000 or less (however,
And one (meth) acrylic acid in the molecule having a molecular weight of 500 or less.
Has a royl group and one hydroxyl or carboxyl group
(Excluding (meth) acrylate) 10 to 95 parts by weight
Active energy combined to total 100 parts by weight
A radiation-curable resin composition. Embedded image (Where R represents a hydrogen atom or a methyl group, and X represents (CH ₂ CH ₂ O) _n or (CH ₂ CH ₂ CH ₂ O) _n
And n is 1 to 8. ) [0007] In the present invention used as the component (A), the following one
Di (meth) of a diol represented by the general formula (I), wherein 1 to 8 mol of an alkylene oxide having 2 to 3 carbon atoms is added to 1 mol of 1,4-cyclohexanedimethanol which is liquid at ordinary temperature.
Acrylate is a liquid component at room temperature . for that reason,
The workability of preparation and coating when making a curable resin composition using this is good . Further, compared with the conventional resin composition using unmodified 1,4-cyclohexanedi (meth) acrylate which is solid at ordinary temperature, the component (A) is used.
The stored resin composition has good storage stability. Embedded image (Where R represents a hydrogen atom or a methyl group, and X represents (CH ₂ CH ₂ O) _n or (CH ₂ CH ₂ CH ₂ O) _n
And n is 1 to 8. Further, it has excellent crosslinking properties upon irradiation with active energy rays, is a low-viscosity liquid, and has particularly excellent adhesion of a cured product to a substrate. When used as a diluent for an active energy ray-curable compound, the resulting composition has excellent storage stability and excellent curability, as well as good adhesion of the cured product to a substrate. be able to. The composition comprises 5 to 90 parts by weight of component (A) and 95 to 10 parts by weight of component (B).
When used in a ratio of parts by weight, it exhibits its properties well. The di (meth) component (A) used in the present invention
Acrylate is produced as follows. First, 1,
1 to 8 mol of ethylene oxide or propylene oxide is added to 1 mol of 4-cyclohexanedimethanol,
Preferably, after adding 3 to 5 mol, the compound is (meth) acrylated by a known method such as esterification with (meth) acrylic acid or transesterification with (meth) acrylic acid ester. . Here, although the number of addition of the alkylene oxide to 1,4-cyclohexanedimethanol exceeds 8 mol, the viscosity of di (meth) acrylate is increased, so that the workability of the resin composition containing the compound is reduced. Or the curability thereof is lowered, which is not preferable. Specific examples of the polyfunctional (meth) acrylate having 3 or more functional groups and a molecular weight of 2,000 or less used as the component (B) in practicing the present invention include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (Meth) acrylate, ethylene oxide-added dimethylolpropanetetra (meth) acrylate, propylene oxide-added dimethylolpropanetetra (meth) acryl Over DOO, ethylene oxide adduct of pentaerythritol tetra (meth) acrylate, propylene oxide adduct of pentaerythritol tetra (meth) acrylate, ethylene oxide adduct of dipentaerythritol hexa (meth) acrylate. Among them, dipentaerythritol hexaacrylate is particularly preferable in terms of curability and adhesion to a substrate. When an ultraviolet ray is used as the active energy ray, the composition of the present invention usually contains a photopolymerization initiator,
It is preferable to include a photocatalyst compound composed of at least one of a photo-promoting agent, a photo-enhancing agent and the like. Examples of photopolymerization initiators include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthofluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, and 4-methylacetophenone.
Chlorobenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, 4-oxanthon, camphorquinone, 2-methyl-1- [4 (methylthio) phenyl] -2-morpholino-propan-1-one and the like. Further, a photopolymerization initiator having at least one acryloyl group or methacryloyl group in the molecule can also be used. Examples of the photosensitizer include 2-chlorothioxanthone, 2,4-diethylthioxanthone,
4-diisopropylthioxanthone and the like can be mentioned. Examples of the photo-promoting agent include 2-n-butoxyethyl p-dimethylaminobenzoate, isoamyl benzoate, 2-n-butoxyethyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and the like. Can be mentioned. The active energy ray-curable resin composition of the present invention may contain another radical polymerizable compound as long as the performance is not impaired. The radical polymerizable compound can be appropriately selected from various known reactive oligomers and vinyl monomers and used. The reactive oligomer is not particularly limited, but as a specific example, it can be obtained by reacting a polybasic acid such as phthalic acid and adipic acid with a polyhydric alcohol such as ethylene glycol and butanediol and (meth) acrylic acid. Polyester poly (meth) acrylate, epoxy poly (meth) acrylate obtained by reaction of epoxy resin with (meth) acrylic acid, urethane obtained by reaction of polyol with polyisocyanate and hydroxyl group-containing monomer such as 2-hydroxyethyl acrylate Poly (meth) acrylate, polysiloxane poly (meth) acrylate obtained by reaction of polysiloxane with (meth) acrylic acid compound, polyamide poly (meth) acrylate obtained by reaction of polyamide with (meth) acrylic acid compound Is mentioned. The radically polymerizable vinyl monomer is not particularly limited. For example, methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, Benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate,
2-dicyclopentenoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate,
Tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid, (meth)
Monofunctional (meth) acrylate monomers such as acryloylmorpholine, N-vinyl-2-pyrrolidone, N-vinylimidazole, N-vinylcaprolactam, styrene,
and vinyl monomers such as α-methylstyrene, vinyltoluene, allyl acetate, vinyl acetate, vinyl propionate, and vinyl benzoate. The resin composition of the present invention may contain an organic solvent in order to adjust the viscosity to a desired value. Examples of the organic solvent include ketone compounds such as acetone, methyl ethyl ketone and cyclohexanone; ester compounds such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate and methoxyethyl acetate; diethyl ether, ethylene glycol dimethyl ether, dioxane and the like. Ether compounds; aromatic compounds such as toluene and xylene; aliphatic compounds such as pentane and hexane; halogenated hydrocarbons such as methylene chloride, chlorobenzene and chloroform. To the resin composition of the present invention, if necessary, a polymerization inhibitor, a matting agent, a coloring pigment, a dye, a defoaming agent, a leveling agent, an antistatic agent, a dispersant, a plasticizer, a non-reactive polymer, etc. are added. it can. The resin composition of the present invention comprises an ultraviolet ray, an electron beam,
It is cured by irradiation with active energy rays such as gamma rays, but ultraviolet rays are particularly preferable. Can be In addition, when the resin composition of the present invention is cured by irradiation with an active energy ray, the resin composition can be cured even in an air atmosphere, and thus has good workability. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. Further, “parts” in the examples indicates “parts by weight”. Various substrates used in the examples and evaluation methods are as follows. [Substrate] ABS: Acrylonitrile / butadiene / styrene resin PET: Polyethylene terephthalate PC: Polycarbonate VC: Vinyl chloride white Base: Steel panel surface coated with acrylic resin [Evaluation method] 1) Pencil hardness JIS K-5400 "pencil scratch test" was followed. 2) Use a cutter knife on the adhesive coating film at 10 mm intervals at 1 mm intervals.
100 cross-cuts were cut in a range of 10 mm, and cellophane tape was pressure-bonded, and then vigorously peeled off, and indicated by (100- (number of cross-cuts cut off)) / 100. [Synthesis of Compound A-1] Stirrer, thermometer,
In a four-necked flask equipped with a temperature controller, a reflux condenser, and a water separator, 160 parts of 1,4-cyclohexanedimethanol modified with 4 moles of ethylene oxide,
8 parts, 0.78 parts of hydroquinone, 4.78 parts of p-toluenesulfonic acid, and 300 parts of toluene were stirred while passing air through, and reacted at a liquid temperature of 110 to 115 ° C. to obtain 16.0 parts (theoretical value of 88). (0.9%) was taken as the end point of the reaction. The water-toluene azeotrope distilled off by the reaction was separated by a water separator to remove water from the reaction system. After cooling, the reaction solution was neutralized with a 5% aqueous sodium hydroxide solution, and then washed sequentially with an aqueous sodium chloride solution.
The organic layer was dried over anhydrous sodium sulfate and then filtered. Finally, the organic solvent was distilled off under the conditions of 50 to 70 ° C. and finally about 2 mmHg to obtain 160.2 parts of 1,4-cyclohexanedimethanol diacrylate modified with 4 moles of ethylene oxide which was liquid at ordinary temperature. . [Synthesis of Compound A-2] In the same manner as in Compound A-1, propylene oxide 4
Molarly modified 1,4-cyclohexanedimethanol 188
Part, 82.8 parts of acrylic acid, 0.8 part of hydroquinone,
4.78 parts of p-toluenesulfonic acid and 300 parts of toluene were charged, and the mixture was stirred while ventilated with air.
The reaction was carried out at 0 ° C., and the time when 16.5 parts (92% of theoretical value) of condensed water was distilled off was taken as the end point of the reaction. The water-toluene azeotrope distilled by the reaction is separated by a water separator,
Water was removed outside the reaction. After cooling, the reaction solution was neutralized with a 5% aqueous sodium hydroxide solution, and then washed sequentially with an aqueous sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate and then filtered. Thereafter, the organic solvent was distilled off under the conditions of 50 to 70 ° C. and finally about 2 mmHg to obtain 185 parts of 1,4-cyclohexanedimethanol dimethacrylate modified with 4 moles of propylene oxide which was liquid at ordinary temperature. Reference Example 1 The ethylene oxide 4 mol modified 1,
30 parts of 4-cyclohexanedimethanol diacrylate (Compound A-1), 0.9 parts of Irgacure 184 (manufactured by Nippon Ciba Geigy Co., Ltd.), and Dia-Aid AD-900
2 (manufactured by Mitsubishi Rayon Co., Ltd .; leveling agent) in an amount of 0.06 parts to prepare a resin composition. After applying the composition to various substrates using a bar coater (# 6),
/ Cm high-pressure mercury lamp (Mitsubishi Rayon Engineering Co., Ltd .; trade name UV-2503), set the conveyor speed to 3 m / min, and repeatedly pass through a 20 cm distance from the lamp until tack-free and cure with ultraviolet light I let it. For the cured product obtained in this way,
Table 1 shows the results of the performance test. Example 1 The ethylene oxide 4 mol-modified 1,
15 parts of 4-cyclohexanedimethanol diacrylate (Compound A-1), 15 parts of dipentaerythritol hexaacrylate, 0.9 parts of Irgacure 184 (manufactured by Nippon Ciba Geigy Co., Ltd.), and Diamond Aid AD-9002
(Mitsubishi Rayon Co., Ltd .; leveling agent) A resin composition was prepared in the same manner as in Example 1 except that 0.06 part was blended. Table 1 shows the results of the performance test. REFERENCE EXAMPLE 2 Irgacure 184 (manufactured by Nippon Ciba Geigy Co., Ltd.) was added to 30 parts of the propylene oxide 4 mol-modified 1,4-cyclohexanedimethanol dimethacrylate (compound A-2) obtained in the above synthesis. 9 copies, Diamond Aid AD-
9002 (manufactured by Mitsubishi Rayon Co., Ltd .; leveling agent)
A resin composition was prepared in the same manner as in Example 1 except for mixing 06 parts. Table 1 shows the results of the performance test. Example 2 15 parts of dipentaerythritol hexaacrylate, 15 parts of Irgacure 184 (Japan) were added to 15 parts of propylene oxide 4 mol-modified 1,4-cyclohexanedimethanol dimethacrylate (compound A-2) obtained by the above synthesis. 0.9 parts by Ciba-Geigy Co., Ltd., Dia-Aid AD-9
002 (manufactured by Mitsubishi Rayon Co., Ltd .; leveling agent) 0.0
A resin composition was prepared in the same manner as in Example 1 except for mixing 6 parts. Table 1 shows the results of the performance test. [Table 1] Comparative Example 1 30 parts of 1,4-cyclohexanedimethanol diacrylate, irgacure 184
A resin composition comprising 0.9 parts (manufactured by Ciba-Geigy Japan) and 0.06 parts of DiaAid AD-9002 (manufactured by Mitsubishi Rayon Co., Ltd .; leveling agent) was prepared. Could not. Comparative Example 2 15 parts of 1,4-cyclohexanedimethanol diacrylate, 15 parts of dipentaerythritol hexaacrylate, 0.9 parts of Irgacure 184 (manufactured by Nippon Ciba Geigy Co., Ltd.), DiaAid AD
-9002 (Mitsubishi Rayon Co., Ltd .; leveling agent)
A resin composition consisting of 0.06 parts was prepared, but could not be evaluated for coating because it crystallized at room temperature. EFFECTS OF THE INVENTION 1,4 used as an essential component in the present invention
Since the di (meth) acrylate of diol obtained by adding 1 to 8 moles of alkylene oxide to cyclohexanedimethanol is liquid at room temperature, an active energy ray-curable resin composition using the same is easy to prepare and coat. It has excellent curability and excellent adhesion to a substrate.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI C09D 171/00 C09D 171/00 B (56) References JP-A-62-46687 (JP, A) JP-A-1-87608 ( JP, A) JP-A-60-55072 (JP, A) JP-A-6-270109 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 20/00-20/70 C08F 220/00-220/70 C08F 290/00-290/14 C08F 299/00-299/08 C09D 1/00-201/10

Claims (1)

(57) [Claims] 1. The component (A)Represented by the following general formula (I)
TheTo 1 mol of 1,4-cyclohexanedimethanol,
Addition of 1 to 8 moles of alkylene oxide having 2 to 3 carbon atoms
Di (meth) acrylate of diol5 to 90 parts by weight
And the number of functional groups is 3 or more and the molecular weight is 2000 as the component (B).
The following polyfunctional (meth) acrylates(However, molecular weight 50
0 or less and one (meth) acryloyl group and one in the molecule
(Meth) acrylic acid having a hydroxyl group or a carboxyl group
10 to 95 parts by weight (excluding rate)And 100 parts by weight in total
Energy ray-curable resin combined so that
Composition. Embedded image (Where R represents a hydrogen atom or a methyl group, and X represents
(CH₂CH₂O)_nOr (CH₂CH₂CH₂O)_n
And n is 1 to 8. )