JP3310330B2 - New energy ray-curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful energy ray-curable resin composition, and more particularly, to an epoxy compound and a compound having at least one unsaturated double bond as essential components. some of the unsaturated double bonds of the compound obtained from motor having at least one active hydrogen
And a resin A obtained by neutralizing a compound obtained by adding a noamine compound. And the energy ray-curable resin composition of the present invention can be arbitrarily diluted in water or an organic solvent, and can form a cured coating film having excellent adhesion to a substrate and chemical resistance, and Since the uncured coating film can be redissolved in water or a dilute acid aqueous solution, it is a very useful resin composition suitable for a wide range of uses such as inks, coatings, and the like.

[0002]

2. Description of the Related Art There are various types of resins that can be cured, especially those that are cured by a radical polymerization reaction, such as unsaturated polyester resins, vinyl ester resins, various oligoacrylates, and diallyl phthalate prepolymers. Has been widely used. However, the energy ray-curable resin composition using such a resin,
Since water cannot be diluted when applying, etc., it must be diluted with a large amount of organic solvent, and since the organic solvent is used for cleaning the jig used for application, environmental pollution, deterioration of working conditions, and fire hazard There are problems such as the above, and improvement thereof is desired. Thus, from the viewpoints of environmental pollution, improvement of working conditions, etc., the demand for water-based conversion in each application field is becoming stronger and stronger, but the water-based energy without deteriorating the performance of the resin composition in various applications. A resin composition curable by wire has not yet been obtained.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has been made to solve the above-described problems. Or, it can be arbitrarily diluted in an organic solvent, can form a coating film with excellent adhesion to the substrate and chemical resistance, and the uncured coating film can be redissolved in water or a dilute aqueous acid solution. It is an object of the present invention to provide a very useful resin composition suitable for a wide range of uses such as ink, coating, and the like. That is, an object of the present invention is, firstly, to provide an energy beam-curable resin composition which can be arbitrarily diluted in water or an organic solvent, and the uncured coating film can be redissolved in water or a dilute acid aqueous solution. For the purpose, secondly, it has good sensitivity and easily reacts and cures with energy rays,
The purpose of the present invention is to provide an energy beam-curable resin composition which can be arbitrarily diluted in water or an organic solvent, and the uncured coating film can be redissolved in water or a dilute aqueous acid solution. The purpose of the present invention is to provide an energy-ray-curable resin composition which can be arbitrarily diluted in water or an organic solvent, and which can be cured even by heat, and whose uncured coating film can be redissolved in water or a dilute aqueous acid solution. Fourth, the cured product cured by light or heat is excellent in alkali resistance, adhesion, chemical resistance, surface hardness, moisture resistance, and water resistance, and can be arbitrarily diluted in water or an organic solvent. The purpose of the film is to provide an energy ray-curable resin composition that can be redissolved in water or a dilute aqueous acid solution.

[0004]

According to the present invention, in order to achieve the above object, the unsaturated double bond of a compound obtained from an epoxy compound and a compound having at least one unsaturated double bond is obtained. An energy ray-curable resin composition comprising, as an essential component, a resin A obtained by neutralizing a compound obtained by adding a monoamine compound having at least one or more active hydrogens, and the resin An energy ray-curable resin composition comprising A and photopolymerization initiator B as essential components is provided. The energy ray-curable resin A is, specifically, a group which reacts with the epoxy group of the compound having all or a part of the epoxy compound, a group which reacts with the epoxy group, and an unsaturated double bond. And / or, if the epoxy compound has a hydroxyl group, from a reaction between a group that reacts with a hydroxyl group and a compound having an unsaturated double bond. Reacting a monoamine compound having active hydrogen with some unsaturated double bonds of the obtained compound,
Next, it is obtained by neutralizing the obtained compound with an acid.

Here, the above-mentioned energy ray-curable resin (hereinafter also referred to as resin A) is obtained by reacting an epoxy compound with a compound having a group which reacts with an epoxy group and an unsaturated double bond. A resin A obtained by adding a monoamine compound having active hydrogen to a part of the unsaturated double bond of the compound obtained and neutralizing the monoamine compound. As the resin A, of course, any material can be used as long as it is a product obtained by reacting various compounds as described above. Among them, if only typical ones are exemplified, first, An epoxy compound (hereinafter abbreviated as (a-1)) and a compound having at least one unsaturated double bond (hereinafter referred to as (a-2)
Abbreviated. ) To the specific reactant (hereinafter abbreviated as (a-3)), and an amino compound having an active hydrogen at a part of the unsaturated double bond of (a-3) (hereinafter, abbreviated as (a-3)). This is abbreviated as (a-4).) And a resin obtained by neutralizing the resultant.

Among them, a typical epoxy compound (a-1) for preparing the above (a-3) is as follows. A glycidyl ether-based epoxy resin, for example, bisphenol A and epichlorohydrin can be prepared in the presence of an alkali. There are bisphenol A-based epoxy resins obtained by the reaction, epoxidized resins obtained by condensation reaction of bisphenol A and formalin, and those using brominated bisphenol A instead of bisphenol A. Further, there is a novolak type epoxy resin obtained by reacting a novolak resin with epichlorohydrin and glycidyl etherified, such as a modified epoxy resin such as a phenol novolak type, an orthocresol novolak type, and a p-tert-butylphenol novolak type. Further, there are a bisphenol F-based epoxy resin obtained by reacting epichlorohydrin with bisphenol F, a brominated epoxy resin derived from tetrahydrobisphenol A, and the like. Furthermore, a cycloaliphatic epoxy resin having a cyclohexene oxide group, a tricyclodecene oxide group, or a cyclopentene oxide group, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl-p-oxy Glycidyl ester resins such as benzoic acid and glycidyl dimer acid, tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, diglycidyl aniline, diglycidyl toluidine, tetraglycidyl meta-xylylene diamine, diglycidyl tribromoaniline, tetraglycidyl bisaminomethyl Glycidylamine resins such as cyclohexane, hydantoin type epoxy resins in which the hydantoin ring is glycidylated,
And triglycidyl isocyanurate having a triazine ring. These may be used alone or in combination of two or more.

The compound (a-2) having an unsaturated double bond for preparing the above (a-3) includes, for example,
Addition reaction between carboxyl group and epoxy group, addition reaction between hydroxyl group and epoxy group, esterification reaction between carboxyl group and hydroxyl group when epoxy compound has hydroxyl group, addition reaction between isocyanate group and hydroxyl group, reaction between acid anhydride and hydroxyl group A compound which reacts with the epoxy compound (a-1) using a reaction, a transesterification reaction between an ester group and a hydroxyl group, or the like is considered. As typical examples, compounds having a polymerizable unsaturated group and a carboxyl group capable of utilizing an addition reaction between a carboxyl group and an epoxy group include (meth) acrylic acid, crotonic acid, monoalkyl itaconate, monoalkyl maleate, Monoalkyl fumarate and the like can be mentioned. Examples of those which can utilize an addition reaction between a hydroxyl group and an epoxy group include 2-hydroxyethyl (meth) acrylate, allyl alcohol, N-methylol (meth) acrylamide, and the like. Further, as those capable of utilizing the addition reaction between the hydroxyl group and the isocyanate group in the epoxy compound, an equimolar addition product of a monoalcohol having a polymerizable unsaturated double bond and a polyvalent isocyanate, for example, tolylene diisocyanate and 2-hydroxy A method of adding a reaction product with ethyl (meth) acrylate, 2-isocyanate ethyl methacrylate, methacrylic isocyanate, or the like can also be used.
As the hydroxyl group, a hydroxyl group generated by an addition reaction between the carboxyl group and the epoxy group or the like can be used. These may be used alone or in combination of two or more.

Representative examples of the monoamine compound (a-4) having at least one active hydrogen include ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine,
Aliphatic primary amines such as heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, cetylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine , dibutylamine, diamylamine, diethanolamine, aliphatic secondary amines such as Moruhori emissions; allylamine, aliphatic unsaturated amines such as diallylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, alicyclic amines and the like; di And aromatic amines such as benzylamine and diphenylamine. These may be used alone or in combination of two or more.

As the acid used for neutralization, conventionally known acids can be used. Specifically, acetic acid, formic acid, trimethylacetic acid, acrylic acid, methacrylic acid, lactic acid, hydroxyacetic acid, crotonic acid, chloroacetic acid, Monomethyl maleate, monomethyl fumarate, monomethyl itaconic acid and the like can be mentioned.

Next, typical examples of the above-mentioned photopolymerization initiator B include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, acetophenone, 2,2- Dimethoxy-2
-Phenylacetophenone, 2,2-diethoxy-2-
Anthraquinones such as phenylacetophenone, 1,1-dichloroacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2,4
-Thioxanthones such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal, and benzophenones or xanthones such as benzophenone. However, the photopolymerization initiator B can be used in combination with one or more known and common photopolymerization accelerators such as benzoic acid or tertiary amine.

Further, an organic solvent can be used if necessary. Representative examples thereof include ketones such as methyl ethyl ketone and cyclohexane, aromatic hydrocarbons such as toluene and xylene, cellosolves such as cellosolve and butyl cellosolve, carbitol and butyl. There are carbitols such as carbitol, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate and acetate esters such as butyl carbitol acetate, and these are used as one kind or a mixture of two or more kinds.

The thus obtained resin composition of the present invention may further comprise, if necessary, β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, glycidyl acrylate, β-hydroxyethyl acryloyl phosphate, dimethylaminoethyl acrylate, diethylaminoethyl Acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate,
Triethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate,
Tripropylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Alternatively, tris (2-acryloyloxyethyl) isocyanurate or methacrylates of the above acrylates, mono-, di-, tri- and polybasic acids and hydroxyalkyl (meth) acrylates
Alternatively, a monomer, oligomer or prepolymer having an ethylenically unsaturated double bond, such as a polyester or a bisphenol A type epoxy acrylate, a novolak type epoxy acrylate or a urethane acrylate, can be added. Further, known and commonly used fillers such as barium sulfate, silicon sulfide, talc, clay and calcium carbonate, known and commonly used coloring pigments such as phthalocyanine blue, phthalocyanine green, titanium oxide and carbon black, defoamers, and adhesion promoters Alternatively, various additives such as a leveling agent, or known and commonly used polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and phenothiazine may be added.

[0013]

The energy-ray-curable resin composition of the present invention comprises an unsaturated double bond of a compound obtained by reacting an epoxy compound with a compound having an unsaturated double bond and a group capable of reacting with an epoxy group. some of the mono having an active hydrogen
An energy-curable resin A obtained by adding an amine compound and neutralizing the same is contained as an essential component. The energy-ray-curable resin A forms a protic ammonium salt by neutralizing the amino group. Before curing, it can be arbitrarily diluted with water or an organic solvent before curing, and the reaction of an epoxy compound with a compound having an unsaturated double bond and a group that reacts with an epoxy group. Because the compound obtained by the above is used as a resin skeleton, it is a highly sensitive substance, and after curing by energy ray irradiation, has water resistance,
A cured coating having excellent solvent resistance and chemical resistance can be formed, and the uncured coating can be redissolved in water or a dilute aqueous acid solution. Further, the energy ray-curable resin composition of the present invention can be thermoset by adding a thermosetting catalyst such as a peroxide. The term "energy beam" as used in the present invention is a general term for electron beams, α-rays, β-rays, γ-rays, X-rays, neutron beams, or ionizing radiation or light such as ultraviolet rays.

[0014]

Next, the present invention will be described more specifically with reference to examples and application examples. In the following, "part"
Unless otherwise specified, all items are on a weight basis. Example 1 In a flask equipped with a thermometer, a stirrer, and a reflux condenser,
After adding and dissolving 216 g of cresol novolac type epoxy resin (Epiclon N-680, epoxy equivalent 216, manufactured by Dainippon Ink and Chemicals, Inc.) and 216 g of dipropylene glycol monomethyl ether, 1.3 g of hydroquinone monomethyl ether and 72 g of acrylic acid were added. After reacting at 90 ° C. until the acid value became 1 or less, 63 g of diethanolamine was added thereto and reacted at 60 ° C. for 4 hours to obtain a reaction product. After the temperature was lowered to 40 ° C., 54.1 g of lactic acid was further added thereto for neutralization to obtain a target energy ray-curable resin. Hereinafter, this is abbreviated as resin A-1.

Example 2 In a flask equipped with a thermometer, a stirrer, and a reflux condenser,
After adding and dissolving 216 g of cresol novolac type epoxy resin (Epiclon N-680, epoxy equivalent 216, manufactured by Dainippon Ink and Chemicals, Inc.) and 216 g of dipropylene glycol monomethyl ether, 1.3 g of hydroquinone monomethyl ether and 72 g of acrylic acid were added. At 90 ° C. until the acid value becomes 1 or less, 148 g of pentaerythritol triacrylate and tolylene diisocyanate previously reacted in equimolar amounts were added thereto, and urethanation reaction was carried out at 80 ° C. Was. It was confirmed by infrared absorption analysis that no isocyanate groups remained. Further, 69.3 g of diethanolamine was added to the reaction product and reacted at 60 ° C. for 5 hours. The temperature was lowered to 40 ° C., and 60.4 g of lactic acid was added for neutralization to obtain a target energy ray-curable resin. Hereinafter, this is abbreviated as resin A-2.

Comparative Example 1 In a flask equipped with a thermometer, a stirrer, and a reflux condenser,
After adding and dissolving 432 g of cresol novolac type epoxy resin (Epiclon N-680, epoxy equivalent 216, manufactured by Dainippon Ink and Chemicals, Inc.) and 432 g of dipropylene glycol monomethyl ether, 1.3 g of hydroquinone monomethyl ether and 144 g of acrylic acid
And reacted at 90 ° C. until the acid value becomes 1 or less,
Further, 152 g of tetrahydrophthalic anhydride was added thereto, and the reaction was carried out at 90 ° C. until the acid value reached 78 to obtain an energy ray-curable resin. Hereinafter, this is abbreviated as resin C-1.

[0017]

[Application example]

Application Example 1 The following components were mixed with the resin A-1 obtained in Example 1, and the components were sufficiently mixed and stirred to obtain a paint. Resin A-1 100 parts 1-Hydroxycyclohexyl phenyl ketone 3 parts Thereafter, the obtained coating material was applied to a water-sharpened tin plate at a thickness of 20 μm. This is put in hot air at 80 ° C for 1
After drying for 0 minutes, a height of 15
Irradiated from cm for 30 seconds to cure. Table 1 shows the results of the performance evaluation test of the obtained coating film.

Application Example 2 In Application Example 1, except that the same amount of the resin A-2 obtained in Example 2 was used instead of the resin A-1,
When a coating film was obtained in the same manner as in Application Example 1, and the same performance evaluation was performed, the results shown in Table 1 were obtained.

Application Example 3 The following components were mixed with the resin A-1 obtained in Example 1, and the components were mixed well and stirred to obtain a coating material. Resin A-1 100 parts 1-Hydroxycyclohexylphenyl ketone 3 parts Ion-exchanged water 10 parts After that, the obtained coating material was applied to a water-sharpened tin plate with a thickness of 20 μm. This is put in hot air at 80 ° C for 1
After drying for 0 minutes, a height of 15
Irradiated from cm for 30 seconds to cure. Table 1 shows the results of the performance evaluation test of the obtained coating film.

Application Example 4 In Application Example 3, except that the same amount of the resin A-2 obtained in Example 2 was used instead of the resin A-1,
When a coating film was obtained in the same manner as in Application Example 3, and the same performance evaluation was performed, the results shown in Table 1 were obtained.

Comparative Application Example 1 In Application Example 1, except that the same amount of the resin C-1 obtained in Comparative Example 1 was used instead of the resin A-1,
When a coating film was obtained in the same manner as in Application Example 1, and the same performance evaluation was performed, the results shown in Table 1 were obtained.

[Table 1]

The evaluation of each performance in Table 1 was performed in the following manner. Water dilutability: 10 g of water was mixed with 10 g of the prepared paint, and the appearance was visually judged. ◎: completely dissolved ×: not dissolved, water and resin separated

Water resolubility: 8 tinplates coated with paint
After drying in hot air at 0 ° C. for 10 minutes, the film was immersed in ion-exchanged water for 5 minutes to visually determine the dissolution state of the coating film. ：: No coating film remained on the tin surface. ：: Almost no coating film remained on the tin surface. Δ: Some coating film remains on the tin surface. X: The coating film remains on the tin surface.

Curability: 80 ° C. of the coating film applied to the tin plate
After being dried in warm air for 10 minutes, it was passed through a 15 cm position under a high-pressure mercury lamp of 80 W / cm at a speed of 50 m / min, and the number of passes until the inside was cured was measured.

Water resistance: 80 ° C.
2000mJ / cm after drying in warm air for 10 minutes
The cured film was irradiated with ultraviolet rays of No. ² to form a cured film having a thickness of 30 μm, and the reduced amount of the film after rubbing the cured film with gauze soaked with ion-exchanged water 20 times was measured. ◎: Film thickness reduction amount of less than 0 to 5 μm ○: Film thickness reduction amount of less than 5 to 10 μm Δ: Film thickness reduction amount of less than 10 to 15 μm ×: Film thickness reduction amount of 15 μm or more

Solvent resistance: The paint film applied to a tin plate is 80
2000mJ / c after drying for 10 minutes in warm air of
The cured film was irradiated with m ² ultraviolet rays to form a cured film having a thickness of 30 μm, and the amount of decrease in the film thickness after rubbing the cured film with gauze soaked with acetone 20 times was measured. ◎: Film thickness reduction amount of less than 0 to 5 μm ○: Film thickness reduction amount of less than 5 to 10 μm Δ: Film thickness reduction amount of less than 10 to 15 μm ×: Film thickness reduction amount of 15 μm or more

Alkali resistance: The coating film applied to a tin plate was dried in warm air at 80 ° C. for 10 minutes, and then 2,000 mJ
/ Cm ² was applied to form a cured film having a thickness of 30 μm, and the cured film was rubbed with a gauze soaked with a 10% aqueous sodium hydroxide solution 20 times, and the amount of decrease in the film thickness was measured. ◎: Film thickness reduction amount of less than 0 to 5 μm ○: Film thickness reduction amount of less than 5 to 10 μm Δ: Film thickness reduction amount of less than 10 to 15 μm ×: Film thickness reduction amount of 15 μm or more

[0028]

As is clear from the results shown in Table 1, the energy ray-curable resin and the resin composition of the present invention can be arbitrarily diluted with water or an organic solvent, thereby improving environmental pollution and working conditions. At the same time, it can be cured with energy rays, can form a coating film with excellent adhesion to the substrate and chemical resistance, and since the uncured coating film can be redissolved with water or a dilute acid aqueous solution, It is a very useful resin composition suitable for a wide range of uses such as ink, coating and the like. Further, the energy ray-curable resin composition of the present invention can be cured not only by energy rays but also by heat depending on the addition of a catalyst, and has alkali resistance, adhesion, chemical resistance, surface hardness, moisture resistance, and water resistance. This gives a cured coating film with excellent properties. Further, according to the method of the present invention, an energy ray-curable resin which is an essential component of the energy ray-curable resin composition having the above-mentioned excellent effects can be synthesized industrially stably.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI G03F 7/027 515 G03F 7/027 515 (72) Inventor Teruo Saito 388 Oya, Okura, Arashiyama-cho, Hiki-gun, Saitama, Japan Taiyo Ink Manufacturing Stock (72) Inventor Morio Suzuki Moriya Suzuki 388, Okura, Okura, Arashiyama-cho, Hiki-gun, Saitama Taiyo Ink Manufacturing Co., Ltd. Taiyo Ink Manufacturing Co., Ltd. Arashiyama Plant (56) References JP-A-5-140251 (JP, A) JP-A-4-345610 (JP, A) JP-A-1-110517 (JP, A) JP JP-A-4-253722 (JP, A) JP-A-52-17515 (JP, A) JP-A-5-247404 (JP, A) JP-A-5-339307 (J , A) JP-B-47-41759 (JP, B1) JP-B-47-36519 (JP, B1) JP-B-46-22348 (JP, B1) JP-A-8-504218 (JP, A) 3-500785 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 299/00-299/08 C08F 290/00-290/14 C08G 59/14 C09D 11/10 C09D 163 / 10 G03F 7/027 511 G03F 7/027 515

Claims (5)

(57) [Claims] 1. A monoamine compound having at least one active hydrogen at a part of an unsaturated double bond of a compound derived from an epoxy compound and a compound having an unsaturated double bond as an essential component. An energy ray-curable resin composition comprising a resin A obtained by neutralizing a compound obtained by the addition. 2. A photocurable resin composition comprising the resin A according to claim 1 and a photopolymerization initiator B as essential components. 3. The method according to claim 1, wherein the monoamine compound is an aliphatic secondary alcohol.
3. The tree according to claim 1, wherein the tree is min.
Fat composition. 4. A monoamine having at least one active hydrogen at a part of an unsaturated double bond of a compound derived from an epoxy compound and a compound having an unsaturated double bond.
By adding an emission compound and then neutralizing the resulting compound, characterized in, synthesis method of the energy ray-curable resin A. 5. The method according to claim 1, wherein the monoamine compound is an aliphatic secondary alcohol.
5. The method of claim 4, wherein the compound is min.
Law.