JP2001187806A - Active energy ray curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray curable composition excellent in curability and flexibility of the cured product. SOLUTION: The active energy ray curable composition comprises (A) a (meth)acrylate represented by general formula (1), (B) a compound represented by general formula (2), and/or (C) a composition comprising a compound represented by general formula (3), and the ratio of component (B) and/or component (C) to the sum total of components (A), (B) and (C) is 0.1-20 wt.% (wherein, in formulas (1), (2) and (3), R1 is a hydrogen atom or methyl group; R2 is an alkylene group; R3 and R4 are each independently a hydrogen atom and/or 1-4C alkyl group or saturated or unsaturated hydrocarbon groups that form in a unit a 5-membered or 6-membered ring; n is an integer of 1-6; and the dotted line in an imide 5-membered ring means a single bond or double bond).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable composition.
It can be used for various applications such as coatings, paints, printing inks, adhesives, fillers, molding materials, stereolithography (3D modeling) systems, lens sheets, electronic materials and resists, and is awarded in these technical fields. Can be done.

[0002]

2. Description of the Related Art Active energy ray-curable compositions can rapidly reduce the energy and time required for drying compared with conventional solvent-drying resin compositions due to their rapid curing properties. And the like can save space.Moreover, since the composition requires only a small amount of solvent or does not need to use it at all, the amount used every year as an environmentally friendly material is reduced. Is increasing.

In recent years, utilizing the speed of the curing speed,
In order to cope with products of various kinds in small quantities, the line speed has been increasingly increased. However, in the conventional active energy ray-curable composition, if the line speed is increased, the curing becomes insufficient, or if the curing is insufficient, skin irritation and odor derived from unreacted monomers may cause a problem. And it has been desired to further improve the curing speed.

[0004]

DISCLOSURE OF THE INVENTION As an active energy ray-curable composition having excellent curability and having no problem of odor of the cured product, the present inventors have proposed a composition comprising a (meth) acrylate having a cyclic imide group. (WO98 / 5
No. 8912). However, although the composition has no problem with the curing speed and the odor, the cured product may be insufficient in flexibility.

[0005]

Means for Solving the Problems The present inventors have conducted various studies to solve the above problems, and as a result, it has been found that a composition comprising (meth) acrylate having two specific types of cyclic imide groups has a curing rate of And also found that the cured product had excellent flexibility, and completed the present invention. In the present specification, acrylate and / or methacrylate are represented by (meth) acrylate, acryloyl group and / or methacryloyl group are represented by (meth) acryloyl group, and acrylic acid and / or methacrylic acid are represented by (meth) acrylic acid. .

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS 1. Component (A) The component (A) in the composition of the present invention is a (meth) acrylate represented by the following general formula (1).

[0007]

Embedded image

[However, in the formula (1), R ₁ is a hydrogen atom or a methyl group, and R ₂ is an alkylene group. R ₃ and R
₄ is an independent hydrogen atom and / or an alkyl group having 4 or less carbon atoms, or a saturated or unsaturated hydrocarbon group forming a 5- or 6-membered ring together.
n is an integer of 1 to 6. The dotted line in the 5-membered imide ring means a single bond or a double bond. ]

The alkylene group is preferably one having 1 to 6 carbon atoms, and may be linear or branched.

1-2. Method for Producing Component (A) The component (A) can be synthesized from an acid anhydride, an amino alcohol and (meth) acrylic acid by the methods described in the following documents and patents. Kato Kiyoshi et al., Journal of Synthetic Organic Chemistry, 30 (10), 897,
(1972) Javier de Abajo et al., Polymer, vol 33.
(5), (1992) JP-A-56-53119, JP-A-1-24256
No. 9

The acid anhydrides used as raw materials include phthalic anhydride and its derivatives, 1,2,3,6-tetrahydrophthalic anhydride and its derivatives, 3,4,5,6-tetrahydrophthalic anhydride Products and their derivatives, 1, 2,
3,4-tetrahydrophthalic anhydride and derivatives thereof,
2,3,4,5-tetrahydrophthalic anhydride and its derivatives, hexahydrophthalic anhydride and its derivatives,
Succinic anhydride and its derivatives, monoalkyl succinic anhydride and its derivatives, dialkyl succinic anhydride and its derivatives, maleic anhydride and its derivatives, monoalkyl maleic anhydride and its derivatives, and dialkyl maleic anhydride And derivatives thereof.

Examples of the amino alcohol include alkanolamines such as ethanolamine, propanolamine and hexanolamine, and substituted alkanolamines such as ethoxyethanolamine and propoxypropanolamine.

Further, the above-mentioned manufacturing method mainly includes two steps. In the first step, an alcohol having a cyclic imide group (hereinafter referred to as imide alcohol) is obtained by reacting an acid anhydride with an amino alcohol to add an amino group of the amino alcohol to the acid anhydride, followed by a dehydration / cyclization reaction. This is the step of manufacturing. The second step is a step of performing a (meth) acrylation reaction of the imide alcohol obtained in the first step. Hereinafter, each step will be described.

1-2-1. First Step In the first step, as a method of reacting the acid anhydride with the amino alcohol, there is a method of heating and stirring the acid anhydride and the amino alcohol. In this case, the reaction may be performed without a catalyst, or a catalyst may be used if necessary. Examples of the catalyst include an inorganic acid such as sulfuric acid, and an acid catalyst such as sulfonic acids such as methanesulfonic acid and paratoluenesulfonic acid. The reaction temperature may be appropriately set according to the components used and the purpose, but is preferably 70 ° C to 140 ° C.
° C. When the reaction temperature is lower than 70 ° C., the reaction becomes slow. On the other hand, when the reaction temperature exceeds 140 ° C., the reaction system becomes unstable and impurities may be generated. In the first step, it is preferable to use an organic solvent having low solubility in water, to azeotropically evaporate water generated in the reaction, and to discharge water to the outside of the reaction system. Examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, and ketones such as methyl ethyl ketone and cyclohexanone.

1-2-2. Second Step In the second step, the imide alcohol obtained above is converted to (meth) acryloyl to obtain the component (A). Examples of the (meth) acryloylation reaction of imido alcohol include an esterification reaction of dehydrating ester of imido alcohol and (meth) acrylic acid, a transesterification reaction of reacting imido alcohol with alkyl (meth) acrylate, and a reaction of imido alcohol with (meth) acrylic acid. A reaction with acrylic acid halide is mentioned, and an esterification reaction is preferable. Examples of the esterification reaction include a method of heating and stirring imide alcohol and (meth) acrylic acid. In this case, it is preferable to use an acid catalyst, and specific examples include those mentioned in the first step. The reaction temperature may be appropriately set according to the components to be used and the purpose.
C is preferred. When the reaction temperature is lower than 70 ° C., the reaction becomes slow, while when the reaction temperature exceeds 140 ° C.,
The reaction system becomes unstable, and impurities may be generated or gelled. In the ester reaction, it is preferable to use an organic solvent having low solubility in water, to azeotropically evaporate water generated in the reaction, and to discharge water to the outside of the reaction system. As the organic solvent to be used, the same organic solvents as described above can be used. The organic solvent may be distilled off under reduced pressure after the reaction, or may be used as it is, if necessary, for adjusting the viscosity of the composition. Further, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, and phenothiazine for suppressing radical polymerization of the (meth) acryloyl group may be used.

2. Component (B) and / or (C) Component In the composition of the present invention, the component (A) is further added to the compound represented by the following general formula (2). The component (C) of the compound represented by the following general formula (3) is used in combination.

[0017]

Embedded image

[However, in the formula (2), R ₂ , R ₃ , R ₄ and n have the same meaning as in the formula (1). ]

[0019]

Embedded image

[However, in the formula (3), R ₁ , R ₂ , R ₃ ,
R ₄ and n have the same meaning as in the above formula (1). ]

2-2. Method for Producing Components (B) and (C) The component (B) can be produced by reacting 2 mol of imide alcohol with 1 mol of acid anhydride. That is, a compound having a cyclic imide group and a carboxyl group is generated by an addition reaction of imide alcohol with an acid anhydride, and the component (B) is obtained by an esterification reaction between the compound and imide alcohol. In addition to the method, a transesterification reaction of an imide alcohol with a dialkyl ester of a dibasic acid, a condensation reaction of an imide alcohol with an acid halide of a dibasic acid, and the like can also be mentioned. As the reaction conditions, the same conditions as in the above-mentioned production method (A) are employed.

The component (C) can be produced by reacting the component (A) with an imide alcohol and subjecting the component (A) to Michael addition with the imide alcohol.

As the components (B) and (C), those produced as a by-product in the production of the component (A) can be used as they are. That is, the component (B) is obtained by a reaction between the imide alcohol generated in the first step and the raw acid anhydride, and a reaction between the imide alcohol and the unreacted acid anhydride in the second step. The component (C) is obtained in the second step by a Michael addition reaction of the unreacted imide alcohol to the component (A) of the final product.

In this case, the component (B) or (C) can be produced at an arbitrary ratio by adjusting conditions such as the amount of the acid anhydride and the reaction temperature. When producing the component (B), the amount of the acid anhydride used is used in excess of the amount of the amino alcohol. Specifically, the amount of the acid anhydride is preferably 1.05 times, more preferably 1.1 times or more the amount of the amino alcohol. In order to generate the component (C), there are a method of setting the reaction temperature higher than usual and a method of increasing the reaction time. The reaction temperature in this case is preferably 90 ° C. or higher, more preferably 100 ° C. or higher.

In the present invention, the proportion of the component (B) and / or the component (C) can be 0.1 to 20% by weight based on the total amount of the components (A), (B) and (C). Must. When the proportion of the component (B) and / or the component (C) is less than 0.1% by weight, the curability of the composition and the flexibility of the cured product become insufficient. , And the hardness and flexibility of the cured product are reduced.

3. Other Components In the composition of the present invention, a reactive monomer or oligomer having a radically polymerizable unsaturated double bond in the molecule is added, if necessary, in addition to the above essential components. be able to. The proportion of the reactive monomer and oligomer having a radical polymerizable unsaturated double bond in the molecule, (A), (B) and (C) 100 parts by weight of the total amount of the components, 1 to 100 parts by weight
00 parts by weight, more preferably 10 to 1000 parts by weight.
Department.

Examples of the reactive monomer include amide compounds such as N-vinylpyrrolidone, N-vinylcaprolactam and acryloylmorpholine; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and Hydroxyalkyl (meth) acrylates such as -hydroxy-3-phenylpropyl acrylate; phenols of alkylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and their halogen nuclei; ) Monomers of glycols such as acrylates, mono (meth) acrylates of methoxyethylene glycol, mono or di (meth) acrylates of tetraethylene glycol, mono or di (meth) acrylates of tripropylene glycol Or di (meth) acrylates;
Polyol poly (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate and dipentaerythritol hexaacrylate; poly (meth) of alkylene oxide adduct of polyol Acrylate; and di- or tri (meth) acrylate modified with ethylene oxide isocyanurate.

Examples of the oligomer include urethane acrylate, polyester (meth) acrylate and epoxy (meth) acrylate.

Examples of the urethane (meth) acrylate oligomer include a reaction product obtained by further reacting a hydroxyl group-containing (meth) acrylate with a polyol and an organic polyisocyanate reaction product. Here, examples of the polyol include low-molecular-weight polyols, polyethylene glycol and polyester polyol, and examples of the low-molecular-weight polyol include ethylene glycol, propylene glycol, cyclohexanedimethanol, and 3-methyl-1,5-pentanediol. And polyether polyols such as polyethylene glycol and polypropylene glycol. Polyester polyols include these low molecular weight polyols and / or polyether polyols and adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid. And a reaction product with an acid component such as a dibasic acid or an anhydride thereof. Examples of the organic polyisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

Examples of the polyester (meth) acrylate oligomer include a dehydration condensate of a polyester polyol and (meth) acrylic acid. As the polyester polyol, ethylene glycol, polyethylene glycol, cyclohexanedimethanol, 3-methyl-
Low molecular weight polyols such as 1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol and trimethylolpropane, and polyols such as alkylene oxide adducts thereof, and adipic acid, succinic acid, phthalic acid, A reaction product from a dibasic acid such as hexahydrophthalic acid and terephthalic acid or an acid component such as an anhydride thereof is exemplified.

Epoxy acrylate is obtained by subjecting an epoxy resin to an addition reaction with an unsaturated carboxylic acid such as (meth) acrylic acid. Epoxy (meth) acrylate of bisphenol A type epoxy resin, phenol or epoxy of cresol novolak type epoxy resin is used. (Meth) acrylates and (meth) acrylic acid addition reactants of diglycidyl ethers of polyethers and the like can be mentioned.

When the composition of the present invention is cured by ultraviolet rays, a photopolymerization initiator may be used if necessary. Examples of the photopolymerization initiator include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, and their alkyl ethers; acetophenone, 2,2-dimethoxy-2-
Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexylphenylketone, and 2-methyl-1- [4
Acetophenones such as-(methylthio) phenyl] -2-morpholino-propan-1-one; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2,
Thioxanthones such as 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 2,4,6-trimethylbenzoyldiphenylphosphine Monoacylphosphine oxides or bisacylphosphine oxides such as oxides; benzophenones such as benzophenone; and xanthones. These photopolymerization initiators can be used alone or in combination with a benzoic acid-based or amine-based photopolymerization initiator.

The preferred mixing ratio of these photopolymerization initiators is 0.1 parts by weight or more and 10 parts by weight to 100 parts by weight of the composition.
It is not more than 1 part by weight, more preferably not less than 1 part by weight and not more than 5 parts by weight.

The composition may contain, if necessary, fillers such as barium sulfate, silicon oxide, talc, clay and calcium carbonate; coloring pigments such as phthalocyanine blue, phthalocyanine green, titanium oxide and carbon black; Various additives such as an adhesion-imparting agent and a leveling agent, and a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, phenothiazine, and aluminum salt of N-nitrosophenylhydroxylamine can also be blended.

When these are blended, the blending ratio is preferably 100 parts by weight or less based on the present composition. When the polymerization inhibitor is compounded, the compounding ratio is preferably 0.1% by weight to 2% by weight with respect to the present composition.

[0036]

The present invention will be described more specifically with reference to the following Examples and Comparative Examples. In the following, "parts" means parts by weight, and "%" means% by weight.

Production Example 1 46.2 g (0.3 mol) of hexahydrophthalic anhydride and 80 g of toluene were charged into a flask equipped with a stirrer, a condenser, and a Dean-Stark trap (water separator). To dissolve. To this, 18.3 g (0.3 mol) of ethanolamine was added dropwise over 30 minutes, and then the mixture was refluxed for 3 hours while maintaining the liquid temperature at 115 to 120 ° C., and 5.4 g of water remained in the water separator. Issued. After cooling the reaction solution, furthermore, hexahydrophthalic anhydride 23.
1 g (0.15 mol) was added, and the mixture was stirred for 2.5 hours while maintaining the liquid temperature at 90 to 100 ° C. Thereafter, 3.3 g of sulfuric acid was added, and the mixture was refluxed for 3 hours while maintaining the liquid temperature at 115 to 120 ° C., and 2.7 g of water was distilled out into the water separator. After cooling, the reaction solution was transferred to a separating funnel and extracted once with 80 g of water. The organic layer was evaporated under reduced pressure to remove the light yellow liquid product.
g was obtained. ^{By 1} H-NMR, it was confirmed that a compound of the following formula (4) was obtained.

[0038]

Embedded image

Production Example 2 169.4 g (1.1 mol) of hexahydrophthalic anhydride and 300 g of xylene were placed in the same flask as in Production Example 1.
And heated to 50 ° C. to dissolve it. To this, 61 g (1.0 mol) of ethanolamine was added dropwise over 30 minutes, and then the mixture was refluxed for 5 hours while keeping the liquid temperature at 125 to 135 ° C., and 17.5 g of water was distilled out into the water separator. . After cooling the reaction solution, 72 g (1.0 mol) of acrylic acid, 0.15 g of hydroquinone and 8.4 g of concentrated sulfuric acid were added, and the solution was refluxed for 3.5 hours while maintaining the solution temperature at 120 to 132 ° C.
16.5 g of water distilled off in the water separator. After cooling, the reaction solution was transferred to a separating funnel and extracted once with 50 g of water and once with 200 g of a 20% aqueous NaOH solution. The solvent was distilled off from the organic layer under reduced pressure to obtain 181 g of a pale yellow liquid reaction solution. ¹ H-NM
By R and GPC, it was confirmed that a mixture of the compound of the above formula (4), the compound of the following formula (5) and the compound of the following formula (6) was obtained. The weight ratio is (4) :( 5) :( 6) = 2:
8:90.

[0040]

Embedded image

[0041]

Embedded image

Production Example 3 The mixture obtained in Production Example 2 was purified by distillation to obtain only the compound of the formula (6).

Example 1 15 parts of the reaction solution obtained in Production Example 1, 85 parts of the reaction solution obtained in Production Example 3, urethane acrylate having two acryloyl groups [Aronix M1600 manufactured by Toagosei Co., Ltd.
20 parts of M1600] and 2 parts of a photopolymerization initiator benzyl dimethyl ketal [Irgacure 651 manufactured by Ciba Specialty Chemicals Co., Ltd., hereinafter abbreviated as Irg651] are stirred and mixed according to a conventional method, and the active energy ray-curable composition is mixed. Was manufactured. The resulting composition was evaluated for curability, flex resistance and pencil hardness according to the methods described below. Table 1 shows the results.

{Curability} A 0.2 mm-thick electroplated tin plate or aluminum plate was used as a base plate, and the composition was coated thereon with a bar coater so that the coating thickness became 10 μm. 80W / c
m, 10cm below the condensing high pressure mercury lamp,
It was repeatedly passed under a mercury lamp under the condition of a conveyor speed of 20 m / min, and evaluated by the number of passes (the number of passes) until the surface was free of tackiness.

(4) Flexibility With respect to the cured film after the curability test, flexibility was evaluated using a mandrel having a diameter of 4 mm in accordance with a bending resistance test according to JIS K5400. ：: No cracks or peeling in the coating film △: Slight cracks or peeling ×: Cracks or peeling all over the bent part

(4) Pencil hardness The cured film after the curability test was evaluated in accordance with JIS K5400.

Examples 2 and 3 An active energy ray-curable composition was produced in the same manner as in Example 1 except that the compounds shown in Table 1 below were used. The obtained composition was evaluated in the same manner as in Example 1. Table 1 shows the results. In Table 1,
M1200 means urethane acrylate having two acryloyl groups [Aronix M1200 manufactured by Toagosei Co., Ltd.].

[0048]

[Table 1]

Comparative Examples 1 and 2 An active energy ray-curable composition was produced in the same manner as in Example 1 except that the compounds shown in Table 2 below were used. The obtained composition was evaluated in the same manner as in Example 1. Table 2 shows the results.

[0050]

[Table 2]

[0051]

EFFECTS OF THE INVENTION The composition of the present invention has a high curing speed and excellent flexibility, so that coatings, paints, printing inks, adhesives, fillers, molding materials, stereolithography (3D modeling) systems, lens sheets, It can be used for various uses such as electronic materials and resist agents.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yasunori Muramatsu 1Funamicho, Minato-ku, Nagoya City, Aichi Prefecture Toagosei Co., Ltd. Nagoya Research Laboratory F-term (reference) 4J011 QA03 QA15 QA19 QA25 QA36 QA39 SA21 SA31 SA51 SA90 UA01 WA02 WA05 WA06 4J100 AM54P AM54Q AM55R BA02R BA15R CA05 JA01 JA03 JA07 JA33

Claims (1)

[Claims] (1) (A) a (meth) acrylate represented by the following general formula (1), (B) a compound represented by the following general formula (2) and / or (C) a compound represented by the following general formula (3) A composition containing the compound represented, wherein the proportion of the component (B) or / and (C) component (A), (B)
And an active energy ray-curable composition, which is 0.1 to 20% by weight based on the total amount of component (C). Embedded image [However, in the formula (1), R ₁ is a hydrogen atom or a methyl group,
R ₂ is an alkylene group. R ₃ and R ₄ are each independently a hydrogen atom or / and an alkyl group having 4 or less carbon atoms, or a saturated or unsaturated hydrocarbon group forming a 5- or 6-membered ring together. is there. n is an integer of 1 to 6. The dotted line in the 5-membered imide ring means a single bond or a double bond. [Chemical formula 2] [However, in the formula (2), R ₂ , R ₃ , R ₄ and n have the same meaning as in the formula (1). [Chemical formula 3] [However, in the formula (3), R ₁ , R ₂ , R ₃ , R ₄ and n
Has the same meaning as in the above formula (1). ]