JP2001181355A - Actinic ray curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an actinic ray curable composition excellent in curability and flexibility of a cured product. SOLUTION: The actinic ray curable composition comprises (A) a (meth) acrylate represented by formula (1) and (B) a (meth)acrylate represented by formula (2) the ratio of component B to sum total of components A and B being 0.1-20 wt.% (wherein, in formulas (1) and (2), R1 and R5 each represent 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 a saturated or unsaturated hydrocarbon group that forms in a unit a 5-membered or 6-membered ring, n is an integer of 1-6, m is an integer of 1-20, and the dotted line portion of the imide 5-membered ring is a single 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. In some cases, it has been desired to further improve the curability.

[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, the composition was insufficient in flexibility in spite of no problem of curing speed and odor.

[0005]

Means for Solving the Problems The present inventors have made various studies to solve the above-mentioned problems, and as a result, a composition comprising (meth) acrylate having two specific types of cyclic imide groups has been obtained. 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 (meth) acrylate represented by the following formula (1).

[0007]

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[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. ]

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. Kiyoshi Kato et al., Journal of Synthetic Organic Chemistry, 30 (10), 897, (1972) Javier de
Abajo et al., Polymer, vol 33 (5), (19)
92) JP-A-56-53119, JP-A-1-24
No. 2569

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.

[0012] The above-mentioned manufacturing method mainly comprises 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, adding an amino group of the amino alcohol to the acid anhydride, and performing a subsequent 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, a method of reacting the acid anhydride with the amino alcohol includes 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, azeotropically azeotrope the water generated in the reaction, and discharge the water out 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 described 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) In the composition of the present invention, the following formula is further added to the component (A).
The component (B) which is the (meth) acrylate represented by (2) is used in combination.

[0016]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ and n have the same meaning as in the above formula (1). R ₅ is a hydrogen atom or a methyl group. m is an integer of 1 to 20. The dotted line in the 5-membered imide ring means a single bond or a double bond. ]

2-2. Method for Producing Component (B) The method for producing component (B) includes a dehydration ester reaction between imide alcohol and (meth) acrylic acid polymer, and a reaction between imide alcohol and (meth) acrylic acid polymer. Examples thereof include a transesterification reaction of an alkyl ester and a condensation reaction of an imide alcohol and an acid halide of a (meth) acrylic acid polymer. The reaction conditions in this case include the same method as the method for producing the component (A).

As the component (B), a by-product produced in the production of the component (A) can be used. That is, in the esterification reaction between imide alcohol and (meth) acrylic acid, it is formed by the esterification reaction between (meth) acrylic acid polymer produced in the reaction system and imide alcohol. In this case, the ratio of the (meth) acrylic acid polymer formed in the reaction system can be arbitrarily adjusted by adjusting the reaction temperature, the amount of (meth) acrylic acid charged, and the like. In particular, when the reaction temperature is increased or when the charged amount of (meth) acrylic acid is set to be larger than that of imido alcohol, it can be efficiently produced. The preferred reaction temperature at that time is 90 ° C. or higher, more preferably 100 ° C. or higher. Further, the preferable charging amount of (meth) acrylic acid is 1.05 times or more, more preferably 1.1 times or more with respect to imide alcohol.

In the present invention, the ratio of the component (B) is 0.1 to 20 with respect to the total amount of the components (A) and (B).
% By weight. When the proportion of the component (B) is less than 0.1% by weight, the curability of the composition and the flexibility of the cured product become insufficient, and when it exceeds 20% by weight, the curability of the composition and the cured product become insufficient. Hardness is reduced.

3. Other Components In the composition of the present invention, in addition to the above essential components, a reactive monomer or oligomer having a radical polymerizable unsaturated double bond in the molecule may be added, if necessary. be able to.

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.

The polyester (meth) acrylate oligomer includes 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 adding an unsaturated carboxylic acid such as (meth) acrylic acid to an epoxy resin, and is an epoxy (meth) acrylate of bisphenol A type epoxy resin, phenol or epoxy of cresol novolac type epoxy resin. (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 part by weight or more and 10 parts by weight or more based on 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 blended, the blending ratio is preferably 0.00001 to 2% by weight based on the composition.

[0031]

The present invention will now be described more specifically with reference to examples and comparative examples. In the following, "%" means% by weight. Production Example 1 123 g (0.8 mol) of hexahydrophthalic anhydride and 350 g of toluene were charged into a flask equipped with a stirrer, a condenser, and a Dean-Stark trap (water separator), and heated to 50 ° C. Dissolved. To this, 48.9 g (0.8 mol) of ethanolamine was added dropwise over 30 minutes, and then the mixture was refluxed for 3.5 hours while maintaining the liquid temperature at 115 to 120 ° C. Distilled in. After cooling the reaction solution, a mixture of acrylic acid and an acrylic acid polymer [Aronix M5600 manufactured by Toagosei Co., Ltd., average molecular weight 222 determined from acid value, compound of the following formula (3)] 177.
When 7 g (0.8 mol), 0.17 g of hydroquinone and 13.8 g of concentrated sulfuric acid were added and the mixture was refluxed for 2.0 hours while maintaining the liquid temperature at 115 to 120 ° C., 15.8 g of water was distilled off into the water separator. did. After cooling the reaction solution, it was transferred to a separating funnel, and water 6
The mixture was extracted once with 0 g and once with 150 g of a 20% aqueous NaOH solution. The solvent was distilled off from the organic layer under reduced pressure to obtain 252 g of a pale yellow liquid product. ¹ H-NMR confirmed that the compound of the following formula (4) was obtained. According to the analysis by GPC, the ratio of the compound with m = 0 [component (A)] in this mixture was 11.3%.

[0032]

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[0033]

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Production Example 2 In the same flask as in Production Example 1, 154 g (1.0 mol) of hexahydrophthalic anhydride and 300 g of ethylbenzene were placed.
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 2.5 hours while maintaining the liquid temperature at 125 to 135 ° C., and 17.5 g of water remained in the water separator. Issued. After cooling the reaction solution, 86.4 g (1.2 mol) of acrylic acid,
0.15 g of hydroquinone and 8.4 g of concentrated sulfuric acid were added,
When the liquid temperature was maintained at 125 to 135 ° C. and refluxed for 3.0 hours, 17.0 g of water was distilled out into the water separator. After cooling the reaction solution, it was transferred to a separating funnel, and once with 50 g of water, 20% NaOH
Extracted once with 200 g of aqueous solution. The solvent was distilled off from the organic layer under reduced pressure to obtain 212 g of a pale yellow liquid product. ¹ H-NMR
And GPC to give the compound of the following formula (5) [component (B)].
It was confirmed that a compound of the following formula (6) containing 2% [component (A)] was obtained.

[0035]

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[0036]

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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 20 parts of the reaction solution obtained in Production Example 1, 80 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} An electroplated tin plate or aluminum plate having a thickness of 0.2 mm was used as a base plate, and the composition was applied thereon using a bar coater so that the coating thickness became 10 μm. 80W
/ Cm, 10 cm from the bottom of the condensing high-pressure mercury lamp, at a conveyor speed of 20 m / min, repeatedly under the mercury lamp, and the number of passes (number of passes) until the surface loses tackiness. Was evaluated.

(4) Flex resistance The cured film after the curability test was evaluated using a 4 mm diameter mandrel in accordance with the flex resistance test of JIS K5400. ：: No cracks or peeling in the coating film △: Slight cracks or peeling ×: Cracks or peeling all over the bent part

Pencil hardness The cured film after the curability test was evaluated according to 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.

[0043]

[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 1 shows the results.

[0045]

[Table 2]

[0046]

The composition of the present invention is very fast-curing and has high flexibility of the cured product, so that coatings, paints, printing inks, adhesives, fillers, molding materials, stereolithography can be obtained.
(3D modeling) It can be used for various applications such as system, lens sheet, electronic material and resist agent.

Continued on the front page F term (reference) 4J011 QA03 QB14 SA01 SA04 SA06 SA07 SA21 SA31 SA34 SA41 SA51 SA63 SA64 SA84 UA01 WA01 WA02 WA05 WA06 WA07 4J027 AA02 AB10 AB15 AB16 AB18 AB19 AB23 AB24 AB25 AD02 AE02 AE03 AE04 AG13 AG04 AG03 AG24 AG27 AG33 BA07 BA08 BA13 BA15 BA19 BA20 BA23 BA26 BA28 CA12 CA16 CA18 CA20 CA25 CA34 CA36 CB10 CD04 CD08 CD09 CD10 4J100 AL08P AL08Q BA21Q BC66P BC66Q CA04

Claims (1)

[Claims] 1. A composition comprising (A) a (meth) acrylate represented by the following formula (1) and (B) a (meth) acrylate represented by the following formula (2), wherein (B) An active energy ray-curable composition, wherein the proportion of the component is 0.1 to 20% by weight based on the total amount of the component (A) and the component (B). 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, R ₁ , R ₂ , R ₃ , R ₄ and n have the same meaning as in the above formula (1). R ₅ is a hydrogen atom or a methyl group.
m is an integer of 1 to 20. The dotted line in the 5-membered imide ring means a single bond or a double bond. ]