JP2019199436A - Morpholine ring-containing (meth)acrylate compound and polymerizable composition using same - Google Patents

Abstract

To provide a (meth)acrylate compound that provides a fast curing speed accompanied by reaction, an excellent base material adhesion to inorganic base material, and yet a high coating film hardness.SOLUTION: The above problem is solved by a (meth)acrylate compound having a morpholine ring and having (meth)acrylate group by two or more, and also by the (meth)acrylate compound in which the ratio of (meth)acryloyl group to morpholine ring is 1: 1 to 1: 3.SELECTED DRAWING: Figure 1

Description

  The present invention includes a molding resin, a casting resin, an optical modeling resin, a sealant, a dental polymerization resin, a printing ink, a printing varnish, a paint, a printing plate photosensitive resin, a printing color proof, a color filter resist, Black matrix resist, liquid crystal photo spacer, rear projection screen material, optical fiber, plasma display rib material, dry film resist, printed circuit board resist, solder resist, semiconductor photoresist, microelectronics resist, micromachine parts manufacturing Resist, etching resist, microlens array, insulating material, hologram material, optical switch, waveguide material, overcoat agent, powder coating, adhesive, adhesive, release agent, optical recording medium, adhesive , Release coating agent, micro Composition for image recording materials using capsule, in the field of various devices, and reactive monomer and the polymerizable composition using the same in order to obtain a polymer having good physical properties.

  It is known that reactive monomers represented by (meth) acrylate compounds easily undergo a polymerization reaction and form a reaction cured product by active species generated from a polymerization initiator by heating or irradiation with active energy rays. It has been.

  (Meth) acrylate monomers are roughly classified into 1 to 2 functional low-functional (meth) acrylates and 3 or more polyfunctional (meth) acrylates.

  In general, polyfunctional (meth) acrylates are characterized by a high curing speed and a high crosslink density due to curing, so that the strength of the cured coating is very high. Further, there are problems such as adhesion to a substrate and curling property due to high curing shrinkage accompanying curing.

  In order to reduce the cure shrinkage, which is a problem of polyfunctional (meth) acrylate, etc., the alkylene oxide modified material of the raw material polyol may be acrylated and used, but the chain length extension may lower the curability and the crosslinking density. is there. Moreover, a viscosity may rise or adhesiveness and a weather resistance may fall (for example, patent document 1 and nonpatent literature 1).

  Patent Document 2 discloses a triacrylate compound that exhibits an excellent balance of physical properties with respect to a low curing shrinkage rate, flexibility, flex resistance, low curling property, adhesion, and the like. However, since the compound has almost no structure that can be expected to have a chemical action on the substrate interface such as an alkylene oxide structure, a hydroxyl group, or an amino group, there is a problem in adhesion to an inorganic substrate such as glass. .

  On the other hand, low-functional (meth) acrylates have a relatively low degree of curing shrinkage and are excellent in substrate adhesion regardless of organic / inorganic, but on the other hand, since the crosslinking density is low, the strength of the cured coating film Are weak and often insufficient for some applications.

  In order to increase the strength of a cured film of low-functional (meth) acrylate, monomers linked with a special skeleton such as a cyclic (polycyclic) alkyl group and bisphenol A tetraethoxydiacrylate are known.

  Monomers linked with cyclic alkyls have the effect of slightly improving the strength of the cured coating film due to the skeleton, but are far from the strength of polyfunctional acrylates (Patent Document 3, Paragraph 0012) It is suggested that it may be added, which means that strength alone may be insufficient).

  On the other hand, monomers connected with a bisphenol skeleton have a relatively high strength, but many of them have a high viscosity, and handling properties are extremely poor. Furthermore, while these low-functional (meth) acrylates improve the strength of the cured coating film, the reaction rate and substrate adhesion may decrease.

  For this reason, polyfunctional (meth) acrylates and low functional (meth) acrylates are often used in combination in order to compensate for the merits and demerits of both, and it is necessary to examine the blending according to the characteristics required for each application. .

  Therefore, even when used alone, a (meth) acrylate compound is desired which has a high curing rate associated with the reaction, excellent substrate adhesion to an inorganic substrate, and high coating film hardness.

JP 1994-271623 A WO2016 / 063919 JP 2012-107237 A

Kunihiro Ichimura, Chapter 5 Radical Polymerization Monomers / Oligomers, UV Curing Basics and Practice, Yoneda Publishing, October 7, 2010, see pages 55-69

  An object of the present invention is to provide a (meth) acrylate compound that has a high curing rate associated with the reaction, is excellent in substrate adhesion to an inorganic substrate, and provides very high coating film hardness.

  That is, the present invention relates to a (meth) acrylate compound having a morpholine ring and having two or more (meth) acryloyl groups.

  The present invention also relates to the (meth) acrylate compound described above, wherein the ratio of the (meth) acryloyl group to the morpholine ring is 1: 1 to 1: 3.

  The present invention also relates to a polymerizable composition containing the (meth) acrylate compound described above and a radical polymerization initiator.

  The present invention also relates to the polymerizable composition as described above, wherein the radical polymerization initiator is a photo radical polymerization initiator.

  In addition, the present invention further includes at least one selected from the group consisting of a polymerizable monomer and a polymerizable oligomer other than the (meth) acrylate compound having a morpholine ring and having two or more (meth) acryloyl groups. The present invention relates to the polymerizable composition described above.

  According to the present invention, (meth) acrylate, which could not be realized with a conventional (meth) acrylate compound, has a fast curing speed with reaction, excellent substrate adhesion to an inorganic substrate, and gives very high coating film hardness. A compound and a polymerizable composition using the compound could be provided.

FIG. 1 is a ¹ H-NMR spectrum of Compound A.

  Hereinafter, embodiments of the present invention will be described in detail. In the present specification, acrylic acid or methacrylic acid is (meth) acrylic acid, acrylic acid chloride or methacrylic acid chloride is (meth) acrylic acid chloride, acrylate or methacrylate is (meth) acrylate, acryloyl group or A methacryloyl group is referred to as a (meth) acryloyl group.

  The (meth) acrylate compound having a morpholine ring and having two or more (meth) acryloyl groups in the present invention can be produced by the following method or the like.

  For example, esterification reaction between a morpholine compound having two or more hydroxyl groups and (meth) acrylic acid or (meth) acrylic chloride, or a bifunctional or higher functional (meth) acrylate compound containing 4-hydroxylinyl and 4-morpholinyl An esterification reaction with carbonyl chloride is mentioned.

  The esterification reaction described above can be performed by a generally known method. For example, in an organic solvent such as toluene, xylene or cyclohexane, the above morpholine compound having two or more hydroxyl groups, acid catalyst such as (meth) acrylic acid, paratoluenesulfonic acid or sulfuric acid, hydroquinone, hydroquinone monomethyl ale, catechol Alternatively, there may be mentioned a method in which a polymerization inhibitor such as phenothiazine is mixed and heated with stirring to perform dehydration esterification. As the organic solvent, those which are difficult to dissolve in water are preferable because separation of the by-product water can be facilitated and the dehydration reaction can easily proceed. The purification method of the obtained compound may follow a conventional method, for example, a method of removing the solvent by vacuum distillation after washing the reaction solution with water.

  Further, for example, in a solvent such as tetrahydrofuran, hexane, diethyl ether or the like, a polymerization inhibitor such as the above morpholine compound having two or more hydroxyl groups, triethylamine, hydroquinone, hydroquinone monomethyl ale, catechol or phenothiazine is mixed. A method in which meth) acrylic acid chloride is dropped and stirred at room temperature for esterification can be mentioned. As the organic solvent, triethylamine hydrochloride which is a by-product that is difficult to dissolve is preferable because the reaction can easily proceed and the purification process can be facilitated. The method for purifying the obtained compound may be in accordance with a conventional method, for example, a method in which triethylamine hydrochloride precipitated from the reaction solution is filtered off, and then the solvent is removed by distillation under reduced pressure.

  In addition, for example, polymerization of a hydroxyl group-containing bifunctional or higher functional (meth) acrylate compound, an amine catalyst such as pyridine or triethylamine, and hydroquinone, hydroquinone monomethyl ale, catechol, or phenothiazine in an organic solvent such as dichloromethane or chloroform. An example is a method in which an inhibitor is mixed, 4-morpholinylcarbonyl chloride is added dropwise with stirring at 0 ° C., the reaction is gradually returned to room temperature, and the reaction is carried out. As the organic solvent, a dehydrated one is preferable. The purification method of the obtained compound may follow a conventional method, for example, a method of removing the solvent by vacuum distillation after washing the reaction solution with water.

  In the present invention, the (meth) acrylate compound having a morpholine ring and having two or more (meth) acryloyl groups has a ratio of the (meth) acryloyl group to the morpholine ring for the purpose of maintaining the coating strength of the cured product. It is desirable that the ratio is 1: 1 to 1: 3.

  Preferred examples of the (meth) acrylate compound having a morpholine ring and having two or more (meth) acryloyl groups in the present invention are shown below, but are not limited thereto.

  The polymerizable composition of the present invention can be cured by heating or light by incorporating a radical polymerization initiator.

  In the case of thermosetting mainly using a thermal energy source such as a heating furnace, infrared rays, and microwaves, a thermal radical polymerization initiator is blended. Examples of the thermal radical polymerization initiator suitably used include azo compounds such as azoisobutyronitrile, ketone peroxides such as methyl ethyl ketone peroxide or cyclohexanone peroxide, hydroperoxides such as diisopropylbenzene hydroperoxide, or the like. Various organic peroxides such as alkyl peroxides such as dicumyl peroxide, acyl peroxides such as benzoyl peroxide or toluoyl peroxide, and peroxy esters such as cumyl peroxy octoate or butyl peroxy isobutyrate And inorganic peroxides such as ammonium persulfate.

  When it is allowed to stand at room temperature for heat curing, or when it is heat cured at a relatively low temperature of 100 ° C. or less, it is preferable to blend a polymerization accelerator together with the above thermal polymerization initiator. As a preferable polymerization accelerator, for example, cobalt , Organometallic salts of metals such as iron or manganese and naphthenic acid, linoleic acid or acetylacetone, reducing amines such as dimethyl paratoluidine and ascorbic acid, and other reducing substances.

  When the composition is cured by irradiation with ultraviolet rays or visible light, a generally used radical photopolymerization initiator is blended. Specifically, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane , Oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl Acetophenones such as phenyl} -2-methylpropan-1-one; benzoin, benzoin methyl ether, benzo Benzoins such as inethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Other examples include phenylglyoxylic methyl ester.

  In the case of photocuring, a sensitizer can be used in combination for the purpose of further improving sensitivity and improving the film properties after reaction curing.

  Sensitizers that can be used together in the present invention include benzophenone derivatives, chalcone derivatives, unsaturated ketone derivatives typified by dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, and benzoin derivatives , Fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, Thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, tria Methane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, Examples include annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, and organic ruthenium complexes.

  Of the sensitizers described above, benzophenone derivatives, thioxanthone derivatives, or acridone derivatives are desirable from the viewpoints of curability and availability.

  When the polymerizable composition is cured by using both photocuring and thermal heavy curing, the photoradical polymerization initiator and the thermal radical polymerization initiator may be used in combination.

  The blending amount of these thermal radical polymerization initiators and photo radical polymerization initiators may be in accordance with conventional methods, and is generally preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the curable component. If the amount is less than 0.01 part, the composition cannot be sufficiently polymerized. If the amount exceeds 20 parts, the amount of the curable component is relatively reduced, and the properties of the cured product may be deteriorated. The amount of the radical polymerization initiator used is particularly preferably 0.1 to 10 parts.

  The polymerizable composition of the present invention can be used in combination with at least one selected from the group consisting of other polymerizable monomers and polymerizable oligomers, if necessary.

  Other polymerizable monomers and polymerizable oligomers are not particularly limited, and can be appropriately selected from polymerizable compounds that are usually used according to the purpose and the like. The other polymerizable monomer may be any polymerizable monomer other than a (meth) acrylate compound having a morpholine ring and having two or more (meth) acryloyl groups, such as a (meth) acrylic group having a (meth) acryl group. And monomers and styrene derivatives.

  Below, the specific example of the other polymerizable monomer in this invention is given.

Examples of acrylates:
Examples of monofunctional alkyl acrylates:
Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate , Dicyclopentenyloxyethyl acrylate, benzyl acrylate.

Examples of monofunctional hydroxy acrylates:
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-allyloxypropyl acrylate, acrylic acid-2-hydroxy- 3-allyloxypropyl, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, 4-hydroxybutyl acrylate.

Examples of monofunctional halogenated acrylates:
2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1H-hexafluoroisopropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 2H, 2H- Heptadecafluorodecyl acrylate, 2,6-dibromo-4-butylphenyl acrylate, 2,4,6-tribromophenoxyethyl acrylate, 2,4,6-tribromophenol 3EO addition acrylate.

Examples of monofunctional ether-containing acrylates:
2-methoxyethyl acrylate, 1,3-butylene glycol methyl ether acrylate, butoxyethyl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol # 400 acrylate, methoxydipropylene glycol acrylate, methoxytripropylene glycol acrylate, methoxypolypropylene glycol acrylate, Ethoxydiethylene glycol acrylate, ethyl carbitol acrylate, 2-ethylhexyl carbitol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, cresyl polyethylene glycol acrylate, acrylic Acrylic acid 2- (vinyloxy) ethyl, p- nonyl phenoxyethyl acrylate, p- nonylphenoxy polyethylene glycol acrylate, glycidyl acrylate.

Examples of monofunctional carboxyl acrylates:
β-carboxyethyl acrylate, succinic acid monoacryloyloxyethyl ester, ω-carboxypolycaprolactone monoacrylate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2- Acryloyloxypropyltetrahydrophthalate.

Examples of other monofunctional acrylates:
N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, morpholinoethyl acrylate, trimethylsiloxyethyl acrylate, diphenyl-2-acryloyloxyethyl phosphate, 2-acryloyloxyethyl acid phosphate, caprolactone-modified-2-acryloyl Oxyethyl acid phosphate, 2-hydroxy-1-acryloxy-3-methacryloxypropane.

Examples of bifunctional acrylates:
1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200 diacrylate, polyethylene glycol # 300 Diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol # 400 diacrylate, polypropylene glycol # 700 diacrylate, neo Pentyl glycol diacrylate, ne Pentyl glycol PO modified diacrylate, hydroxypivalic acid neopentyl glycol ester diacrylate, caprolactone adduct diacrylate of hydroxypivalic acid neopentyl glycol ester, 1,6-hexanediol bis (2-hydroxy-3-acryloyloxypropyl) ether Bis (4-acryloxypolyethoxyphenyl) propane, 1,9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol diacrylate monobenzoate, bisphenol A diacrylate, EO-modified bisphenol A diacrylate, PO-modified bisphenol A diacrylate, hydrogenated bisphenol A diacrylate EO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A diacrylate, bisphenol F diacrylate, EO modified bisphenol F diacrylate, PO modified bisphenol F diacrylate, EO modified tetrabromobisphenol A diacrylate, tricyclodecandi Methylol diacrylate, isocyanuric acid EO-modified diacrylate, 2-hydroxy-1,3-diacryloxypropane.

Examples of trifunctional acrylates:
Glycerin PO-modified triacrylate, trimethylolpropane triacrylate, trimethylolpropane EO-modified triacrylate, trimethylolpropane PO-modified triacrylate, isocyanuric acid EO-modified triacrylate, isocyanuric acid EO-modified ε-caprolactone-modified triacrylate, 1,3 5-triacryloylhexahydro-s-triazine, pentaerythritol triacrylate, dipentaerythritol triacrylate tripropionate.

Examples of tetra- or higher functional acrylates:
Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, oligoester tetraacrylate, tris (acryloyloxy) phosphate.

Examples of methacrylates:
Examples of monofunctional alkyl methacrylates:
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate , Dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, benzyl methacrylate.

Examples of monofunctional hydroxymethacrylates:
2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-allyloxypropyl methacrylate, 2-methacryloyloxyethyl-2 -Hydroxypropyl phthalate.

Examples of monofunctional halogenated methacrylates:
2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H-hexafluoroisopropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 2H, 2H- Heptadecafluorodecyl methacrylate, 2,6-dibromo-4-butylphenyl methacrylate, 2,4,6-tribromophenoxyethyl methacrylate, 2,4,6-tribromophenol 3EO addition methacrylate.

Examples of monofunctional ether-containing methacrylates:
2-methoxyethyl methacrylate, 1,3-butylene glycol methyl ether methacrylate, butoxyethyl methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethylene glycol # 400 methacrylate, methoxydipropylene glycol methacrylate, methoxytripropylene glycol methacrylate, methoxypolypropylene glycol methacrylate, Methacrylic acid-2- (vinyloxyethoxy) ethyl, ethoxydiethylene glycol methacrylate, 2-ethylhexyl carbitol methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxy polyethylene glycol methacrylate, Jill polyethylene glycol methacrylate, p- nonyl phenoxyethyl methacrylate, p- nonylphenoxy polyethylene glycol methacrylate, glycidyl methacrylate.

Examples of monofunctional carboxyl-containing methacrylates:
β-carboxyethyl methacrylate, succinic acid monomethacryloyloxyethyl ester, ω-carboxypolycaprolactone monomethacrylate, 2-methacryloyloxyethyl hydrogen phthalate, 2-methacryloyloxypropyl hydrogen phthalate, 2-methacryloyloxypropyl hexahydrohydrogen phthalate, 2- Methacryloyloxypropyl tetrahydrophthalate.

Examples of other monofunctional methacrylates:
Dimethylaminomethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, morpholinoethyl methacrylate, trimethylsiloxyethyl methacrylate, diphenyl-2-methacryloyloxyethyl phosphate, 2-methacryloyloxyethyl acid phosphate, caprolactone Modified-2-methacryloyloxyethyl acid phosphate and the like.

Examples of bifunctional methacrylates:
1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 300 Dimethacrylate, polyethylene glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol # 400 dimethacrylate, polypropylene glycol # 700 dimethacrylate, neopenty Glycol dimethacrylate, neopentyl glycol PO modified dimethacrylate, hydroxypivalic acid neopentyl glycol ester dimethacrylate, caprolactone adduct dimethacrylate of hydroxypivalic acid neopentyl glycol ester, 1,6-hexanediol bis (2-hydroxy-3- (Methacryloyloxypropyl) ether, 1,9-nonanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate monostearate, pentaerythritol dimethacrylate monobenzoate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane Bisphenol A dimethacrylate, EO modified bisphenol A dimethacrylate, PO modified bisphenol A-dimethacrylate, hydrogenated bisphenol A dimethacrylate, EO-modified hydrogenated bisphenol A dimethacrylate, PO-modified hydrogenated bisphenol A dimethacrylate, bisphenol F dimethacrylate, EO-modified bisphenol F dimethacrylate, PO-modified bisphenol F dimethacrylate, EO-modified tetrabromobisphenol A dimethacrylate, tricyclodecane dimethylol dimethacrylate, isocyanuric acid EO-modified dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane.

Examples of trifunctional methacrylates:
Glycerin PO modified trimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane EO modified trimethacrylate, trimethylolpropane PO modified trimethacrylate, isocyanuric acid EO modified trimethacrylate, isocyanuric acid EO modified ε-caprolactone modified tri Methacrylate, 1,3,5-trimethacryloyl hexahydro-s-triazine, pentaerythritol trimethacrylate, dipentaerythritol trimethacrylate tripropionate.

Examples of tetrafunctional or higher methacrylates:
Pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate, dipentaerythritol hexamethacrylate, tetramethylolmethane tetramethacrylate, oligoester tetramethacrylate, tris (methacryloyloxy) phosphate.

Examples of arylates:
Allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, isocyanuric acid triarylate.

Examples of acid amides:
Acrylamide, N-methylolacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, methacrylamide, N-methylolmethacrylamide, diacetone methacrylamide, N, N -Dimethylmethacrylamide, N, N-diethylmethacrylamide, N-isopropylmethacrylamide, methacryloylmorpholine.

Examples of styrenes:
Styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene, pt-butoxycarbonyloxystyrene 2,4-diphenyl-4-methyl-1-pentene.

Examples of other vinyl compounds:
Vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl 2-ethylhexanoate, N-vinylcarbazole, N-vinylpyrrolidone 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, normal propyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, 1,4-butane Diol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol Distearate ether, triethylene glycol divinyl ether.

  The polymerizable monomer can be easily obtained as a commercial product of the manufacturer shown below. For example, “Light acrylate”, “Light ester”, “Epoxy ester”, “Urethane acrylate” and “Highly functional oligomer” series manufactured by Kyoeisha Yushi Chemical Co., Ltd., Shin Nakamura Chemical Co., Ltd. "NK Ester" and "NK Oligo" series, "Fancrill" series manufactured by Hitachi Chemical Co., Ltd., "Aronix M" and "Aclicks" series manufactured by Toagosei Co., Ltd., Daihachi Chemical Industry "Functional Monomer" series manufactured by Co., Ltd., "Special Acrylic Monomer (Chemicals, Electronic Materials)" series manufactured by Osaka Organic Chemical Industry Co., Ltd., "Acryester" manufactured by Mitsubishi Rayon Co., Ltd. and “Diabeam oligomer” series, “Kayarad” and “Kayamar” series manufactured by Nippon Kayaku Co., Ltd. "Lulic acid / methacrylic acid ester monomer", "acrylic acid / methacrylic acid special ester", "(meth) acrylic acid hydroxy monomer", and "(meth) acrylic acid metal salt" series, manufactured by Nippon Synthetic Chemical Industry Co., Ltd. "NICHIGO-UV purple light urethane acrylate oligomer" series, "Denacol acrylate" series manufactured by Nagase ChemteX Corporation, "Epoxy (meth) acrylate", "Urethane acrylate", Shin-Etsu acetic acid manufactured by KSM Co., Ltd. "Carboxylic acid vinyl ester monomer" series manufactured by Vinyl Co., Ltd., "Functional monomer" series manufactured by Kojin Co., Ltd., "Vinyl ether" series manufactured by Maruzen Petrochemical Co., Ltd., Nippon Carbide Industries Co., Ltd. "Alkyl monovinyl ether" "Hydroxyalkyl vinyl" "Tell" "alkyl divinyl ether" series, "Cycloaliphatic divinyl ether monomer" manufactured by Daicel Corporation, "acrylate monomer", "epoxy acrylate", "urethane acrylate", "polyester acrylate" manufactured by Daicel Ornex Co., Ltd. ”,“ Polyether acrylate ”,“ acid group-containing acrylate ”series, and the like.

  In addition, allyl ether compounds represented by “Allyl ethers” series manufactured by Daiso Co., Ltd. are also exemplified as polymerizable monomers.

Moreover, the cyclic compound shown below is also mentioned as a polymerizable monomer.
Examples of three-membered ring compounds:
Vinylcyclopropanes described in Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. Ed.), Volume 17, p. 3169 (1979), Macromolecular Chemie 1-Phenyl-2-vinylcyclopropanes described in Rapid Communication (Makromol. Chem. Rapid. Commun.), Vol. 5, p. 63 (1984), Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. Ed.), Volume 23, page 1931 (1985) and Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Poly). Lett. Ed.), Vol. 21, page 4331 (1983), 2-phenyl-3-vinyloxiranes, Proceedings of the 50th Annual Meeting of the Chemical Society of Japan, 1564 (1985) , 3-Divinyloxiranes.

Examples of cyclic ketene acetals:
Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. Ed.), Volume 20, p. 3021 (1982) and Journal of Polymer Science Polymer Letter -2-methylene-1,3-dioxepane, polymer preprint (Polym. Preprints) described in edition (J. Polym. Sci. Polym. Chem. Ed.), Vol. 21, p. 373 (1983) 34, 152 (1985), dioxolanes, Journal of Polymer Science, Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed.), 20, 361 (1982) Year), macromolecular 2-Methylene-4-phenyl- described in Chemmy (Makromol. Chem.), 183, 1913 (1982) and Macromolecular Chem., 186, 1543 (1985). 1,3-dioxepane, 4,7-dimethyl-2-methylene-1,3-dioxepane described in Macromolecules, Vol. 15, p. 1711 (1982), polymer preprint (Polym. Preprints) ), 34, 154 (1985), 5,6-benzo-2-methylene-1,3-dioxepane.

  Furthermore, the thing as described in the literature shown below as a polymerizable monomer can also be mentioned. For example, edited by Shinzo Yamashita et al., “Cross-linking agent handbook” (1981, Taiseisha), Kiyomi Kato edition, “UV / EB curing handbook (raw material edition)”, (1985, Polymer publication society), Radtech Research Meeting, Kiyoshi Akamatsu, “New Technology for Photosensitive Resins” (1987, CMC), Takeshi Endo, “Refinement of Thermosetting Polymers” (1986, CMC), Takiyama Soichiro, “Polyester Resin Handbook” (1988, Nikkan Kogyo Shimbun), edited by Radtech Study Group, “Application and Market of UV / EB Curing Technology” (2002, CMC).

  The polymerizable composition of the present invention can use a polymerizable oligomer in addition to the above other polymerizable monomers. Specifically, Daicel UCB's “Ebecry” series, “KRM” series, “KRM” series, “IRR” series, “RDX” series, Sartomer's “CN” series, BASF's “Laromer” series, Examples include the “Photomer” series manufactured by Cognis, the “Art Resin” series manufactured by Negami Kogyo, the “Shikko” series manufactured by Nippon Gohsei, and the “Kayarad” series manufactured by Nippon Kayaku.

  The polymerizable composition of the present invention can undergo a polymerization reaction by applying energy such as heat, ultraviolet rays, visible rays, near infrared rays, electron beams, etc., during the polymerization reaction, to obtain a desired polymer. As a light source for applying energy, a light source having a dominant wavelength of light emission in a wavelength region of 250 nm to 450 nm is preferable. Examples of light sources having a dominant wavelength of light emission in the wavelength region of 250 nm to 450 nm include ultrahigh pressure mercury lamps, high pressure mercury lamps, mercury xenon lamps, metal halide lamps, high power metal halide lamps, xenon lamps, pulsed emission xenon lamps, deuterium Various light sources such as lamps, fluorescent lamps, Nd: YAG triple wave lasers, He-Cd lasers, nitrogen lasers, XeCl excimer lasers, XeF excimer lasers, semiconductor excitation solid lasers, LED lamp light sources having emission wavelengths of 365 nm, 375 nm and 385 nm Is mentioned. In addition, the definition of ultraviolet rays, visible light, near infrared rays, and the like referred to in this specification is based on “Iwanami Riken Dictionary 4th Edition” (1987, Iwanami) edited by Ryogo Kubo et al.

  The member to which the polymerizable composition of the present invention is applied can be appropriately selected from the group consisting of plastic, glass, metal and paper. Furthermore, a composite member composed of a plurality of members can also be selected. The plastic film is preferably transparent.

  Examples of the plastic material include transparent polymers such as polyester polymers, cellulose polymers, polycarbonate polymers, and polyacrylic polymers.

  Therefore, various inks, ink-jet inks, overcoat varnishes, various printing plate materials, photoresists, electrophotography, direct printing plate materials, optical fibers, hologram materials, and other photosensitive materials, microcapsules, etc. It can be applied to various recording media, as well as adhesives, pressure-sensitive adhesives, adhesives, release coating agents, sealants, and various paints.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to only the following Example at all. Unless otherwise specified, “%” means “% by weight” and “parts” means “parts by weight”.

Example 1
A reaction vessel equipped with a stirrer and a thermometer was charged with 13.0 parts of 3-morpholino-1,2-propanediol, 180 parts of tetrahydrofuran, 17.95 parts of triethylamine, 0.007 part of hydroquinone monomethyl ether as a polymerization inhibitor, ice It was immersed in a bath and cooled to 10 ° C. or lower. 16.05 parts of acrylic acid chloride and 20 parts of tetrahydrofuran were mixed and slowly added dropwise over 1 hour while cooling so that the temperature of the reaction solution could be maintained at 5 to 10 ° C. After completion of the dropwise addition reacted for 2 hours at room temperature, the reaction with ^{1 H-NMR,} it was confirmed that the was complete. The precipitated triethylamine hydrochloride was filtered off by Kiriyama filtration, water was added to the filtrate, extracted with diethyl ether, washed with water, dried over magnesium sulfate, and the solvent was removed to remove 6.96 parts of the target compound A. Obtained. The structure of the obtained compound A was confirmed by ¹ H-NMR. A ¹ H-NMR chart of Compound A is shown in FIG.

Example 2
In a flask equipped with a stirrer, a thermometer and a water separation pipe with a cooling pipe at the top, 13.0 parts of 3-morpholino-1,2-propanediol, 15.27 parts of methacrylic acid, p-toluenesulfone as a catalyst After charging 1.16 parts of acid, 0.007 part of hydroquinone monomethyl ether as a polymerization inhibitor and 30 parts of toluene as a solvent, the mixture was heated with stirring and subjected to dehydration ester reaction at a reaction temperature of 110 ° C. for 5 hours. After confirming the completion of the reaction by ¹ H-NMR, the reaction solution was washed with water, and toluene was removed by distillation under reduced pressure to obtain 7.13 parts of the target compound, Compound B. The structure of the obtained compound B was confirmed by ¹ H-NMR.

Example 3
A reaction vessel equipped with a stirrer and a thermometer was charged with 14.91 parts of pentaerythritol triacrylate, 4.75 parts of pyridine, 0.04 part of hydroquinone monomethyl ether as a polymerization inhibitor and 80 parts of dehydrated dichloromethane as a solvent, and then iced. It was immersed in a bath and cooled to 5 ° C. or lower. Then, 7.85 parts of 4-morpholinylcarbonyl chloride was mixed and slowly added dropwise over 1 hour with cooling so that the temperature of the reaction solution could be maintained at 5 ° C. or lower. After completion of the dropwise addition was reacted at room temperature for 12 hours, the reaction in ^{1 H-NMR,} it was confirmed that the was complete. The reaction solution was washed with a 5% aqueous sodium hydrogen carbonate solution, and dichloromethane was removed by distillation under reduced pressure to obtain 9.46 parts of the target compound C. The structure of Compound C obtained was confirmed by ¹ H-NMR.

<Examples of polymerizable composition>
Each polymerizable composition was obtained by the formulation shown in Table 1. About the obtained polymeric composition, sclerosis | hardenability, hardness of hardened | cured material, and the base-material adhesiveness to glass were evaluated with the following method.

<Curability evaluation test>
The prepared polymerizable composition was applied onto a polyethylene terephthalate (PET) substrate with a bar coater so that the wet film thickness was 20 μm. The obtained coated material was irradiated with ultraviolet rays at a conveyor speed of 40 m / min in an air atmosphere using a belt conveyor type ultraviolet irradiation device (high pressure mercury lamp 160 W / cm 1 lamp). After each irradiation, the surface of the cured product was rubbed with a cotton cloth to check whether the surface of the cured product was damaged. Ultraviolet irradiation was repeated until the surface of the cured product was not damaged, and the curability was determined. It was judged that the lower the number of UV irradiations, the better the curability. Judgment criteria are as follows.

Judgment criteria ◎: 1 time (very good)
○: 2 to 4 times (good)
Δ: 5 to 10 times (somewhat poor)
X: 11 times or more (defect)

<Hardness evaluation test of cured product>
The prepared polymerizable composition was applied onto a polycarbonate substrate with a bar coater so that the wet film thickness was 10 μm. The obtained coated material was subjected to ultraviolet irradiation 5 times at a conveyor speed of 10 m / min in an air atmosphere using a belt conveyor type ultraviolet irradiation device (high pressure mercury lamp 160 W / cm 1 lamp) to obtain a cured product. . The obtained cured product was tested based on JIS standard (K5600-5-4) (hardness range: 6B to HB to 6H).

<Adhesion>
The prepared polymerizable composition was applied onto a glass substrate with a bar coater so that the wet film thickness was 10 μm. The obtained coated material was subjected to ultraviolet irradiation 5 times at a conveyor speed of 10 m / min in an air atmosphere using a belt conveyor type ultraviolet irradiation device (high pressure mercury lamp 160 W / cm 1 lamp) to obtain a cured product. . The obtained cured product was tested by a cross-cut tape method based on JIS standard (K5400-8-5-2) using a cross cut guide manufactured by Co-Tech Co., Ltd. The one with less peeling in the 100 square grid was judged to have good adhesion. Judgment criteria are as follows.

Criteria ◎: No peeling (very good)
○: 1 to 5 mass peeling (good)
(Triangle | delta): 6-20 mass peeling (slightly bad)
X: Peeling 21 squares or more (defect)

The raw materials in Table 1 are shown below.
A-TMPT: Trimethylolpropane triacrylate (Shin Nakamura Chemical Co., Ltd.)
PETA (pentaerythritol triacrylate): Biscoat # 300 (Osaka Organic Chemical Co., Ltd.)
ACMO: acryloylmorpholine (KJ Chemicals)
EO-TMPTA (ethylene oxide 3 molar modified trimethylolpropane triacrylate): Aronix M-350 (Toagosei Co., Ltd.)
TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (BASF)
Irg184: 1-hydroxy-cyclohexyl-phenyl-ketone (BASF)

  The (meth) acrylate compound of the present invention having a morpholine ring and having two or more (meth) acryloyl groups has a fast curing speed accompanying the reaction, excellent substrate adhesion to an inorganic substrate, and high coating. It became clear that film hardness was given (Examples 4-7).

  The (meth) acrylate compound of the present invention having a morpholine ring and having two or more (meth) acryloyl groups is blended with at least one selected from the group consisting of other polymerizable monomers and polymerizable oligomers. Even in the case, it became clear that the curing speed accompanying the reaction was high, the substrate adhesion to the inorganic substrate was excellent, and the coating film hardness was high (Examples 8 to 10).

  With conventional (meth) acrylate compounds, due to the effects of crosslink density and cure shrinkage, it was not possible to satisfy the balance between physical properties of curing speed, adhesion to inorganic substrates, and coating film hardness due to reaction (Comparative Example) 1-5).

As described above, the (meth) acryloyl group having a morpholine ring, which is a (meth) acrylate compound that has a fast curing speed with the reaction, excellent base material adhesion to an inorganic base material, and gives high coating film hardness. It was possible to provide a (meth) acrylate compound having two or more and a polymerizable composition using the same.

Claims (5)

  A (meth) acrylate compound having a morpholine ring and having two or more (meth) acryloyl groups.   The (meth) acrylate compound according to claim 1, wherein the ratio of the (meth) acryloyl group to the morpholine ring is 1: 1 to 1: 3.   A polymerizable composition comprising the (meth) acrylate compound according to claim 1 or 2 and a radical polymerization initiator.   The polymerizable composition according to claim 3, wherein the radical polymerization initiator is a photo radical polymerization initiator.   5 or 4 further comprising at least one selected from the group consisting of a polymerizable monomer and a polymerizable oligomer other than the (meth) acrylate compound having a morpholine ring and having two or more (meth) acryloyl groups. The polymerizable composition as described.