Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
  • C07C69/54—Acrylic acid esters; Methacrylic acid esters

Definitions

• the present invention relates to a di (meth) acrylate useful for use as an ultraviolet curable or electron beam curable coating agent, paint, printing ink, adhesive or diluent thereof.
• 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and trimethylolpropane triacrylate have a problem that they have strong skin irritation.
• Japanese Patent Application Laid-Open No. 63-250347 / 1991 discloses 3-methyl-1,5-pentanedioyl dimethacrylate and the like, and Japanese Patent Application Laid-Open No. Hei 3-666643 discloses 2-petit It discloses ru-2-ethyl-1,3-propanediol dimethacrylate, but none of these dimethacrylates is practically satisfactory in terms of toughness and flexibility. Disclosure of the invention
• the present invention provides di (meth) acrylate represented by the following general formula (I), that is, diacrylate or dimethacrylate.
• R 1 and R 2 are the same or different and represent a hydrogen atom or CH 3
• R 3 and R 4 are the same or different and represent a lower alkyl having 1 to 6 carbon atoms.
• lower alkyl having 1 to 6 carbon atoms R 3 and R 4 represent a straight-chain or branched one, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Represents tert-butyl, pentyl, isopentyl, neopentyl, hexyl, etc.
• the di (meth) acrylate of the present invention has no skin irritation.
• a curable composition which can be easily cured by ultraviolet rays, an electron beam, heat or the like can be obtained.
• the crosslinked cured product obtained from the curable composition has hydrolysis resistance, excellent durability, and excellent flexibility.
• the di (meth) acrylate of the present invention comprises: (1) an esterification reaction of 2,4-dialkyl-1,5-pentanediol with (meth) acrylic acid; (2) 2,4-dialkyl acrylate; Transesterification of 2,5-pentanedyldiol with (meth) acrylates such as methyl (meth) acrylate or ethyl (meth) acrylate, (3) 2,4-dialkyl-1,1,5-pentanediol It can be produced by a reaction with (meth) acrylic acid halide such as (meth) acrylic acid chloride.
• 2,4-dialkyl-1,5-pentanediol examples include 2,4-dimethyl-1,5-pentanediol, 2-ethyl-4-monomethyl-1,5-pentanediol, and 2-methyl —4—Propyl—1,5-Pentanediol, 2-dipropyl—4-Methyl-1,5-pentanediol, 2,4-Getyl—1,5_pentanediol, 2-Ethyl-4-propyl—1 , 5-Pentanediol, 2-Ethyl-4-1-isopropyl-1,5-pentanediol, 2,4-Dipropyl-1,5-pentanediol, 2-Isopropyl-4-propyl-1 1,5-pentanediol, 2,4-diisopropyl-1,5-pentanediol
• 2,4-Dialkyl-1,5-pentanediol can be prepared by a known method, preferably 2-butenal as described in Japanese Patent Application Laid-Open No. 8-48642, ⁇ 080717 ⁇ . It can be obtained by reacting a derivative with formaldehyde and hydrogenating the obtained reaction product.
• the amount of (meth) acrylic acid used is about 2 to 10 moles per mole of 2,4-dialkyl-1,5-pentyldiol.
• the esterification reaction of (meth) acrylic acid with 2,4-dialkyl-1,5-pentyldiol is usually carried out at about 60 to 140, preferably 75 to 100.
• a catalyst may be used.
• the catalyst include sulfuric acid, p-toluenesulfonic acid, Examples include acid catalysts such as phosphoric acid, metal oxides such as zinc oxide and germanium oxide, and esterification catalysts such as tin octylate and tetrabutyl titanate. It is used at a concentration of 0.001 to 5% by weight.
• an azeotropic solvent may be used to efficiently remove water generated during the esterification reaction.
• the azeotropic solvent include hexane, cyclohexane, benzene, toluene, xylene and the like, or a mixture thereof.
• the desired product can be purified by a purification method commonly used in synthetic organic chemistry, for example, filtration, extraction, washing, drying, concentration, or distillation.
• a purification method commonly used in synthetic organic chemistry for example, filtration, extraction, washing, drying, concentration, or distillation.
• the organic layer is separated by filtration, the organic layer is neutralized with unreacted (meth) acrylic acid, acid catalyst, etc. with an aqueous solution of sodium hydroxide or the like, washed with water, and then subjected to solvent distillation. Purification is performed by distillation under reduced pressure.
• reaction conditions and purification conditions for this transesterification reaction can be carried out in the same manner as in the above (1).
• the reaction can also be performed under reduced pressure.
• the amount of (meth) acrylic halide used is about 2 to 4 mol per mol of 2,4-dialkyl-1,5-pentanediol.
• the reaction of the (meth) acrylic acid halide with 2,4-dialkyl-1,5-pentanediol is usually carried out at a temperature of about 150 or less, preferably 10 o: the following.
• Tertiary amines for example, triethylamine, pyridine and the like may be used as the catalyst, and the catalyst can make the reaction proceed efficiently in a short time.
• the reaction solvent include hexane, cyclohexane, benzene, toluene, xylene and the like, or a mixture thereof.
• the desired product can be obtained by washing with alkaline water and then with water, and purifying by distilling off the solvent and distilling.
• the above-mentioned reactions (1) to (3) are preferably performed in the presence of a polymerization inhibitor in order to suppress polymerization of a double bond derived from (meth) acrylic acid which occurs during the reaction.
• the polymerization inhibitor is preferably used at a concentration of 0.1 to 5% by weight based on the reaction mixture. Examples thereof include hydroquinone, hydroquinone monomethyl ether, 2,4-dimethyl-6-t-butylphenol, and phenothiazine. The known ones can be used.
• di (meth) acrylate of the present invention those in which R 1 and R 2 in the general formula (I) are the same are preferable.
• an ultraviolet curable composition By using the di (meth) acrylate of the present invention, an ultraviolet curable composition, an electron beam curable composition, and a thermosetting composition can be obtained. These compositions give a cross-linked cured product, which is excellent in hydrolysis resistance and flexibility.
• the di (meth) acrylate of the present invention can be used as an ultraviolet-curing or electron beam-curing coating agent, paint, printing ink, adhesive or diluent thereof.
• the di (meth) acrylate of the present invention may be used in combination with a photopolymerization initiator, a radical initiator, other acrylates, a polymerization inhibitor, a filler, a coloring agent, depending on the purpose and application. It is used as a composition with agents, waxes and the like. These compositions can be easily cured by irradiating with radiation such as electron beams or ultraviolet rays or by thermal means. For example, after applying the compositions to iron, glass, woodcut, etc.
• a cured film can be obtained by irradiating such as radiation or heating.
• a photopolymerization initiator for example, a benzoin ether derivative such as benzoin butyl ether or benzoin isopropyl ether, or ⁇ -hydroxyisobutyl phenone, 2,2-dimethoxy-2 Acetofphenone derivatives such as phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, and phenothiazine may be used alone or in combination.
• the use amount of the photopolymerization initiator is preferably 0.1 to 10% by weight of the composition.
• a radical initiator such as an organic peroxide or an azobis compound may be used.
• the di (meth) acrylate of the present invention can be used by mixing with other polyfunctional (meth) acrylates or copolymerizable oligomers and polymers.
• polyfunctional (meth) acrylates that may be used with the di (meth) acrylate of the present invention include, for example, trimethylolpropane triacrylate, Examples include dipentyl erythritol hexaacrylate or 1,6-hexanediol diacrylate.
• copolymerizable oligomer and polymer examples include polyethylene glycol or polypropylene glycol diacrylate, bisphenol A ethylene oxide adduct diacrylate, polyurethane acrylate, or polyester acrylate, epoxy resin acrylate, Examples of the resin include unsaturated group-containing resins such as polybutadiene acrylate and unsaturated polyester.
• the content of the di (meth) acrylate of the present invention in the composition is appropriately determined depending on the use.
• the content of the di (meth) acrylate of the present invention is about 3 parts by weight or more based on 100 parts by weight of the total amount of the polyfunctional (meth) acrylates and the like and the di (meth) acrylate of the present invention. Is preferable.
• the obtained product had a viscosity of 11 cps (at 25), a bromine value of 117 and a saponification value of 417.
• 1 H-NMR, 13 C-NMR and IR measurement results of the obtained product are shown below.
• Injection temperature 290: Detector temperature: 29 ⁇ Column temperature: 100 to 290 (10 min)
• Air flow rate 50 k ⁇ , H 2 flow rate: 60 k P, N 2 flow rate: 40 m 1 Bruno min Example 2
• Table 1 shows the viscosities at 25 of di (meth) acrylate and commercially available (meth) acrylate synthesized in Examples 1 and 2 and Comparative Examples 1 to 3.
• Table 1 Physical properties (viscosity) of various (meth) acrylates
• Bending test As a method of evaluating flexibility, the obtained film was bent and the bending angle at which the film was broken was examined. The smaller the bending angle, the better the film was bent before breaking.
• Hydrolysis resistance (Evaluation method): A 5% hydrochloric acid aqueous solution was placed in a glass container, and the cured film was immersed in the glass container and stored for 90 to 10 days. ).
• the cured film using the di (meth) acrylate of the present invention has good hydrolysis resistance and also shows excellent flexibility from a bending test.
• Test examples 7, 8 The skin irritation of the di (meth) acrylate obtained in Examples 1 and 2 was examined by the following method. Table 3 shows the results of the skin irritation test.
• the di (meth) acrylate of the present invention is hypoallergenic to skin, Industrial applicability
• the di (meth) acrylate of the present invention is easy to handle because it has low irritation to the skin. Further, the composition containing the di (meth) acrylate is easily cured by ultraviolet rays, electron beams, heat, and the like, and gives a cured product excellent in durability, flexibility and the like.
• the di (meth) acrylate of the present invention is useful for use as a UV-curable or electron beam-curable coating agent, paint, printing ink, adhesive or diluent thereof.
• the composition containing di (meth) acrylate of the present invention is suitable as a binder, an adhesive, a coating agent, and the like for optical disks, optical fibers, magneto-optical disks, and the like.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Dental Preparations (AREA)

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Citations (3)

• 1998
  • 1998-03-02 TW TW087102968A patent/TW473472B/zh not_active IP Right Cessation
  • 1998-03-03 CA CA002253493A patent/CA2253493A1/en not_active Abandoned
  • 1998-03-03 EP EP98905733A patent/EP0909752B1/en not_active Expired - Lifetime
  • 1998-03-03 DE DE69801554T patent/DE69801554T2/de not_active Expired - Fee Related
  • 1998-03-03 AU AU61191/98A patent/AU6119198A/en not_active Abandoned
  • 1998-03-03 JP JP53835798A patent/JP3987125B2/ja not_active Expired - Fee Related
  • 1998-03-03 AT AT98905733T patent/ATE205179T1/de not_active IP Right Cessation
  • 1998-03-03 WO PCT/JP1998/000862 patent/WO1998039285A1/ja not_active Ceased
  • 1998-10-30 KR KR1019980708767A patent/KR100271872B1/ko not_active Expired - Fee Related

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