KR0160451B1 - Process for preparing epoxy acrylate and its uv curable resin composition - Google Patents
Process for preparing epoxy acrylate and its uv curable resin composition Download PDFInfo
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- KR0160451B1 KR0160451B1 KR1019950010766A KR19950010766A KR0160451B1 KR 0160451 B1 KR0160451 B1 KR 0160451B1 KR 1019950010766 A KR1019950010766 A KR 1019950010766A KR 19950010766 A KR19950010766 A KR 19950010766A KR 0160451 B1 KR0160451 B1 KR 0160451B1
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- acrylate
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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000011342 resin composition Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000004593 Epoxy Substances 0.000 claims abstract description 10
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims abstract description 10
- 238000009826 distribution Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 6
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 3
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 12
- 239000004917 carbon fiber Substances 0.000 abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 8
- 239000004033 plastic Substances 0.000 abstract description 7
- 229920003023 plastic Polymers 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003848 UV Light-Curing Methods 0.000 abstract description 3
- 238000001723 curing Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 150000002118 epoxides Chemical class 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- -1 lithium halide Chemical class 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- ZNAAXKXXDQLJIX-UHFFFAOYSA-N bis(2-cyclohexyl-3-hydroxyphenyl)methanone Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C(=O)C1=CC=CC(O)=C1C1CCCCC1 ZNAAXKXXDQLJIX-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Epoxy Resins (AREA)
Abstract
본 발명은 카본화이어 플라스틱소재의 접착 및 상도코팅용으로 사용되고 자외선 경화시에 접착성, 투명성, 내충격성 및 내후성등이 우수하고 새로운 에폭시 아크릴레이트를 제조하는 방법, 그리고 상기 에폭시 아크릴레이트를 이용한 자외선경화형 수지조성물에 관한 것으로, 비스페놀 A 변성 에폭시화물과 (메타) 아크릴산과의 반응물제조과정에 4차 암모늄염과 이온교환수를 조합촉매로 하여 가드너 색수 1이하, 평균 분자량 분포 1 -1.1 정도인 에폭시 아크릴레이트혼합물의 제조방법과, 비스페놀 A 변성 에폭시 화물과 (메타) 아크릴산과의 반응물제조과정에 4차 암모늄염과 이온교환수를 조합촉매로 하여 가드너 색수 1이하, 평균 분자량 분포 1 -1.1 정도로 제조되는 에폭시 아크릴레이트혼합물, 분자중에 아크릴로일기를 함유한 (메타)아크릴레이트 모노머 및 광증감제를 함유한 자외선경화형 수지조성물.The present invention is used for adhesion and top coat coating of carbon fiber plastic materials, and is excellent in adhesiveness, transparency, impact resistance and weather resistance when UV curing and new epoxy. A method for producing an acrylate, and an ultraviolet curable resin composition using the epoxy acrylate, comprising: bisphenol A-modified epoxide and (meth) Epoxy having a Gardner color number of 1 or less and an average molecular weight distribution of about 1 -1.1 using a combination catalyst of quaternary ammonium salts and ion-exchanged water in the production of reactants with acrylic acid In the preparation method of the acrylate mixture and the reaction of bisphenol A modified epoxy cargo with (meth) acrylic acid, quaternary ammonium salt and ion-exchanged water were used as a combined catalyst. Epoxy acrylate mixtures produced with a Gardner color number of 1 or less and an average molecular weight distribution of about 1 -1.1, (meth) acrylate monomers containing acryloyl group in the molecule And an ultraviolet curing resin composition containing a photosensitizer.
Description
본 발명은 새로운 에폭시 아크릴레이트(epoxy-acrylate)의 제조방법 및 이를 이용한 자외선경화형 수지조성물에 관한 것으로, 더욱 상세하게는 카본화이버 플라스틱소재의 접착 및 상도코팅용으로 사용되고 자외선 경화시에 접착성, 투명성, 내충격성 및 내후성등이 우수하고 새로운 에폭시 아크릴레이트를 제조하는 방법, 그리고 상기 에폭시 아크릴레이트를 이용한 자외선경화형 수지 조성물에 관한 것이다.The present invention relates to a new epoxy acrylate (epoxy-acrylate) production method and UV-curable resin composition using the same, more specifically It is used for adhesion and top coat coating of carbon fiber plastic materials. It is excellent in adhesiveness, transparency, impact resistance and weather resistance when UV curing. It relates to a method for producing and an ultraviolet curable resin composition using the epoxy acrylate.
현재 자외선 경화형 수지조성물은 성자원화, 성에너지화, 공해방지 및 작업성, 그리고 생산성의 향상등과 같은 이유로서 많은 이용되고 있는 바, 플라스틱분야인 카본화이버(carbon fiber) 플라스틱소재를 이용한 분야에 있어서도 상기와 같은 이유들 때문에 열경화형 조성물로부터 자외선 경화형 조성물로 바뀌어 가는 실정이다.Currently, UV-curable resin compositions are frequently used for reasons such as sex resources, sex energy, pollution prevention and workability, and productivity improvement. In the field of using carbon fiber plastic material, which is a plastic field, UV curing type from a thermosetting composition for the same reasons as described above. The situation is changing to a composition.
그러나, 플라스틱분야에서 적용하고 있는 자외선 경화형 조성물은, 주로 우레탄 아크릴레이트(urethane acrylate)나 폴리에스테르 아크릴레이트(polyester acrylate)의 바니쉬(varnish)로서 박막 형성성, 유연성, 내충격성은 우수하겠지만 내열, 내약품성 및 내습성이 요구되고, 접착력과 두꺼운 도막형성성등이 요구되고 있는 카본화이버의 낚시대에서는 사용하기 어렵다는 사실을 감지하게 되었다.However, UV curable compositions applied in plastics are mainly urethane acrylate or polyester. Varnish of acrylate (polyester acrylate), thin film formation, flexibility, impact resistance, but heat, chemical resistance and moisture resistance It has been found to be difficult to use in carbon fiber fishing rods, which are required and require adhesion and thick film formation.
따라서, 이러한 물성요구로 인하여 에폭시 아크릴레이트가 적합하다는 것으로 판단하였으나, 목공용 도료, 오버 프린트바니쉬(over-print varnish), 잉크용으로 사용되고 있는 에폭시 아크릴레이트조성물로는 유연성, 내충격성, 투명성 및 내후성등의 물성에서 부적합함을 알게 되었다.Therefore, the epoxy acrylate was determined to be suitable due to such physical properties, but woodwork paints and over-print varnishes (over-print) varnish), the epoxy acrylate composition used for ink is not suitable for physical properties such as flexibility, impact resistance, transparency and weather resistance It became.
이에 본 발명은 상기와 같은 문제점을 해소하기 위해 발명한 것으로, 비스페놀 A(bisphennol A)와 에피클로로히드린과의 반응으로 제조된 비스페놀 A 변성 에폭시 화물을 이용하여 새로운 에폭시 아크릴레이트를 제조함으로써 카본화이버 플라스틱소재의 접착 및 상도코팅용으로 사용되며 평균분자량의 폭이 매우 적고 투명성이 우수한 새로운 에폭시 아크릴레이트의 제조방법을 제공할 수 있고, 또 상기 에폭시 아크릴레이트의 제조방법을 이용하여 접착성, 후도막성, 내열, 내약품, 내습성이 양호하고 내충격성이 우수한 카본화이버 낚시대에 적합한 자외선경화형 수지조성물을 제공하고자 함에 그 목적이 있다.Therefore, the present invention is invented to solve the above problems, bisphenol A prepared by the reaction of bisphenol A (bisphennol A) and epichlorohydrin A new epoxy acrylate is prepared using modified epoxy cargo. It is used for the adhesion and top coat of carbon fiber plastic materials. It is possible to provide a new method for producing a very small and excellent transparency of epoxy acrylate, and also by using the method of producing the epoxy acrylate adhesive, Its purpose is to provide a UV-curable resin composition suitable for carbon fiber fishing rods with good thick film resistance, heat resistance, chemical resistance, moisture resistance, and impact resistance. have.
상기 목적을 달성하기 위한 본 발명의 에폭시 아크릴레이트혼합물을 제조하는 방법은, 비스페놀 A 변성 에폭시화물과 (메타)아크릴산((meta)-acrylic acid)과의 반응물제조과정에 4차 암노늄염과 이온교환수를 조합촉매로 하여 가드너 색수 1이하, 평균 분자량 분포 1 - 1.1 정도인 것을 특징으로 한다.Method for producing an epoxy acrylate mixture of the present invention for achieving the above object is a bisphenol A modified epoxide and Gardner color number 1 or less, average molecular weight, using a combination catalyst of quaternary ammonium salt and ion-exchanged water in the process of preparing reactant with (meth) acrylic acid It is characterized by having a distribution of 1 to 1.1.
또 본 발명의 자외선경화형 수지조성물은, 비스페놀 A 변성 에폭시화물과 (메타) 아크릴산과의 반응물제조과정에 4차 암모늄염과 이온교환수를 조합촉매로 하여 가드너 색수 1이하, 평균 분자량 분포 1 - 1.1 정도로 제조되는 에폭시 아크릴레이트혼합물(A), 분자중에 아크릴로일기(CH2= CHCO-, acryloyl functional Group)를 함유한 (메타) 아크릴레이트 모노머(B) 및, 광증감제(C)를 함유한 것을 특징으로 한다.In the ultraviolet curable resin composition of the present invention, a quaternary ammonium salt and ion-exchanged water are combined catalysts for the reaction of bisphenol A-modified epoxide and (meth) acrylic acid, and the Gardner color number is 1 or less, and the average molecular weight distribution is about 1-1.1. Epoxy acrylate mixture (A) to be produced, containing a (meth) acrylate monomer (B) containing acryloyl group (CH 2 = CHCO-, acryloyl functional group) in the molecule, and a photosensitizer (C) It features.
본 발명에서 이용되는 아크릴 레이트합성은 일반적으로 에폭시 수지와 (메타) 아크릴산을 촉매 존재하에 부가반응시켜 그 말단기에 아크릴로일기를 도입함으로 이루어진다.The acrylate synthesis used in the present invention is generally obtained by addition reaction of epoxy resin and (meth) acrylic acid in the presence of a catalyst to introduce acryloyl group at its terminal. Is done.
이때 촉매로는 암니계, 암모늄계, 할로겐화 리듐등이 사용되고, 보통 반응온도는 90 - 130℃에서 행하여 진다.Amni-based, ammonium-based, lithium halide, etc. are used as a catalyst at this time, and reaction temperature is normally performed at 90-130 degreeC.
이와 같은 방법으로 비스페놀 A 변성 에폭시화물을 이용하여 에폭시 아크릴레이트를 제조할 때 가드너색수가 높고 변색되고 평균 분자량 분포 1.1 이상되고 자외선경화형 수지조성물을 제조하여 카본화이버 낚시대에 적용할 때 접착성과 투명성이 떨어짐을 알게 되었다.In this way, when the epoxy acrylate is prepared using bisphenol A modified epoxide, the Gardner color number is high, the color is changed, and the average molecular weight distribution is 1.1 or more. UV curable resin composition was found to be inferior in adhesion and transparency when applied to carbon fiber fishing rods.
따라서, 본 발명의 에폭시 아크릴레이트혼합물의 제조방법은, 상기와 같은 문제점을 개선하기 위해 비스페놀 A 변성 에폭시 화물 대 (메타) 아크릴산의 몰비를 0.7-1.4로 하고 더욱 상세히는 0.9-1.1정도, 두물질의 합계 중량부에 대해 0.1-5%에 해당하는 중량부의 4차 암모늄염계 촉매와 이 4차 암모늄염계 촉매의 0.2 - 2배에 해당하는 이온교화수량을 넣고 불활성기체의 공급하에 반응온도 60-100℃에서 에폭시 아크릴레이트를 제조할 수 있다.Thus, the process for preparing the epoxy acrylate mixture of the present invention is to improve the above problems by using bisphenol A modified epoxy cargo versus (meth) acrylic acid. The molar ratio of 0.7-1.4 and more specifically 0.9-1.1, part by weight of the quaternary ammonium salt catalyst and 0.1-5% of the total weight of the two materials Epoxy acrylate can be prepared at a reaction temperature of 60-100 ° C. under the supply of an inert gas, with the amount of ionization water equivalent to 0.2-2 times the quaternary ammonium salt catalyst. have.
이때 반응시 중합방지를 위해 하이드로 퀴논(HQ), 톨로 하이드로 퀴논(T-HQ), 파라 벤조 퀴논(PBQ) 등을 반응화합물에 대하여 0.005 - 0.5% 에 해당하는 양을 글리콜류에 완전 용해하여 첨가하고, 반응 희석제를 10-40% 중량부를 넣는다.At this time, hydroquinone (HQ), tolo hydroquinone (T-HQ), para benzoquinone (PBQ) and the like were added to the reaction compounds to prevent polymerization. An amount equivalent to 0.5% is completely dissolved in glycols and added, and 10-40% by weight of the reaction diluent is added.
한편, 본 발명의 자외선경화형 수지조성물은 상기한 바와 같이 제조되는 에폭시 아크릴레이트 화물(A)의 30-80% 중량부에 분자중에 아클리로일기를 함유한 (메타) 아크릴레이트 모노머 (B), 예를 들면 2-하이드록시에틸(메타)아크릴레이트 (2-HE(M)A), 2-에틸헥실 (메타)아크릴레이트(2-HE(M)A), N-비닐피로디딘(NVP), 라우릴(메타)아크릴레이트(L(M)A), 폴리에틸렌 글리콜 (메타) 아크릴레이트(PEG(M)A), 트리 프로필렌 글리콜 디(메타)아크릴레이트(TPGD(M)A), 트리 메티롤프로판 트리(메타)아크릴레이트(TPGD(M)A), 1.6-헥산디올 디(메타)아크릴레이트(HDD(M)A), 스티렌등이고, 필요에 따라 1종류 또는 2종류이상을 에폭시 아크릴레이트화물(A)에 대하여 20-60% 중량부를 혼합한다.On the other hand, the ultraviolet curable resin composition of the present invention contains an acryloyl group in the molecule in 30-80% by weight of the epoxy acrylate (A) prepared as described above (Meth) acrylate monomer (B), for example 2-hydroxyethyl (meth) acrylate (2-HE (M) A), 2-ethylhexyl (Meth) acrylate (2-HE (M) A), N-vinylpyrrididine (NVP), lauryl (meth) acrylate (L (M) A), polyethylene glycol (meth) Acrylate (PEG (M) A), tripropylene glycol di (meth) acrylate (TPGD (M) A), trimetholpropane Tri (meth) acrylate (TPGD (M) A), 1.6-hexanediol di (meth) acrylate (HDD (M) A), styrene and the like, and one or two or more 20-60% by weight of the epoxy acrylate (A) is mixed.
여기에 배합한 후 저장안정성 및 컬러가 양호한 광증감제(C), 예를 들면 벤조인 에틸-에테트, 벤조인 알킬에테르, 하이드록시 사이클로 헥실 페닐케톤, 벤질 디메틸케탈, 2.2 - 디에톡시 아세토 페논등이고, 이것도 필요에 따라 1종류 또는 2종류이상을 에폭시 아클릴레이트 화물(A)와 (메타)아크릴레이트 모노머(B)의 합계에 대하여 0.5 - 10% 중량부를 혼합한다.Photosensitizers (C) having good storage stability and color after being formulated therein, such as benzoin ethyl-ether, benzoin alkyl ether, hydroxy cyclohexyl phenyl ketone, Benzyl dimethyl ketal, 2.2-diethoxy acetophenone, and the like, and one or two or more of these may be combined with epoxy acrylate (A), if necessary. 0.5-10% by weight of the total of the (meth) acrylate monomer (B) is mixed.
이렇게 조성된 자외선경화형 수지조성물은 카본화이버 낚시대에 적용될 때 도막성능을 향상시키기 위해 레벨링제, 소포제, 산화방지제등과 같은 첨가제가 더 첨가된다.The UV-curable resin composition thus prepared has additives such as leveling agents, antifoaming agents, antioxidants, etc. to improve the coating performance when applied to carbon fiber fishing rods. Is added.
이하, 본 발명의 구체적인 실시예를 들면 다음과 같다.Hereinafter, specific examples of the present invention will be described.
먼저, 본 발명의 에폭시 아크릴레이트혼합물을 제조하는 방법에 대한 실시예들은 다음과 같다.First, the embodiments of the method for producing the epoxy acrylate mixture of the present invention are as follows.
[실시예 1]Example 1
교반기, 온도조절장치, 온도계, 응축기, 불활성가스 도입라인, 적가장치를 갖춘 반응기에 비스페놀 A 변성 에폭시 화물 493.2 중량부를 넣고 교반하면서 4차 암모늄염계 촉매 3 중량부, 이온교환수 1.5 중량부와 톨로하이드로퀴논 0.3 중량부를 프로필렌 글리콜 3 중량부에 용해하여 60℃ 반응온도에서 첨가한다.493.2 parts by weight of bisphenol A modified epoxy cargo was added to a reactor equipped with a stirrer, a thermostat, a thermometer, a condenser, an inert gas introduction line, and a dropping device. 3 parts by weight of the quaternary ammonium salt catalyst, 1.5 parts by weight of ion-exchanged water, and 0.3 parts by weight of tolohydroquinone were dissolved in 3 parts by weight of propylene glycol, at a reaction temperature of 60 캜. Add.
여기에 아크릴산 180.6 중량부와 트리멜틸롤프로판 트리 아크레잇 250 중량부를 넣고 반응온도 75-80℃를 유지하면서 산가 6이하로 떨어질 때까지 반응을 시킨다.180.6 parts by weight of acrylic acid and 250 parts by weight of trimellitrol propane triacrylate are added until the acid value falls below 6 while maintaining the reaction temperature of 75-80 ° C. Let reaction.
이렇게 생성된 에폭시 아크릴레이트혼합물은 다음과 같은 물성을 갖는다.The epoxy acrylate mixture thus produced has the following physical properties.
색수(가드너) 1이하Color number (Gardner) 1 or less
산가(mg KOH/g) 3.1Acid value (mg KOH / g) 3.1
점도(25℃ PO ISE) 780Viscosity (25 ° C PO ISE) 780
평균분자량 분포도(Mw/Mn) 1.06Average Molecular Weight Distribution (Mw / Mn) 1.06
[실시예 2]Example 2
교반기, 온도조절장치, 온도계, 응축기, 불활성가스 도입라인, 적가장치를 갖춘 반응기에 비스페놀 A 변성 에폭시 화물 499.2 중량부와 4차 암모늄염계 촉매 5 중량부와 톨로하이드로 퀴논 0.4 중량부를 프로필렌 글리콜 4 중량부에 용해하여 60℃반응온도에서 첨가한다.499.2 parts by weight of bisphenol A modified epoxy cargo and quaternary ammonium salt system in reactor equipped with stirrer, temperature controller, thermometer, condenser, inert gas introduction line, and dropping device 5 parts by weight of catalyst and 0.4 parts by weight of tolohydroquinone are dissolved in 4 parts by weight of propylene glycol and added at a reaction temperature of 60 ° C.
여기에 아크릴산 170.2 중량부와 트리메틸롤프로판 트리 아크레이트 250 중량부를 넣고 반응온도 80-85℃를 유지하면서 산가 6이하로 떨어질 때까지 반응을 시킨다.170.2 parts by weight of acrylic acid and 250 parts by weight of trimethylolpropane triacrylate are added thereto until the acid value falls below 6 while maintaining the reaction temperature of 80-85 ° C. Let reaction.
이렇게 생성된 에폭시 아크릴레이트혼합물은 다음과 같은 물성을 갖는다.The epoxy acrylate mixture thus produced has the following physical properties.
색수(가드너) 1이하Color number (Gardner) 1 or less
산가(mg KOH/g) 2.5Acid value (mg KOH / g) 2.5
점도(25℃ PO ISE) 850Viscosity (25 ° C PO ISE) 850
평균분자량 분포도(Mw/Mn) 1.1Average Molecular Weight Distribution (Mw / Mn) 1.1
이어 본 발명의 에폭시 아크릴레이트를 이용한 자외선경화형 수지조성물에 대한 실시예는 다음과 같다.Next, an embodiment of the ultraviolet curing resin composition using the epoxy acrylate of the present invention is as follows.
[실시예 1]Example 1
상기 에폭시 아크릴레이트의 실시예 1에서 제조된 비스페놀 A 변성 에폭시 아크릴레이트 혼합물 74 중량부, 트리 프로필렌 글리콜 디 아크릴레이트 17 중량부, 2-에틸헥실 아크릴레이트 6 중량부, 실리콘 오일 0.5 중량부, UVICURE-204(삼정산업사의 광증감제) 4 중량부를 넣고 30-40℃에서 균일하게 혼합한다.74 parts by weight of the bisphenol A modified epoxy acrylate mixture prepared in Example 1 of the epoxy acrylate, tripropylene glycol diacrylate 17 Parts by weight, 6 parts by weight of 2-ethylhexyl acrylate, 0.5 parts by weight of silicone oil, 4 parts by weight of UVICURE-204 Mix uniformly at 30-40 ° C.
이렇게 얻어진 자외선경화형 수지조성물을 카본화이버 소재에 적용하여 자외선 경화시키면 다음과 같은 도막물성을 얻는다.The ultraviolet curable resin composition thus obtained is applied to a carbon fiber material to cure ultraviolet rays to obtain the following coating properties.
연필경도 HBPencil Hardness HB
접착력테스트(Cross Cut) 100% 접착Adhesion Test (Cross Cut) 100% Adhesion
광택(60°g loss) 95Glossiness (60 ° g loss) 95
[실시예 2]Example 2
상기 에폭시 아크릴레이트의 실시예 2에서 제조된 비스페놀 A 변성 에폭시 아크릴레이트 혼합물 70 중량부, 1.6-헥산디올 디 아크릴레이트 혼합물 10 중량부, 트리 플로필렌 글리콜 디 아크릴레이트 5 중량부, 2-에틸헥실 아크릴레이트 4 중량부, 스티렌 모노머 4 중량부, 실리콘 오일 0.5 중량부, Darocure-1173(Merck사의 광증감제) 2 중량부, lrgacure-184(CIBAGEIGY사의 광증감제) 2 중량부를 넣고 30-40℃에서 균일하게 혼합한다.70 parts by weight of the bisphenol A modified epoxy acrylate mixture prepared in Example 2 of the epoxy acrylate, 1.6-hexanediol diacrylate mixture 10 Parts by weight, 5 parts by weight of triflohylene glycol diacrylate, 4 parts by weight of 2-ethylhexyl acrylate, 4 parts by weight of styrene monomer, 0.5 parts by weight of silicone oil, 2 parts by weight of Darocure-1173 (a photosensitizer from Merck) and 2 parts by weight of lrgacure-184 (a photosensitizer from CIBAGEIGY) at 30-40 ° C Mix evenly.
이렇게 얻어진 자외선경화형 수지조성물을 카본화이버 소재에 적용하여 자외선 경화시키면 다음과 같은 도막물성을 얻는다.The ultraviolet curable resin composition thus obtained is applied to a carbon fiber material to cure ultraviolet rays to obtain the following coating properties.
연필경도 HBPencil Hardness HB
접착력테스트(Cross Cut) 100% 접착Adhesion Test (Cross Cut) 100% Adhesion
광택(60°g loss) 95Glossiness (60 ° g loss) 95
이상 설명한 바와 같이 본 발명에 의하면, 변성된 에폭시 화물을 이용하여 새로운 에폭시 아크릴레이트를 제조함으로 카본화이버 플라스틱소재의 접착 및 상도코팅용으로 사용되며 평균 분자량의 폭이 매우 적고 투명성이 우수한 새로운 에폭시 아크릴레이트의 제조방법을 제공할 수 있고, 또 상기 에폭시 아크릴레이트의 제조방법을 이용하여 접착성, 후도막성, 내열, 내약품 내습성이 양호하고 표면경도는 낮으나 내충격성이 우수한 카본화이버 낚시대에 적합한 자외선경화형 수지조성물을 제공할 수 있다.As described above, according to the present invention, by producing a new epoxy acrylate using the modified epoxy cargo, the adhesion of the carbon fiber plastic material and It is possible to provide a method for preparing a new epoxy acrylate, which is used for top coat and has a very small width of the average molecular weight and excellent transparency. It is suitable for carbon fiber fishing rod with good adhesiveness, thick film resistance, heat resistance, chemical resistance and moisture resistance, low surface hardness but excellent impact resistance by using acrylate manufacturing method. UV curable resin composition can be provided.
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| KR1019950010766A KR0160451B1 (en) | 1995-05-02 | 1995-05-02 | Process for preparing epoxy acrylate and its uv curable resin composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019950010766A KR0160451B1 (en) | 1995-05-02 | 1995-05-02 | Process for preparing epoxy acrylate and its uv curable resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR960041212A KR960041212A (en) | 1996-12-19 |
| KR0160451B1 true KR0160451B1 (en) | 1999-01-15 |
Family
ID=19413617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019950010766A KR0160451B1 (en) | 1995-05-02 | 1995-05-02 | Process for preparing epoxy acrylate and its uv curable resin composition |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR0160451B1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100669857B1 (en) * | 2005-03-08 | 2007-01-16 | 삼화페인트공업주식회사 | Thermoplastic epoxy-modified acrylic resin composition or polyester resin composition, and heating dry type clear paint composition containing the same |
| KR20210128771A (en) | 2020-04-17 | 2021-10-27 | 한국화학연구원 | Acrylate monomer having hydrophilic end group and a method for preparing the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101872224B1 (en) * | 2016-11-22 | 2018-06-28 | 애경화학 주식회사 | Non VOC urethane modified epoxy acrylate and the method of manufacturing the same |
-
1995
- 1995-05-02 KR KR1019950010766A patent/KR0160451B1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100669857B1 (en) * | 2005-03-08 | 2007-01-16 | 삼화페인트공업주식회사 | Thermoplastic epoxy-modified acrylic resin composition or polyester resin composition, and heating dry type clear paint composition containing the same |
| KR20210128771A (en) | 2020-04-17 | 2021-10-27 | 한국화학연구원 | Acrylate monomer having hydrophilic end group and a method for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR960041212A (en) | 1996-12-19 |
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