CN117987073A - UV moisture curing adhesive for electronic components and preparation method thereof - Google Patents
UV moisture curing adhesive for electronic components and preparation method thereof Download PDFInfo
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- CN117987073A CN117987073A CN202410155779.8A CN202410155779A CN117987073A CN 117987073 A CN117987073 A CN 117987073A CN 202410155779 A CN202410155779 A CN 202410155779A CN 117987073 A CN117987073 A CN 117987073A
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- moisture curing
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- 239000004839 Moisture curing adhesive Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 37
- IQJVBAIESAQUKR-UHFFFAOYSA-N isocyanic acid;prop-2-enoic acid Chemical compound N=C=O.OC(=O)C=C IQJVBAIESAQUKR-UHFFFAOYSA-N 0.000 claims abstract description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 229920002635 polyurethane Polymers 0.000 claims abstract description 24
- 239000004814 polyurethane Substances 0.000 claims abstract description 24
- 239000003381 stabilizer Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract 3
- 238000003756 stirring Methods 0.000 claims description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 229920005862 polyol Polymers 0.000 claims description 14
- 150000003077 polyols Chemical class 0.000 claims description 14
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- 239000012024 dehydrating agents Substances 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- -1 polydimethylsiloxane Polymers 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims description 9
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- VLJQDHDVZJXNQL-UHFFFAOYSA-N 4-methyl-n-(oxomethylidene)benzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)N=C=O)C=C1 VLJQDHDVZJXNQL-UHFFFAOYSA-N 0.000 claims description 5
- 239000004359 castor oil Substances 0.000 claims description 5
- 235000019438 castor oil Nutrition 0.000 claims description 5
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- RDHSUTIDSFVNJL-UHFFFAOYSA-N OC(=O)C=C.CCCCCCCCCCCC(O)=O Chemical compound OC(=O)C=C.CCCCCCCCCCCC(O)=O RDHSUTIDSFVNJL-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- YMCOIFVFCYKISC-UHFFFAOYSA-N ethoxy-[2-(2,4,6-trimethylbenzoyl)phenyl]phosphinic acid Chemical compound CCOP(O)(=O)c1ccccc1C(=O)c1c(C)cc(C)cc1C YMCOIFVFCYKISC-UHFFFAOYSA-N 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000001723 curing Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 235000004443 Ricinus communis Nutrition 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000009471 action Effects 0.000 description 5
- 230000002085 persistent effect Effects 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000013008 moisture curing Methods 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- WELLGRANCAVMDP-UHFFFAOYSA-N isocyanatoethane;prop-2-enoic acid Chemical compound CCN=C=O.OC(=O)C=C WELLGRANCAVMDP-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本申请涉及功能粘接材料领域,具体公开一种用于电子元器件的UV湿气固化胶及其制备方法。一种用于电子元器件的UV湿气固化胶由以下重量份的原料制得:聚氨酯丙烯酸酯25‑45份、异氰酸丙烯酸酯6‑15份、丙烯酸酯单体30‑50份、光引发剂3‑8份、稳定剂2‑6份、除水剂1‑2份、抗氧化剂0.1‑0.6份和催化剂0.05‑0.2份;制备方法:丙烯酸酯单体、稳定剂和抗氧化剂制得混合物A;加入聚氨酯丙烯酸酯制得混合物B;加入除水剂制得混合物C;加入异氰酸丙烯酸酯制得混合物D;加入光引发剂和催化剂制得UV湿气固化胶。本申请的制备工艺简单,制得的UV湿气固化胶的交联稳定性好,对电子元器件贴合稳定性好。The present application relates to the field of functional adhesive materials, and specifically discloses a UV moisture curing adhesive for electronic components and a preparation method thereof. A UV moisture curing adhesive for electronic components is prepared from the following raw materials in parts by weight: 25-45 parts of polyurethane acrylate, 6-15 parts of isocyanate acrylate, 30-50 parts of acrylate monomer, 3-8 parts of photoinitiator, 2-6 parts of stabilizer, 1-2 parts of dewatering agent, 0.1-0.6 parts of antioxidant and 0.05-0.2 parts of catalyst; preparation method: acrylate monomer, stabilizer and antioxidant are used to prepare mixture A; polyurethane acrylate is added to prepare mixture B; dewatering agent is added to prepare mixture C; isocyanate acrylate is added to prepare mixture D; photoinitiator and catalyst are added to prepare UV moisture curing adhesive. The preparation process of the present application is simple, and the prepared UV moisture curing adhesive has good cross-linking stability and good bonding stability to electronic components.
Description
技术领域Technical Field
本申请涉及功能粘接材料的领域,更具体地说,它涉及一种用于电子元器件的UV湿气固化胶及其制备方法。The present application relates to the field of functional adhesive materials, and more specifically, to a UV moisture curing adhesive for electronic components and a preparation method thereof.
背景技术Background technique
随着电子产品逐渐转向小型化、集成化、多功能化,电子元器件,例如显示屏、芯片等在组装过程对组装的精度和轻薄化程度的要求越来越高,对组装后的电子产品的安全性能及稳定性的要求也越来越高。As electronic products gradually move towards miniaturization, integration and multi-functions, the requirements for assembly precision and thinness of electronic components, such as display screens and chips, are becoming increasingly higher during the assembly process, and the requirements for the safety performance and stability of the assembled electronic products are also becoming increasingly higher.
由于UV湿气固化胶具有粘接稳定性好,可以在室温下快速固化,同时也可以在潮湿的环境中进行稳定固化,对使用场所的条件要求不苛刻,具有较好的使用便捷性,因此,目前在电子元器件的组装、贴合和防护中,一般会使用UV湿气固化胶。Because UV moisture curing adhesive has good bonding stability, can be quickly cured at room temperature, and can also be stably cured in a humid environment, it is not demanding on the conditions of the use site and has good convenience of use. Therefore, UV moisture curing adhesive is generally used in the assembly, bonding and protection of electronic components.
UV湿气固化胶一般由湿气固化聚氨酯树脂、反应单体、光引发剂剂和其他助剂,例如抗氧化剂等组成,通过光引发剂引发反应单体与聚氨酯树脂进行聚合,从而制得UV湿气固化胶,这种UV湿气固化胶虽然具有较好的固化性能和初粘性能,但是当电子产品在长期使用时,电子元器件长期处于运行的状态,轻薄化的UV湿气固化胶膜层会出现持粘性降低的问题,使得对电子元器件的贴合稳定性和防护性降低,进而降低电子产品的使用寿命。UV moisture curing adhesive is generally composed of moisture curing polyurethane resin, reactive monomers, photoinitiators and other additives, such as antioxidants. The reactive monomers and polyurethane resin are polymerized by the photoinitiator to obtain UV moisture curing adhesive. Although this UV moisture curing adhesive has good curing performance and initial adhesion performance, when electronic products are used for a long time, the electronic components are in operation for a long time, and the thin UV moisture curing adhesive film layer will have the problem of reduced adhesion, which reduces the bonding stability and protection of electronic components, thereby reducing the service life of electronic products.
发明内容Summary of the invention
为了解决目前的UV湿气固化胶应用于电子元器件中,长期使用会出现持粘性降低的问题,对电子元器件的贴合稳定性和防护性降低,降低了电子产品的使用寿命,本申请提供一种用于电子元器件的UV湿气固化胶及其制备方法。In order to solve the problem that the current UV moisture curing adhesive is used in electronic components, the long-term use will reduce the adhesion, reduce the bonding stability and protection of electronic components, and shorten the service life of electronic products, the present application provides a UV moisture curing adhesive for electronic components and a preparation method thereof.
第一方面,本申请提供一种一种用于电子元器件的UV湿气固化胶,采用如下的技术方案:In a first aspect, the present application provides a UV moisture curing adhesive for electronic components, which adopts the following technical solution:
一种用于电子元器件的UV湿气固化胶,由以下重量份的原料制得:A UV moisture curing adhesive for electronic components is prepared from the following raw materials in parts by weight:
通过采用上述技术方案,本申请制得的UV湿气固化胶适用于轻薄型的电子产品中,可以在紫外线和常温条件下进行固化,固化形成的UV湿气固化胶膜具有较为适中的初粘性和较好的持粘性,贴合的电子元器件长期使用不易出现贴合不稳定的情况,提升电子产品的使用寿命。By adopting the above technical scheme, the UV moisture curing adhesive prepared in the present application is suitable for thin and light electronic products, and can be cured under ultraviolet light and room temperature conditions. The UV moisture curing adhesive film formed by curing has a relatively moderate initial adhesion and good lasting adhesion. The bonded electronic components are not prone to unstable bonding during long-term use, thereby improving the service life of electronic products.
聚氨酯丙烯酸酯的分子中含有丙烯酸官能团和氨基甲酸酯键,固化制得的UV湿气固化胶固化后具有聚氨酯的高耐磨性、粘附力、柔韧性、高剥离强度和优良的耐低温性能,同时还具有聚丙烯酸酯的光学性能和耐候性,向UV湿气固化胶中引入聚氨酯丙烯酸酯,能够在光引发剂的作用下,与丙烯酸酯单体进行聚合,制备得到粘接性好的UV湿气固化胶,同时向体系中加入异氰酸丙烯酸酯,异氰酸丙烯酸酯是一种含有异氰酸活性基团的丙烯酸酯,能够与聚氨酯丙烯酸酯产生较好的协同作用,在稳定剂和催化剂的作用下,制得的UV湿气固化胶吸收空气中的水分进行常温交联固化,具有较好的固化稳定性,稳定剂能够进一步提升异氰酸丙烯酸酯和聚氨酯丙烯酸酯的复配稳定性,以此制得的UV湿气固化胶具有较好的光固化性和湿气固化性,固化后形成的UV湿气固化胶膜的持粘性较好,对电子元器件的贴合稳定性较好,除水剂具有较好的键合水分子的作用,提升制得的UV湿气固化胶的稳定性,抗氧化剂可以提升制得的UV湿气固化胶的耐老化性,提升使用寿命。The molecules of polyurethane acrylate contain acrylic functional groups and urethane bonds. The UV moisture curing adhesive obtained by curing has the high wear resistance, adhesion, flexibility, high peel strength and excellent low temperature resistance of polyurethane after curing. It also has the optical properties and weather resistance of polyacrylate. The introduction of polyurethane acrylate into the UV moisture curing adhesive can polymerize with the acrylate monomer under the action of the photoinitiator to prepare a UV moisture curing adhesive with good adhesion. At the same time, isocyanate acrylate is added to the system. Isocyanate acrylate is an acrylate containing isocyanate active groups, which can produce good synergy with polyurethane acrylate. Under the action of stabilizer and catalyst, the prepared UV moisture curing adhesive absorbs moisture in the air to cross-link and cure at room temperature, and has good curing stability. The stabilizer can further improve the compounding stability of isocyanate acrylate and polyurethane acrylate. The prepared UV moisture curing adhesive has good light curing and moisture curing properties. The UV moisture curing adhesive film formed after curing has good adhesion and good bonding stability to electronic components. The dehydrating agent has a good effect of bonding water molecules, thereby improving the stability of the prepared UV moisture curing adhesive. The antioxidant can improve the aging resistance of the prepared UV moisture curing adhesive and improve the service life.
优选的,所述异氰酸丙烯酸酯由以下重量份的原料制得:Preferably, the isocyanate acrylate is prepared from the following raw materials in parts by weight:
二异氰酸酯 25-35份Diisocyanate 25-35 parts
羟基丙烯酸酯 10-20份Hydroxyacrylate 10-20 parts
蓖麻油改性多元醇 2-4份Castor oil modified polyol 2-4 parts
聚乙二醇二缩水甘油醚 0.5-2份Polyethylene glycol diglycidyl ether 0.5-2 parts
催化剂 0.05-0.15份Catalyst 0.05-0.15 parts
阻聚剂 0.02-0.08份。Inhibitor 0.02-0.08 parts.
优选的,所述异氰酸酯为六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、4,4-二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯和四甲基间苯二亚甲基二异氰酸酯中的一种或多种。Preferably, the isocyanate is one or more of hexamethylene diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, xylylene diisocyanate and tetramethyl-meta-xylylene diisocyanate.
优选的,所述羟基丙烯酸酯为丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯或甲基丙烯酸羟丙酯中的任意一种或几种。Preferably, the hydroxyacrylate is any one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate.
优选的,所述异氰酸丙烯酸酯制备过程中使用的催化剂为有机锡催化剂,所述阻聚剂为对苯二酚、对羟基苯甲醚中的任意一种。Preferably, the catalyst used in the preparation process of the isocyanate acrylate is an organic tin catalyst, and the inhibitor is any one of hydroquinone and p-hydroxyanisole.
通过采用上述技术方案,为了进一步提升制得的UV湿气固化胶的持粘性,本申请通过使用二异氰酸酯提供异氰酸活性基团,羟基丙烯酸酯提供活性羟基,在催化剂的作用下进行反应,制备得到含有异氰酸酯基团的丙烯酸酯,在反应的过程中,向体系中加入蓖麻油改性多元醇和聚乙二醇二缩水甘油醚,蓖麻油改性多元醇具有柔韧性好的分子链段和活性反应羟基,而聚乙二醇二缩水甘油醚具有可挠性的柔软醚基链段,蓖麻油改性多元醇和聚乙二醇二缩水甘油醚产生较好的协同作用,能够进一步与二异氰酸酯进行交联,制得的异氰酸丙烯酸酯具有网状交织的分子结构,以此制得的异氰酸丙烯酸酯制得的UV湿气固化胶具有较好的持粘性,贴合稳定性好,阻聚剂具有较好的控制反应,同时提升制得的异氰酸丙烯酸酯的储存稳定性。By adopting the above technical scheme, in order to further improve the stickiness of the prepared UV moisture curing adhesive, the present application uses diisocyanate to provide isocyanate active groups and hydroxy acrylate to provide active hydroxyl groups, and reacts under the action of a catalyst to prepare an acrylate containing an isocyanate group. During the reaction, castor oil-modified polyol and polyethylene glycol diglycidyl ether are added to the system. The castor oil-modified polyol has a flexible molecular chain segment and active reactive hydroxyl groups, and the polyethylene glycol diglycidyl ether has a flexible soft ether group segment. The castor oil-modified polyol and the polyethylene glycol diglycidyl ether produce a good synergistic effect and can be further cross-linked with the diisocyanate. The prepared isocyanate acrylate has a network-interwoven molecular structure. The UV moisture curing adhesive prepared from the isocyanate acrylate has good stickiness and good lamination stability. The inhibitor has good control over the reaction, and the storage stability of the prepared isocyanate acrylate is improved.
优选的,所述异氰酸丙烯酸酯由以下步骤制得:将二异氰酸酯、羟基丙烯酸酯、蓖麻油改性多元醇和聚乙二醇二缩水甘油醚加入至反应设备中,搅拌均匀后加入催化剂和阻聚剂,在温度为70-80℃、真空度为-0.8MPa--1.0MPa的条件下反应2-3h,制得异氰酸丙烯酸酯。Preferably, the isocyanate acrylate is prepared by the following steps: adding diisocyanate, hydroxy acrylate, castor oil modified polyol and polyethylene glycol diglycidyl ether to a reaction device, stirring evenly, adding a catalyst and an inhibitor, and reacting for 2-3 hours at a temperature of 70-80°C and a vacuum degree of -0.8MPa--1.0MPa to obtain isocyanate acrylate.
通过采用上述技术方案,在较优的反应条件下,制备得到性能稳定的具有异氰酸活性基团的异氰酸丙烯酸酯。By adopting the above technical scheme, isocyanate acrylate with isocyanate active groups having stable performance is prepared under better reaction conditions.
优选的,所述丙烯酸酯单体由重量比为(1.5-2):(0.8-1.2):(0.3-0.6)的丙烯酸异冰片酯、月桂酸丙烯酸酯和环三羟甲基丙烷甲缩醛丙烯酸酯组成。Preferably, the acrylate monomers are composed of isobornyl acrylate, lauric acid acrylate and cyclotrimethylolpropane formal acrylate in a weight ratio of (1.5-2):(0.8-1.2):(0.3-0.6).
通过采用上述技术方案,采用上述丙烯酸酯单体进行聚合,制得的UV湿气固化胶在具有适中的硬度的同时,还具有较好的柔韧性和粘接稳定性。By adopting the above technical solution and polymerizing the above acrylate monomer, the prepared UV moisture curing adhesive has moderate hardness as well as good flexibility and bonding stability.
优选的,所述稳定剂由重量比为重量比为(0.2-0.5):1的羟基聚醚改性聚二甲基硅氧烷和γ-甲基丙烯酰氧基丙基三甲氧基硅烷组成。Preferably, the stabilizer is composed of hydroxy polyether modified polydimethylsiloxane and γ-methacryloxypropyltrimethoxysilane in a weight ratio of (0.2-0.5):1.
通过采用上述技术方案,羟基聚醚改性聚二甲基硅氧烷是以硅氧烷为主体的并含有聚醚链段和羟基活性基团的的柔软有机硅结构,γ-甲基丙烯酰氧基丙基三甲氧基硅烷为含有有机官能团的硅烷偶联剂,以较优比例的羟基聚醚改性聚二甲基硅氧烷和γ-甲基丙烯酰氧基丙基三甲氧基硅烷进行复配,作为稳定剂,能够较好的提升各个组分在体系中的分散稳定性,与聚氨酯丙烯酸酯和异氰酸丙烯酸酯体系产生较好的协同作用,以此制得的UV湿气固化胶具有较好的固化交联稳定性和耐温稳定性,进而提升固化后形成的UV湿气固化胶膜对电子元器件的持粘性。By adopting the above technical scheme, the hydroxyl polyether modified polydimethylsiloxane is a soft silicone structure with siloxane as the main body and containing polyether segments and hydroxyl active groups, and γ-methacryloxypropyltrimethoxysilane is a silane coupling agent containing organic functional groups. The hydroxyl polyether modified polydimethylsiloxane and γ-methacryloxypropyltrimethoxysilane are compounded in a preferred ratio. As a stabilizer, the dispersion stability of each component in the system can be improved, and a good synergistic effect can be produced with the polyurethane acrylate and isocyanate acrylate system. The UV moisture-curing adhesive prepared in this way has good curing cross-linking stability and temperature resistance stability, thereby improving the adhesion of the UV moisture-curing adhesive film formed after curing to electronic components.
优选的,所述除水剂由重量比为1:(0.1-0.3)的对甲苯磺酰异氰酸酯和乙烯基三甲氧基硅烷组成。Preferably, the dehydrating agent is composed of p-toluenesulfonyl isocyanate and vinyl trimethoxy silane in a weight ratio of 1:(0.1-0.3).
通过采用上述技术方案,较优比例的对甲苯磺酰异氰酸酯和乙烯基三甲氧基硅烷与水反应的活性较高,可以快速地消耗掉体系中的水分,进而提升制得的UV湿气固化胶的储存稳定性。By adopting the above technical solution, the optimal ratio of p-toluenesulfonyl isocyanate and vinyl trimethoxysilane has a higher activity in reacting with water, which can quickly consume the moisture in the system, thereby improving the storage stability of the prepared UV moisture curing adhesive.
优选的,所述光引发剂为2-羟基-2-甲基苯丙酮、1-羟基环己基苯基甲酮、2,4,6-三甲基苯甲酰基苯基膦酸乙酯中的任意一种或组合。Preferably, the photoinitiator is any one or a combination of 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, and ethyl 2,4,6-trimethylbenzoylphenylphosphonate.
通过采用上述技术方案,上述光引发剂具有较好的光引发效率,使得制得的UV湿气固化胶能够稳定地进行交联固化。By adopting the above technical solution, the above photoinitiator has good photoinitiating efficiency, so that the prepared UV moisture curing adhesive can stably perform cross-linking and curing.
优选的,所述抗氧化剂为亚磷酸三(2,4-二叔丁基苯基)酯、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯中的任意一种或组合。Preferably, the antioxidant is any one or a combination of tris(2,4-di-tert-butylphenyl)phosphite and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.
通过采用上述技术方案,上述抗氧化剂具有较好的抗氧化性能,能够提升固化形成的UV湿气固化胶膜的奶老化性能,提升使用寿命。By adopting the above technical solution, the above antioxidant has good antioxidant performance, can improve the milk aging performance of the UV moisture-cured adhesive film formed by curing, and improve the service life.
第二方面,本申请提供一种用于电子元器件的UV湿气固化胶的制备方法,采用如下的技术方案:In a second aspect, the present application provides a method for preparing a UV moisture curing adhesive for electronic components, using the following technical solution:
一种用于电子元器件的UV湿气固化胶的制备方法,包括以下步骤:A method for preparing a UV moisture curing adhesive for electronic components comprises the following steps:
S1、将丙烯酸酯单体、稳定剂和抗氧化剂加入至反应设备中,进行真空搅拌,制得混合物A;S1, adding acrylate monomer, stabilizer and antioxidant into a reaction device, and performing vacuum stirring to obtain a mixture A;
S2、向混合物A中加入聚氨酯丙烯酸酯,真空搅拌,制得混合物B;S2, adding polyurethane acrylate to mixture A, stirring under vacuum, to obtain mixture B;
S3、向混合物B中加入除水剂,真空搅拌,制得混合物C;S3, adding a dehydrating agent to the mixture B, stirring under vacuum, to obtain a mixture C;
S4、向混合物C中加入异氰酸丙烯酸酯,真空搅拌,制得混合物D;S4, adding isocyanate acrylate to mixture C, stirring under vacuum, to obtain mixture D;
S5、向混合物D中加入光引发剂和催化剂,真空搅拌,制得UV湿气固化胶。S5. Add a photoinitiator and a catalyst to the mixture D, stir under vacuum, and prepare a UV moisture curing adhesive.
通过采用上述技术方案,在全程真空搅拌的条件下,先将丙烯酸酯单体、稳定剂和抗氧化剂混合,后加入聚氨酯丙烯酸酯混合,再加入除水剂,去除多余的水分,再加入异氰酸丙烯酸酯,使得异氰酸丙烯酸酯不易与体系中的水分进行反应,提升生产的稳定性,最后加入光引发剂和催化剂,以此制得体系稳定且储存稳定的UV湿气固化胶。By adopting the above technical scheme, under the condition of vacuum stirring throughout the process, the acrylate monomer, stabilizer and antioxidant are first mixed, then polyurethane acrylate is added and mixed, and then a desiccant is added to remove excess water, and then isocyanate acrylate is added to make it difficult for isocyanate acrylate to react with water in the system, thereby improving the stability of production, and finally a photoinitiator and a catalyst are added to obtain a UV moisture-curing adhesive with a stable system and storage stability.
优选的,所述S1-S4步骤中,真空搅拌的真空度均为-0.8MPa--1.0MPa,所述S3步骤中,加入除水剂后,搅拌时间为1.5-2.5h,搅拌并控制水分含量小于500ppm。Preferably, in the steps S1-S4, the vacuum degree of vacuum stirring is -0.8MPa--1.0MPa, and in the step S3, after adding the dehydrating agent, the stirring time is 1.5-2.5h, and the moisture content is stirred and controlled to be less than 500ppm.
通过采用上述技术方案,真空搅拌可以提升原料之间的混合均匀性,同时减少水分杂质的引入,加入除水剂,控制较优的搅拌时间,进行充分搅拌,将水分含量降低至500ppm以下,是为了防止后加入的异氰酸丙烯酸酯与水分进行反应,提升UV湿气固化胶的稳定性。By adopting the above technical solution, vacuum stirring can improve the mixing uniformity between the raw materials, while reducing the introduction of water impurities. Adding a dehydrating agent, controlling the optimal stirring time, and fully stirring to reduce the moisture content to below 500ppm is to prevent the later added isocyanate acrylate from reacting with moisture and improve the stability of the UV moisture curing adhesive.
综上所述,本申请具有以下有益效果:In summary, this application has the following beneficial effects:
1、本申请的用于电子元器件的UV湿气固化胶,通过使用以聚氨酯丙烯酸酯和异氰酸丙烯酸酯作为主体,在催化剂、光引发剂、稳定剂和丙烯酸单体的作用下,制得的UV湿气固化胶能够在紫外线和常温条件下稳定地进行交联固化,可应用于轻薄型的电子产品中,固化后形成的UV湿气固化胶膜具有较为适中的初粘性,对电子元器件的持粘性好,长期使用不易出现粘接不稳的情况,提升了电子产品的使用寿命。1. The UV moisture curing adhesive for electronic components of the present application uses polyurethane acrylate and isocyanate acrylate as the main body. Under the action of catalyst, photoinitiator, stabilizer and acrylic monomer, the prepared UV moisture curing adhesive can stably cross-link and cure under ultraviolet light and room temperature conditions, and can be applied to light and thin electronic products. The UV moisture curing adhesive film formed after curing has a relatively moderate initial viscosity, good adhesion to electronic components, and is not prone to unstable bonding during long-term use, thereby improving the service life of electronic products.
2、通过在催化剂和阻聚剂的作用下,向二异氰酸酯和羟基丙烯酸酯的反应体系中加入蓖麻油改性多元醇和聚乙二醇二缩水甘油醚,蓖麻油改性多元醇和聚乙二醇二缩水甘油醚产生较好的协同作用,能够进一步与二异氰酸酯进行交联,制得的异氰酸丙烯酸酯具有网状交织的分子结构,以此制得的异氰酸丙烯酸酯制得的UV湿气固化胶具有较好的持粘性,贴合稳定性好。2. By adding castor oil-modified polyol and polyethylene glycol diglycidyl ether to the reaction system of diisocyanate and hydroxy acrylate under the action of a catalyst and an inhibitor, castor oil-modified polyol and polyethylene glycol diglycidyl ether produce a good synergistic effect and can be further cross-linked with diisocyanate. The obtained isocyanate acrylate has a network-like interwoven molecular structure. The UV moisture-curing adhesive prepared from the isocyanate acrylate has good tack retention and good bonding stability.
3、通过使用较优比例的羟基聚醚改性聚二甲基硅氧烷和γ-甲基丙烯酰氧基丙基三甲氧基硅烷作为稳定剂,能够与聚氨酯丙烯酸酯、异氰酸丙烯酸酯产生较好的协同作用,能够较好的提升各个组分在体系中的分散稳定性,以此制得的UV湿气固化胶具有较好的固化交联稳定性和耐温稳定性,进而提升固化后形成的UV湿气固化胶膜对电子元器件的持粘性。3. By using a better ratio of hydroxy polyether modified polydimethylsiloxane and γ-methacryloxypropyltrimethoxysilane as stabilizers, it can produce a better synergistic effect with polyurethane acrylate and isocyanate acrylate, and can better improve the dispersion stability of each component in the system. The UV moisture curing adhesive prepared in this way has better curing cross-linking stability and temperature resistance stability, thereby improving the adhesion of the UV moisture curing adhesive film formed after curing to electronic components.
4、本申请的制备工艺,通过先将稳定剂、丙烯酸酯单体、抗氧化剂和聚氨酯丙烯酸酯混合均匀,后加入除水剂充分搅拌,去除多余的水分,再加入异氰酸丙烯酸酯、光引发剂和催化剂进行混合,以此制得的UV湿气固化胶具有较好的稳定性。4. The preparation process of the present application is to first mix the stabilizer, acrylate monomer, antioxidant and polyurethane acrylate evenly, then add the desiccant and stir thoroughly to remove excess water, and then add isocyanate acrylate, photoinitiator and catalyst to mix. The UV moisture curing adhesive prepared in this way has good stability.
具体实施方式Detailed ways
以下结合实施例对本申请作进一步详细说明。The present application is further described in detail below with reference to the embodiments.
异氰酸丙烯酸酯的制备例Preparation Example of Isocyanate Acrylate
制备例1Preparation Example 1
制备例1公开一种异氰酸丙烯酸酯,由以下步骤制得:Preparation Example 1 discloses an isocyanate acrylate, which is prepared by the following steps:
将2.5kg六亚甲基二异氰酸酯作为二异氰酸酯、1kg丙烯酸羟乙酯作为羟基丙烯酸酯、0.2kg蓖麻油改性多元醇和0.05kg聚乙二醇二缩水甘油醚加入至反应釜中,在搅拌速率为300r/min的条件下搅拌20min,搅拌均匀后加入5g辛酸亚锡作为催化剂和2g对羟基苯甲醚作为阻聚剂,在温度为70-80℃、真空度为-0.8MPa--1.0MPa的条件下反应2-3h,制得异氰酸丙烯酸酯;2.5 kg of hexamethylene diisocyanate as diisocyanate, 1 kg of hydroxyethyl acrylate as hydroxy acrylate, 0.2 kg of castor oil-modified polyol and 0.05 kg of polyethylene glycol diglycidyl ether were added to a reactor, stirred at a stirring rate of 300 r/min for 20 min, and after stirring evenly, 5 g of stannous octoate as a catalyst and 2 g of p-hydroxyanisole as a polymerization inhibitor were added, and the mixture was reacted for 2-3 h at a temperature of 70-80° C. and a vacuum degree of -0.8 MPa--1.0 MPa to obtain isocyanate acrylate;
蓖麻油改性多元醇为鞍山创业生物新材料科技有限公司生产,型号CY-009,羟值215-235mgKOH/g,粘度1200-1900mPa.s/20℃,官能团数2.5;聚乙二醇二缩水甘油醚:含量99%,CAS号39443-66-8,密度1.14g/ml,25℃,环氧值0.35-0.40eq/100g。Castor oil modified polyol is produced by Anshan Chuangye Bio-New Material Technology Co., Ltd., model CY-009, hydroxyl value 215-235 mgKOH/g, viscosity 1200-1900 mPa.s/20°C, functional group number 2.5; polyethylene glycol diglycidyl ether: content 99%, CAS number 39443-66-8, density 1.14 g/ml, 25°C, epoxy value 0.35-0.40 eq/100g.
制备例2-3Preparation Example 2-3
制备例2-3与制备例1的区别在于,原料用量和制备条件不同,具体参见下表1。The difference between Preparation Example 2-3 and Preparation Example 1 is that the amount of raw materials used and the preparation conditions are different, see Table 1 below for details.
表1制备例1-3的原料用量和制备条件表Table 1 Raw material dosage and preparation conditions of Preparation Examples 1-3
制备对比例1Preparation Comparative Example 1
制备对比例1与制备例3的区别在于,将聚乙二醇二缩水甘油醚等量替换为蓖麻油改性多元醇,其他与制备对比例1相同。The difference between Preparation Example 1 and Preparation Example 3 is that an equal amount of polyethylene glycol diglycidyl ether is replaced by castor oil-modified polyol, and the rest is the same as Preparation Example 1.
制备对比例2Preparation Comparative Example 2
制备对比例2与制备例3的区别在于,将蓖麻油改性多元醇等量替换为1,4-丁二醇,其他与制备例3相同。The difference between Preparation Comparative Example 2 and Preparation Example 3 is that the castor oil-modified polyol is replaced with an equal amount of 1,4-butanediol, and the rest is the same as Preparation Example 3.
制备对比例3Preparation Comparative Example 3
制备对比例3与制备例3的区别在于,将蓖麻油改性多元醇和聚乙二醇二缩水甘油醚均等量替换为丙烯酸羟乙酯,其他与制备例3相同。The difference between Preparation Comparative Example 3 and Preparation Example 3 is that castor oil-modified polyol and polyethylene glycol diglycidyl ether are replaced by hydroxyethyl acrylate in equal amounts, and the rest is the same as Preparation Example 3.
实施例Example
实施例1Example 1
实施例1公开一种用于电子元器件的UV湿气固化胶,由以下步骤制得:Example 1 discloses a UV moisture curing adhesive for electronic components, which is prepared by the following steps:
S1、将由1.731kg丙烯酸异冰片酯、0.923kg月桂酸丙烯酸酯和0.346kg环三羟甲基丙烷甲缩醛丙烯酸酯组成的丙烯酸酯单体、0.2kgγ-甲基丙烯酰氧基丙基三甲氧基硅烷作为稳定剂和0.01kg四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯作为抗氧化剂加入至反应釜中,在真空度为-0.8MPa的条件下搅拌20min,制得混合物A;S1, adding 1.731kg of isobornyl acrylate, 0.923kg of lauric acid acrylate and 0.346kg of cyclotrimethylolpropane formal acrylate as an acrylate monomer, 0.2kg of γ-methacryloxypropyltrimethoxysilane as a stabilizer and 0.01kg of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate as an antioxidant into a reactor, stirring for 20min under a vacuum degree of -0.8MPa to obtain a mixture A;
S2、向混合物A中加入2.5kg聚氨酯丙烯酸酯,在真空度为-0.8MPa的条件下搅拌20min,制得混合物B;S2, adding 2.5 kg of polyurethane acrylate to mixture A, stirring for 20 min under a vacuum degree of -0.8 MPa to obtain mixture B;
S3、向混合物B中加入0.1kg对甲苯磺酰异氰酸酯作为除水剂,在真空度为-0.8MPa的条件下搅拌1.5h,搅拌至水分含量为450ppm时,停止搅拌,制得混合物C;S3, adding 0.1 kg of p-toluenesulfonyl isocyanate as a dehydrating agent to the mixture B, stirring for 1.5 h under a vacuum degree of -0.8 MPa, stirring until the water content is 450 ppm, stopping stirring, and obtaining a mixture C;
S4、向混合物C中加入0.6kg市售的异氰酸丙烯酸酯,在真空度为-0.8MPa的条件下搅拌20min,制得混合物D;S4, adding 0.6 kg of commercially available isocyanate acrylate to the mixture C, stirring for 20 min under a vacuum degree of -0.8 MPa to obtain a mixture D;
S5、向混合物D中加入由0.2kg 2-羟基-2-甲基苯丙酮和0.1kg 2,4,6-三甲基苯甲酰基苯基膦酸乙酯组成的光引发剂和0.005kg WCAT-WS2催化剂,在真空度为-0.8MPa的条件下搅拌10min,制得UV湿气固化胶;S5, adding a photoinitiator consisting of 0.2 kg 2-hydroxy-2-methylpropiophenone and 0.1 kg ethyl 2,4,6-trimethylbenzoylphenylphosphonate and 0.005 kg WCAT-WS2 catalyst to the mixture D, stirring for 10 min under a vacuum degree of -0.8 MPa to obtain a UV moisture curing adhesive;
实施例1中的聚氨酯丙烯酸酯来源于上海荟研新材料有限公司HY-7902,2官能团,密度(g/cm3,25℃):1.1±0.1;催化剂WCAT-WS2来源于广州优润合成材料有限公司;异氰酸丙烯酸酯来源于克米克,异氰酸丙烯酸乙酯,CAS号13641-96-8,含量98%。The polyurethane acrylate in Example 1 is derived from Shanghai Huiyan New Materials Co., Ltd. HY-7902, 2 functional groups, density (g/cm3, 25°C): 1.1±0.1; the catalyst WCAT-WS2 is derived from Guangzhou Yourun Synthetic Materials Co., Ltd.; the isocyanate acrylate is derived from Kmik, ethyl isocyanate acrylate, CAS No. 13641-96-8, content 98%.
实施例2-3Example 2-3
实施例2-3与实施例1的区别在于,原料用量和制备条件不同,具体参见下表2。The difference between Example 2-3 and Example 1 is that the amount of raw materials used and the preparation conditions are different, see Table 2 below for details.
表2实施例1-3的原料用量和制备条件表Table 2 Raw material dosage and preparation conditions of Examples 1-3
实施例4-9Embodiment 4-9
实施例4-9与实施例3的区别在于,异氰酸丙烯酸酯的来源不同,具体参见下表3。The difference between Examples 4-9 and Example 3 is that the sources of isocyanate acrylate are different, see Table 3 below for details.
表3实施例4-9的异氰酸丙烯酸酯的来源表Table 3 Sources of isocyanate acrylates in Examples 4-9
实施例10Example 10
实施例10与实施例6的区别在于,稳定剂不同,实施例6中的稳定剂由重量比为0.2:1的羟基聚醚改性聚二甲基硅氧烷和γ-甲基丙烯酰氧基丙基三甲氧基硅烷组成,其他与实施例6相同;羟基聚醚改性聚二甲基硅氧烷来源于克拉玛尔8530H,羟基含量1.5%,粘度1000-5000,25℃/cps。The difference between Example 10 and Example 6 is that the stabilizer is different. The stabilizer in Example 6 is composed of hydroxyl polyether modified polydimethylsiloxane and γ-methacryloxypropyltrimethoxysilane in a weight ratio of 0.2:1, and the rest is the same as Example 6; the hydroxyl polyether modified polydimethylsiloxane is derived from Kramar 8530H, with a hydroxyl content of 1.5%, a viscosity of 1000-5000, and 25°C/cps.
实施例11Embodiment 11
实施例11与实施例10的区别在于,实施例11中的稳定剂由重量比为0.5:1的羟基聚醚改性聚二甲基硅氧烷和γ-甲基丙烯酰氧基丙基三甲氧基硅烷组成,其他与实施例11相同。The difference between Example 11 and Example 10 is that the stabilizer in Example 11 is composed of hydroxy polyether modified polydimethylsiloxane and γ-methacryloxypropyltrimethoxysilane in a weight ratio of 0.5:1, and the rest is the same as Example 11.
实施例12Example 12
实施例12与实施例11的区别在于,除水剂不同,实施例12中的除水剂由重量比为1:0.3的对甲苯磺酰异氰酸酯和乙烯基三甲氧基硅烷组成,其他与实施例11相同。The difference between Example 12 and Example 11 is that the dehydrating agent is different. The dehydrating agent in Example 12 is composed of p-toluenesulfonyl isocyanate and vinyltrimethoxysilane in a weight ratio of 1:0.3, and the rest is the same as Example 11.
对比例Comparative Example
对比例1Comparative Example 1
对比例1与实施例1的区别在于,将聚氨酯丙烯酸酯等量替换为异氰酸丙烯酸酯,其他与实施例1相同。The difference between Comparative Example 1 and Example 1 is that an equal amount of polyurethane acrylate is replaced by isocyanate acrylate, and the rest is the same as Example 1.
对比例2Comparative Example 2
对比例2与实施例1的区别在于,将聚氨酯丙烯酸酯和异氰酸丙烯酸酯均等量替换为双重固化聚氨酯丙烯酸酯,来源于湛新EBECRYL 4397,粘度11000S,含量99%,其他与实施例1相同。The difference between Comparative Example 2 and Example 1 is that polyurethane acrylate and isocyanate acrylate are replaced by dual-curing polyurethane acrylate from Allnex EBECRYL 4397, with a viscosity of 11000S and a content of 99%. The rest is the same as Example 1.
对比例3Comparative Example 3
对比例3与实施例1的区别在于,将稳定剂等量替换为异氰酸丙烯酸酯,其他与实施例1相同。The difference between Comparative Example 3 and Example 1 is that the stabilizer is replaced by isocyanate acrylate in equal amount, and the rest is the same as Example 1.
性能检测试验Performance testing
以下对实施例1-12和对比例1-3中制得的用于电子元器件的UV湿气固化胶进行性能测试:(1)拉伸剪切强度测试The following performance tests were conducted on the UV moisture curing adhesives for electronic components prepared in Examples 1-12 and Comparative Examples 1-3: (1) Tensile shear strength test
参照GB/T 7124-2008《胶粘剂拉伸剪切强度的测定》中的测试方法,控制UV湿气固化胶的涂覆厚度为20±0.1μm,将涂覆有UV湿气固化胶的试板放置于紫外箱中进行固化,所用的光源为365nm的紫外光,固化能量为1500mj/cm2,固化时间为5s,后放置于温度为25℃、湿度为45%的恒温恒湿箱中,固化6h,后恢复至室温(25℃),使用拉力试验机进行测试,测试并记录拉伸剪切强度(单位:MPa),记为第一拉伸剪切强度;Referring to the test method in GB/T 7124-2008 "Determination of tensile shear strength of adhesives", the coating thickness of UV moisture curing adhesive was controlled to be 20±0.1μm, and the test plate coated with UV moisture curing adhesive was placed in a UV box for curing. The light source used was 365nm ultraviolet light, the curing energy was 1500mj/ cm2 , and the curing time was 5s. Then, it was placed in a constant temperature and humidity box at a temperature of 25℃ and a humidity of 45% for curing for 6h, and then returned to room temperature (25℃). The tensile testing machine was used for testing, and the tensile shear strength (unit: MPa) was tested and recorded, which was recorded as the first tensile shear strength;
(2)持粘性测试(2) Adhesion test
将参照GB/T 7124-2008《胶粘剂拉伸剪切强度的测定》中的测试方法,控制UV湿气固化胶的涂覆厚度为20±0.1μm,将涂覆有UV湿气固化胶的试板放置于紫外箱中进行固化,所用的光源为365nm的紫外光,固化能量为1500mj/cm3,固化时间为5s,后放置于温度为25℃、湿度为45%的恒温恒湿箱中,固化3h,后恢复至室温(25℃),放置于温度为75℃、湿度为50%的恒温恒湿箱中,测试7天,后恢复至室温(25℃),测试并记录拉伸剪切强度(单位:MPa),记为第二拉伸剪切强度。Referring to the test method in GB/T 7124-2008 "Determination of tensile shear strength of adhesives", the coating thickness of UV moisture curing adhesive was controlled to be 20±0.1μm, and the test plate coated with UV moisture curing adhesive was placed in a UV box for curing. The light source used was 365nm ultraviolet light, the curing energy was 1500mj/ cm3 , and the curing time was 5s. Then, it was placed in a constant temperature and humidity box at a temperature of 25℃ and a humidity of 45% for curing for 3h, and then returned to room temperature (25℃). It was placed in a constant temperature and humidity box at a temperature of 75℃ and a humidity of 50% for testing for 7 days, and then returned to room temperature (25℃). The tensile shear strength (unit: MPa) was tested and recorded, which was recorded as the second tensile shear strength.
以下为实施例1-12和对比例1-3的用于电子元器件的UV湿气固化胶的性能测试数据,具体参见下表4。The following are the performance test data of the UV moisture curing adhesive for electronic components of Examples 1-12 and Comparative Examples 1-3, see Table 4 below for details.
表4实施例1-12和对比例1-3的性能测试数据表Table 4 Performance test data of Examples 1-12 and Comparative Examples 1-3
结合实施例1-3和实施例4-9、对比例1-2并结合表4可以看出,使用本申请的异氰酸丙烯酸酯加入至体系中,制得的UV湿气固化胶的粘接性能和持粘性较好,贴合稳定,实施例6相对于实施例3来说,持粘性提升0.87MPa,而经过耐候性持粘性测试后,实施例6的拉伸剪切强度从原来的0.75MPa提升至5.05MPa,提升4.3MPa,而实施例3从原来的0.45MPa提升至4.18MPa,提升3.73MPa,实施例6中的持粘性提升率更高,对比例1中将聚氨酯丙烯酸酯等量替换为异氰酸丙烯酸酯,对比例2中将聚氨酯丙烯酸酯和异氰酸丙烯酸酯均等量替换为市售的双重固化聚氨酯丙烯酸酯,制得的UV湿气固化胶的持粘性明显降低。Combining Examples 1-3 and Examples 4-9, Comparative Examples 1-2 and Table 4, it can be seen that the isocyanate acrylate of the present application is added to the system, and the bonding performance and persistent adhesion of the obtained UV moisture curing adhesive are good, and the lamination is stable. Compared with Example 3, the persistent adhesion of Example 6 is improved by 0.87 MPa, and after the weather resistance persistent adhesion test, the tensile shear strength of Example 6 is increased from the original 0.75 MPa to 5.05 MPa, an increase of 4.3 MPa, while that of Example 3 is increased from the original 0.45 MPa to 4.18 MPa, an increase of 3.73 MPa. The rate of improvement of persistent adhesion in Example 6 is higher. In Comparative Example 1, polyurethane acrylate is replaced with isocyanate acrylate in equal amounts, and in Comparative Example 2, polyurethane acrylate and isocyanate acrylate are replaced with commercially available dual-curing polyurethane acrylate in equal amounts, and the persistent adhesion of the obtained UV moisture curing adhesive is significantly reduced.
结合实施例1-6和实施例10-11、对比例3并结合表4可以看出,使用本申请的较优比例的羟基聚醚改性聚二甲基硅氧烷和γ-甲基丙烯酰氧基丙基三甲氧基硅烷作为稳定剂,能够进一步提升制得的UV湿气固化胶的粘接性能和持粘性,对比例3中将稳定剂替换为异氰酸丙烯酸酯,相对于实施例1来说,粘接性和持粘性均降低,可能是因为没有稳定剂的分散和进一步交联作用,由此可知,本申请的聚氨酯丙烯酸酯、异氰酸丙烯酸酯和稳定剂具有较好的协同作用。Combining Examples 1-6 and Examples 10-11, Comparative Example 3 and Table 4, it can be seen that the use of the preferred ratio of hydroxy polyether modified polydimethylsiloxane and γ-methacryloxypropyltrimethoxysilane in the present application as a stabilizer can further improve the adhesion and tackiness of the prepared UV moisture curing adhesive. In Comparative Example 3, the stabilizer is replaced with isocyanate acrylate. Compared with Example 1, both the adhesion and tackiness are reduced, which may be due to the lack of dispersion and further cross-linking of the stabilizer. It can be seen that the polyurethane acrylate, isocyanate acrylate and stabilizer of the present application have a good synergistic effect.
本具体实施例仅仅是对本申请的解释,其并不是对本申请的限制,本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改,但只要在本申请的权利要求范围内都受到专利法的保护。This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed. However, as long as it is within the scope of the claims of the present application, it shall be protected by the patent law.
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