CN117126640A - 一种用于微型扬声器的粘合剂 - Google Patents
一种用于微型扬声器的粘合剂 Download PDFInfo
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- CN117126640A CN117126640A CN202210563421.XA CN202210563421A CN117126640A CN 117126640 A CN117126640 A CN 117126640A CN 202210563421 A CN202210563421 A CN 202210563421A CN 117126640 A CN117126640 A CN 117126640A
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- Prior art keywords
- isocyanate
- parts
- resin
- adhesive
- polyol
- Prior art date
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- 239000011347 resin Substances 0.000 claims abstract description 29
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- 239000012948 isocyanate Substances 0.000 claims abstract description 28
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 28
- 239000003085 diluting agent Substances 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- -1 acrylic ester Chemical class 0.000 claims abstract description 6
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- 238000006243 chemical reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
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- 239000000945 filler Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
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- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 claims description 2
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical class CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims description 2
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- QASBHTCRFDZQAM-UHFFFAOYSA-N (2-isocyanato-2-methyl-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(C)(COC(=O)C=C)N=C=O QASBHTCRFDZQAM-UHFFFAOYSA-N 0.000 claims 1
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- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical group C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 6
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical compound C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-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
- FZHFLPZIOJBRGW-UHFFFAOYSA-N 3-(oxolan-2-yl)prop-2-enoic acid Chemical compound OC(=O)C=CC1CCCO1 FZHFLPZIOJBRGW-UHFFFAOYSA-N 0.000 description 1
- ORTCGSWQDZPULK-UHFFFAOYSA-N 3-isocyanatopropyl prop-2-enoate Chemical compound C=CC(=O)OCCCN=C=O ORTCGSWQDZPULK-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- 235000021508 Coleus Nutrition 0.000 description 1
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- 102220560925 Sialidase-3_R45V_mutation Human genes 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
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- 229920013701 VORANOL™ Polymers 0.000 description 1
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- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
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- 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 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
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- 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
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- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
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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
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- 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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- 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
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- 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
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- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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- 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
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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Abstract
本发明公开了一种用于微型扬声器的粘合剂，粘合剂的制备原料包括多元醇树脂，辅助树脂，特殊异氰酸酯，异氰酸酯，光引发剂和助剂，所述特殊异氰酸酯为一端含有丙烯酸酯双键或甲基丙烯酸酯双键，另一端含有异氰酸酯基团(NCO)结构的化合物。本发明不使用传统的小分子丙烯酸酯等单体做稀释剂，光固化后，残留的小分子少，对微型扬声器中气体吸收材料影响小，明显延长扬声器的使用寿命。
Description
技术领域
本发明属于扬声器技术领域，具体涉及一种用于微型扬声器的粘合剂。
背景技术
在微型扬声器装置中，气体吸收材料(活性炭或者沸石等)能够通过对气体的吸收或者释放，使谐振空间明显虚拟增大，改善扬声器的声音产生，实现突出的声学效果。但在实际应用中，装置中的高压力蒸汽会使吸收材料产生不可逆的老化现象，导致声学效果降低。主要原因是高压力蒸汽中往往含有一些有机挥发物质，这些物质可能来自扬声器装置所用材料的微量释放，例如，粘结材料中未完全固化的小分子或者反应分解产生的小分子等，这些小分子的存在，导致气体吸收材料失去活性，产生老化现象。
在微型扬声器结构中，音膜与音圈之间一般用紫外光固化(UV)粘合剂进行粘结，在UV粘合剂中会用到光引发剂和小分子单体，在UV胶固化后，会产生一些引发剂碎片和单体残留，特别是光照不全的地方。扬声器在使用过程中，会产生较高的温度，这些小分子残留就会释放出来，被气体吸收材料吸收，导致气体吸收材料失活老化，扬声器音质变差。
与传统的汞灯相比，UV LED紫外光固化技术具备众多的显著应用优势，更环保(无臭氧或汞排放)，降低基材热量，以及更高的能源效率，非常适合用于电子产品制造领域。UVLED紫外光固化技术使用丙烯酸酯粘合剂，常用波长为365nm、395nm、405nm的紫外光，可以实现可靠、高效的生产工艺过程。在音圈与振膜的粘接中，振膜通常由聚酯薄膜、纸张或金属制造而成，整个过程仅需2-10秒，且UV LED紫外光固化灯的“冷固化”性能不会损坏娇柔易损的振膜材料。凭借UV LED紫外光固化技术，微型扬声器的生产速度可高达6000件/每小时。
现有技术一般采用光固化丙烯酸酯树脂、小分子单官能团活性稀释剂、光引发剂等制备UV粘合剂。例如专利CN103589348A公开了一种紫外光固化胶黏剂，制备原料包括树脂、活性稀释剂、光引发剂、稳定剂和偶联剂；树脂采用丙烯酸树脂，活性剂稀释剂采用丙烯酸酯类化合物，所述胶黏剂与扬声器中的磁液混合后经紫外光固化，可将磁液包覆起来，避免磁液直接受到高温和外力冲击的影响。专利CN114106766A公开一种水性聚氨酯电声胶黏剂，其原料包括异佛尔酮二异氰酸酯、异氰酸酯、聚醚多元醇、二羟甲基丙酸、三乙胺、乙二胺、催化剂、稳定剂和去离子水等，该胶黏剂以水为溶剂，减少了有机溶剂的使用。上述公开的方法容易导致单体反应不完全，残留小分子单体，在使用时尤其是在高温下易挥发，导致气体吸收材料失活、老化，声学效果降低。
有鉴于此，本领域亟需一种新的用于微型扬声器的粘合剂，以解决现有技术的粘合剂易挥发导致气体吸收材料失活的问题。
发明内容
本发明针对现有技术存在的问题，提供了一种微型扬声器用粘合剂及其制备方法，所述粘合剂残留的小分子少，对微型扬声器中气体吸收材料影响小，明显延长扬声器的使用寿命。
为实现上述目的，本发明采用的技术方案如下：
一种用于微型扬声器的粘合剂，所述粘合剂的制备原料按照重量份包括如下组分：
多元醇树脂30-60份，辅助树脂0-30份，特殊异氰酸酯5-45份，异氰酸酯5-20份，光引发剂1-5份，助剂0.1-10份；
进一步优选地，所述粘合剂的制备原料按照重量份包括如下组分：
多元醇树脂30-60份，辅助树脂0-15份，特殊异氰酸酯15-35份，异氰酸酯5-15份，光引发剂1-3份，助剂0.1-5份。
根据本发明的一个实施方式，所述多元醇树脂为聚酯多元醇、聚醚多元醇、聚丁二烯多元醇及生物基多元醇中的一种或多种；进一步地，所述聚酯多元醇的分子量优选为300-3000g/mol，聚酯多元醇具体可以举例为旭川化学XCP-355，帕斯托CAPA3031，可乐丽P-1010，旭化成T5651；进一步地，所述聚醚多元醇的分子量优选为400-3000g/mol，聚醚多元醇具体可以举例为陶氏化学Voranol 220，长华CHE210，德信联邦DDL-400等；进一步地，所述聚丁二烯多元醇的分子量优选为1000-4500g/mol，聚丁二烯多元醇具体可以举例为克雷威利Polybd R45V；进一步地，所述生物基多元醇的分子量优选为为300～3000g/mol，生物基多元醇具体可以列举为凡鲁特斯Polycin T400，D-1000，伊藤制油Uric H-30。
根据本发明的一个实施方式，所述辅助树脂为丙烯酸酯树脂、聚氨酯树脂、聚酯树脂、增粘树脂、乙烯醋酸乙烯共聚物(EVA)中的一种或多种。进一步地，所述辅助树脂具体可以举例为日本三菱MB-2595，聚优化学JY-2598，分子量优选6000～40000g/mol。
根据本发明的一个实施方式，所述特殊异氰酸酯为一端含有丙烯酸酯双键或甲基丙烯酸酯双键，另一端含有异氰酸酯基团(NCO)结构的化合物；优选使用1,1-二(丙烯酰氧基甲基)乙基异氰酸酯(BEI)，2-异氰酸酯基丙烯酸乙酯(AOI)，异氰酸酯基甲基丙烯酸乙酯(MOI)，异氰酸酯基乙氧化甲基丙烯酸乙酯(MOI-EGO)等。
根据本发明的一个实施方式，所述异氰酸酯选自二苯基甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)、多亚甲基多苯基多异氰酸酯(PAPI)、三苯基甲烷三异氰酸酯(TTI)、2,4-甲苯二异氰酸酯三聚体、六甲撑二异氰酸酯(HDI)三聚体中的一种或多种。
根据本发明的一个实施方式，所述光引发剂采用本领域熟知的光引发剂，其具体种类不作限制，可用的光引发剂可以为1-羟基环己基苯基甲酮(UV184)，2-羟基-2-甲基-1-苯基-1-丙酮(光引发剂1173)，2,4,6-三甲基苯甲酰基-二苯基氧化膦(TPO)，苯基双(2,4,6-三甲基苯甲酰基)氧化磷(819)等中的一种或多种。
根据本发明的一个实施方式，所述助剂包括偶联剂、触变剂、荧光剂、催化剂、阻聚剂、填料中的一种或多种。
进一步地，所述偶联剂为硅烷偶联剂，例如KH-560、KH-171、KH-172、-1124等；
进一步地，所述触变剂选自气相二氧化硅R202或卡博特720；
进一步地，所述催化剂选自有机锡类催化剂、钛类催化剂、铋类催化剂、镍催化剂中的任一种；
进一步地，所述阻聚剂选自对叔丁基邻苯二酚、对苯二酚、1,4-萘醌、对甲氧基苯酚中的一种或多种；
进一步地，所述填料选自二氧化硅、碳酸钙、滑石粉中的一种或多种。
本发明还提供了一种上述可用于微型扬声器的粘合剂的制备方法，所述方法包括如下步骤：
(1)将多元醇树脂与辅助树脂在90-150℃下混合溶解，真空除去水分和残留小分子，得混合物1；
(2)向混合物1中加入特殊异氰酸酯，70-90℃反应2-5h，得混合物2；
(3)向混合物2中加入异氰酸酯，60-90℃反应2-5h，得混合物3；
(4)向混合物3中加入光引发剂和助剂继续反应1-2h，得到成品。
根据本发明的一个实施方式，步骤(2)中加入的特殊异氰酸酯的异氰酸酯基与羟基的摩尔比为1-2:2；步骤(3)中加入异氰酸酯与剩余的羟基继续反应，加入的异氰酸酯的异氰酸酯基与羟基的摩尔比为1-2:1；反应体系中总的异氰酸酯基与羟基的摩尔比为1-3:1，可以制备出既能UV固化又能湿气固化的树脂。
根据本发明的一个实施方式，步骤(4)根据所需要的产品粘度，可任选地加入特殊异氰酸酯作为活性稀释剂；步骤(4)在60-90℃下反应1-2h，得到成品。
根据本发明的一个实施方式，上述方法可以根据需要得到不同粘度的产品，包括：
低粘度产品：室温粘度5000～25000cps；
高粘度产品：室温粘度50000～200000cps；
高温热熔胶产品：100℃粘度1000～20000cps。
本发明的粘合剂在微型扬声器中的用胶点主要有：1.音膜(折环)与球顶(Dome)粘接；2.音膜与盆架粘接；3.音膜与音圈粘结；如附图2所示。胶水路径宽度0.35-0.5mm，LED固化10秒左右，LED波长365nm、395nm。
相对于现有技术，本发明具有以下有益效果：
本发明提供的粘合剂使用特殊结构的异氰酸酯，制得的产品既可以UV固化又可以湿气固化，产品在UV固化之后，其光照不全的地方可以继续进行湿气固化反应，直至粘合剂固化完全。本发明与现有技术相比，主要优点在于不使用传统的小分子丙烯酸酯等单体做稀释剂，光固化后，残留的小分子少，对微型扬声器中气体吸收材料影响小，明显延长扬声器的使用寿命。本发明所用的辅助树脂固化后，内聚力高，能显著提高粘合剂的粘结强度。
附图说明
构成本申请的一部分附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。在附图中：
图1为本发明测试例的测试样品示例；
图2为本发明的粘合剂在扬声器中的用胶点示意；
图3为扬声器单体BOX截面图。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。另外，值得说明的是，本发明所涉及的原料如无特殊说明均为普通市售产品。
实施例1
向反应釜中投入聚醚多元醇(PPG)DDL-400，10g，DDL-2000D，32.5g，聚碳酸酯多元醇T5651，150g，加热至100℃，加入丙烯酸酯树脂JY-2598，10g，高温下搅拌溶解，真空条件下除去水分和残留小分子；将温度调整至80℃，加入AOI 10.5g，搅拌反应3h；加入MDI 10g，继续搅拌2h；加入光引发剂TPO2g，触变剂气硅R202 2g，硅烷偶联剂KH560 1g，催化剂DMDEE1g，活性稀释剂AOI 6g，继续搅拌2h，得到成品，出料，避光保存。
实施例2
向反应釜中投入聚醚多元醇DDL-400 8g，聚醚多元醇CHE-220 34.5g，聚酯多元醇XCP-355 15g加热至130℃，加入增粘树脂MB-2595 8g，高温下搅拌溶解，真空条件下除去水分和残留小分子；将温度调整至90℃，加入AOI 10g，搅拌反应2h；加入MDI 9g，继续搅拌2h；加入光引发剂819 1g，触变剂气硅R202 2g，硅烷偶联剂KH560 1g，催化剂DMDEE 1g，荧光剂OB 0.5g，活性稀释剂AOI 10.45g，继续搅拌2h，得到成品，出料，避光保存。
实施例3
向反应釜中投入聚醚多元醇DDL-400 5g，聚醚多元醇CHE-220 42g，聚酯多元醇XCP-355 10g加热至130℃，加入增粘树脂MB-2595 8g，高温下搅拌溶解，真空条件下除去水分和残留小分子；将温度调整至90℃，加入BEI 10.5g，搅拌反应2h；加入MDI 9g，继续搅拌2h；加入光引发剂819 1g，触变剂气硅R202 2g，硅烷偶联剂KH560 1g，催化剂DMDEE 1g，荧光剂OB 0.5g，活性稀释剂BEI 10.45g，继续搅拌2h，得到成品，出料，避光保存。
实施例4
向反应釜中投入聚醚多元醇DDL-400 5g，聚醚多元醇CHE-220 42g，聚酯多元醇CAPA 3031 6g加热至130℃，加入增粘树脂YJ-2598 10g，高温下搅拌溶解，真空条件下除去水分和残留小分子；将温度调整至90℃，加入AOI 12.5g，搅拌反应2h；加入MDI 9g，继续搅拌2h；加入光引发剂TPO 2g，触变剂气硅202R2g，硅烷偶联剂KH560 1g，催化剂DMDEE 1g，荧光剂OB 0.5g，活性稀释剂BEI 9.45g，继续搅拌2h，得到成品，出料，避光保存。
实施例5
向反应釜中投入聚醚多元醇DDL-1000D 18g，生物基多元醇Polycin D-200024.9g，生物基多元醇DB Oil 15g加热至130℃，加入增粘树脂YJ-25988g，高温下搅拌溶解，真空条件下除去水分和残留小分子；将温度调整至90℃，加入AOI 10g，搅拌反应2h；加入MDI 9g，继续搅拌2h；加入光引发剂819 1g，触变剂气硅R202 2g，硅烷偶联剂KH560 1g，催化剂DMDEE 1g，荧光剂OB 0.5g，活性稀释剂AOI 10.05g，继续搅拌2h，得到成品，出料，避光保存。
对比例1
按照实施例1的方法，将活性稀释剂替换为丙烯酸异冰片酯(IBOA)，其余操作与实施例1相同。
对比例2
向反应釜中投入长兴材料公司提供的UV+湿气聚氨酯丙烯酸酯树脂DR-U277(NCO含量1％～3％)60g，室温下加入丙烯酸异冰片酯(IBOA)12g，二甲基丙烯酰胺(DMAA)16.5g，四氢呋喃丙烯酸酯(THFA)5g，光引发剂TPO 2g，气相二氧化硅2g，硅烷偶联剂KH560 1g，催化剂DMDEE 1g，荧光剂0.5g。搅拌0.5～2h得到成品，出料，避光保存。
测试例
测试本发明实施例和对比例制得的粘合剂对于扬声器声学材料的影响，测试方法如下：
1.制备2mm厚的固化胶片，固化能量为10000mj/cm2每面；
2.将厚度约为2mm固化后的胶片裁切成2*3*3mm的小块状颗粒
3.称取0.4g胶片颗粒置于规格为10ml的玻璃中，记为A，空白组空瓶记为B，如附图1所示；
4.称取0.6g吸音颗粒，共两份，分别置于A，B中，拧紧瓶盖；
5.将A，B放置于预先升温到120℃的烘箱中，在此温度下放置4h；
6.共存4h后将A，B取出，放置于25℃下10min，然后将A，B瓶中吸音颗粒倒于玻璃表面皿中铺平，并马上各称取0.1400g吸音颗粒，同时测试1ccbox空腔声学，记为F(空腔)，然后将0.1400g吸音颗粒置于空腔中，密闭BOX，测试声学记为F(填粉)，气体吸附材料(填粉)在扬声器空腔中的位置如附图3所示。
吸音颗粒能有效的降低Hz为：△F0(填粉)＝F(空腔)-F(填粉)，例如，△F0(B)＝F(空腔)-F(填粉B)，△F0(A)＝F(空腔)-F(填粉A)。按照上述测试方法，不断更换填粉A1、A2、A3、A4、A5或者B，等等，依此类推，分别得到F(填粉A1)、F(填粉A2)、F(填粉A3)、F(填粉A4)、F(填粉A5)、F(填粉B)的数值。最后测出A胶水共存影响吸音颗粒的Hz数就为△F0＝△F0(A)-△F0(B)。
判定标准：△F0小于等于8Hz。
实施例1-5及对比例1-2的测试数据如下表所示：
F(填粉A1)、F(填粉A2)、F(填粉A2)、F(填粉A4)、F(填粉A5)、F(填粉对比1)、F(填粉对比2)分别对应实施例1-5和对比例1-2的产物。
以上测试结果表明，首先，将活性稀释剂替换为丙烯酸异冰片酯后，△F0显著增大，丙烯酸异冰片酯是UV光固化最常用的稀释剂，工业品往往含有一些小分子杂质，本身光固化后转化率很难达到100％，也会导致一些小分子残留，影响气体吸附材料的性能，导致扬声器的使用寿命和音质变差。其次，采用对比例2的常规UV加湿气固化配方，添加了较多的丙烯酸酯单体，用于扬声器的固定粘结，结果表明对气体吸附材料的使用寿命具有较大的影响。
最后应当说明的是，以上内容仅用以说明本发明的技术方案，而非对本发明保护范围的限制，本领域的普通技术人员对本发明的技术方案进行的简单修改或者等同替换，均不脱离本发明技术方案的实质和范围。
Claims (10)
1.一种用于微型扬声器的粘合剂，其特征在于，按重量份包括以下原料：多元醇树脂30-60份，辅助树脂0-30份，特殊异氰酸酯5-45份，异氰酸酯5-20份，光引发剂1-5份，助剂0.1-10份。
2.根据权利要求1所述的粘合剂，其特征在于，按重量份包括以下原料：多元醇树脂30-60份，辅助树脂0-15份，特殊异氰酸酯15-35份，异氰酸酯5-15份，光引发剂1-3份，助剂0.1-5份。
3.根据权利要求1或2所述的粘合剂，其特征在于，所述多元醇树脂为聚酯多元醇、聚醚多元醇、聚丁二烯多元醇及生物基多元醇中的一种或多种；所述辅助树脂为丙烯酸酯树脂、聚氨酯树脂、聚酯树脂、增粘树脂、乙烯醋酸乙烯共聚物(EVA)中的一种或多种。
4.根据权利要求1或2所述的粘合剂，其特征在于，所述特殊异氰酸酯为一端含有丙烯酸酯双键或甲基丙烯酸酯双键，另一端含有异氰酸酯基团结构的化合物。
5.根据权利要求4所述的粘合剂，其特征在于，所述特殊异氰酸酯选自1,1-二(丙烯酰氧基甲基)乙基异氰酸酯、2-异氰酸酯基丙烯酸乙酯、异氰酸酯基甲基丙烯酸乙酯、异氰酸酯基乙氧化甲基丙烯酸乙酯中的任一种。
6.根据权利要求1或2所述的粘合剂，其特征在于，所述异氰酸酯选自二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、多亚甲基多苯基多异氰酸酯、三苯基甲烷三异氰酸酯、2,4-甲苯二异氰酸酯三聚体、六甲撑二异氰酸酯三聚体中的任一种。
7.根据权利要求1或2所述的粘合剂，其特征在于，所述助剂包括偶联剂、触变剂、荧光剂、催化剂、阻聚剂、填料中的一种或多种。
8.权利要求1-7任一项所述的粘合剂的制备方法，所述方法包括如下步骤：
(1)将多元醇树脂与辅助树脂在90-150℃下混合溶解，真空除去水分和残留小分子，得混合物1；
(2)向混合物1中加入特殊异氰酸酯，70-90℃反应2-5h，得混合物2；
(3)向混合物2中加入异氰酸酯，60-90℃反应2-5h，得混合物3；
(4)向混合物3中加入光引发剂和助剂继续反应1-2h，得到所述粘合剂。
9.根据权利要求8所述的制备方法，其特征在于，步骤(2)中加入的特殊异氰酸酯的异氰酸酯基与羟基的摩尔比为1-2:2；步骤(3)中加入的异氰酸酯的异氰酸酯基与羟基的摩尔比为1-2:1。
10.根据权利要求8所述的制备方法，其特征在于：步骤(4)根据所需要的产品粘度，可任选地加入特殊异氰酸酯作为活性稀释剂；步骤(4)的反应温度为60-90℃，反应时间为1-2h。
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