CN114901765A - 粘合片 - Google Patents
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- Publication number
- CN114901765A CN114901765A CN202080090547.9A CN202080090547A CN114901765A CN 114901765 A CN114901765 A CN 114901765A CN 202080090547 A CN202080090547 A CN 202080090547A CN 114901765 A CN114901765 A CN 114901765A
- Authority
- CN
- China
- Prior art keywords
- adhesive sheet
- gas
- meth
- electronic component
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 146
- 239000000853 adhesive Substances 0.000 title claims abstract description 144
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000002834 transmittance Methods 0.000 claims abstract description 26
- 230000004888 barrier function Effects 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 29
- 229920000058 polyacrylate Polymers 0.000 claims description 29
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 26
- 238000006073 displacement reaction Methods 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 17
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 230000001678 irradiating effect Effects 0.000 claims description 8
- 238000007689 inspection Methods 0.000 claims description 6
- 238000003672 processing method Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 abstract description 81
- 230000005611 electricity Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 167
- 239000010410 layer Substances 0.000 description 149
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 105
- -1 2- (4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl) -5-hydroxyphenyl Chemical group 0.000 description 71
- 239000000178 monomer Substances 0.000 description 53
- 239000003431 cross linking reagent Substances 0.000 description 43
- 239000000047 product Substances 0.000 description 19
- 229920005601 base polymer Polymers 0.000 description 18
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- 125000000524 functional group Chemical group 0.000 description 17
- 239000012948 isocyanate Substances 0.000 description 17
- 239000003999 initiator Substances 0.000 description 16
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- 239000011347 resin Substances 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 12
- 150000002513 isocyanates Chemical class 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 8
- 229940059574 pentaerithrityl Drugs 0.000 description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 8
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
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- 239000012790 adhesive layer Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 6
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
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- 125000000623 heterocyclic group Chemical group 0.000 description 5
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
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- 239000002243 precursor Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
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- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
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- 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 4
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
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- 229920000728 polyester Polymers 0.000 description 4
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- OLFNXLXEGXRUOI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C(N2N=C3C=CC=CC3=N2)=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 OLFNXLXEGXRUOI-UHFFFAOYSA-N 0.000 description 3
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 3
- SITYOOWCYAYOKL-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(3-dodecoxy-2-hydroxypropoxy)phenol Chemical compound OC1=CC(OCC(O)COCCCCCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 SITYOOWCYAYOKL-UHFFFAOYSA-N 0.000 description 3
- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical compound OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 description 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229920002367 Polyisobutene Polymers 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 125000003700 epoxy group Chemical group 0.000 description 3
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
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- 125000000542 sulfonic acid group Chemical group 0.000 description 3
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- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
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- IAUGBVWVWDTCJV-UHFFFAOYSA-N 1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)NC(=O)C=C IAUGBVWVWDTCJV-UHFFFAOYSA-N 0.000 description 2
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- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 description 2
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- UZUNCLSDTUBVCN-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-6-(2-phenylpropan-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C=1C(C(C)(C)CC(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C(O)C=1C(C)(C)C1=CC=CC=C1 UZUNCLSDTUBVCN-UHFFFAOYSA-N 0.000 description 2
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- QENRKQYUEGJNNZ-UHFFFAOYSA-N 2-methyl-1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(C)C(S(O)(=O)=O)NC(=O)C=C QENRKQYUEGJNNZ-UHFFFAOYSA-N 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
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- 125000001204 arachidyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
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- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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Abstract
本发明提供一种粘合片,其可良好地暂时固定小型电子部件(例如,尺寸为50μm□以下的芯片)且能够良好地剥离。本发明的粘合片具备通过激光照射而产生气体的气体产生层,该气体产生层的利用纳米压痕法得到的弹性模量Er(gas)[单位:MPa]与厚度h(gas)[单位:μm]满足下述式(1)。Log(Er(gas)×106)≥8.01×h(gas)‑0.116…(1)。在一个实施方式中,上述粘合片的波长360nm的透光率为0%~35%。在一个实施方式中,上述粘合片的波长380nm的透光率为10%~100%。
Description
技术领域
本发明涉及粘合片。
背景技术
以往,在对电子部件进行加工、输送等时,有时进行如下操作:在加工、输送等时将电子部件暂时固定于粘合片上,在加工和输送后将电子部件自该粘合片剥离。作为这样的操作中使用的粘合片,有时使用在加工时和输送时(接收电子部件时)具有规定的粘合力、在加工后和输送后(交出电子部件时)粘合力会降低的粘合片。作为这样的粘合片之一,提出了使粘合剂层中含有热膨胀性微球而构成的粘合片(例如专利文献1)。含有热膨胀性微球的粘合片具有如下的特征:具有规定的粘合力,并且通过利用加热使热膨胀性微球膨胀,在粘合面上形成凹凸而使接触面积减小,由此粘合力下降或消失。这样的粘合片具有无外部应力便可容易地剥离被粘物的优点。
然而,近年来,伴随着各种装置的轻量化、搭载数增加的倾向,而推进电子部件的小型化,产生了将小型化为与上述热膨胀性微球相同程度的尺寸的电子部件暂时固定的必要性。在将已小型化的电子部件暂时固定而进行处理,其后进行剥离的情况下,在剥离时需要在比被粘物的贴附面积狭小的范围内在粘合面形成凹凸,并且,需要选择位置地表现出剥离性。但是,对于包含热膨胀性微球的现有粘合片而言,由于粒径的偏差,在存在粒径大的热膨胀性微球的部位,与要剥离的电子部件邻接配置的多个电子部件发生误剥离,或者,在不存在热膨胀性微球的部位,无法在粘贴有要剥离的电子部件的粘合面上形成凹凸等的影响变大,有时无法在该部位进行良好的剥离。
现有技术文献
专利文献
专利文献1:日本特开2001-131507号公报
发明内容
发明要解决的问题
本发明是为了解决上述现有的课题而做出的发明,其目的在于提供一种能够良好地暂时固定小型电子部件(例如,尺寸为50μm□以下的芯片)且良好地剥离的粘合片。
用于解决问题的方案
本发明的粘合片具备通过激光照射而产生气体的气体产生层,该气体产生层的利用纳米压痕法得到的弹性模量Er(gas)[单位:MPa]与厚度h(gas)[单位:μm]满足下述式(1)。
Log(Er(gas)×106)≥8.01×h(gas)-0.116···(1)
在一个实施方式中,上述粘合片的波长360nm的透光率为0%~40%。
在一个实施方式中,上述粘合片的波长380nm的透光率为10%~100%。
在一个实施方式中,上述气体产生层含有紫外线吸收剂,该紫外线吸收剂的最大吸收波长为360nm以下。
在一个实施方式中,上述气体产生层为活性能量射线固化型组合物的固化物。
在一个实施方式中,上述气体产生层含有丙烯酸系聚合物。
在一个实施方式中,上述粘合片在上述气体产生层的至少单侧具备气体阻隔层,该气体阻隔层的利用纳米压痕法得到的弹性模量为0.1MPa~100MPa。
在一个实施方式中,上述气体阻隔层的厚度为0.1μm~50μm。
在一个实施方式中,上述阻隔层表现出粘合性。
在一个实施方式中,上述粘合片的波长500nm的透光率为70%~100%。
在一个实施方式中,上述粘合片的雾度值为50%以下。
在一个实施方式中,上述粘合片的表面通过激光照射而变形。
在一个实施方式中,上述粘合片的表面通过激光照射而变形为凸状。
在一个实施方式中,通过对上述粘合片的激光照射而产生的该粘合片表面的水平位移为50μm以下。
根据本发明的其它方面,提供一种电子部件的处理方法。该电子部件的处理方法包括:将电子部件贴附于上述粘合片上;及对该粘合片照射激光而自该粘合片剥离该电子部件。
在一个实施方式中,上述电子部件的剥离选择位置地进行。
在一个实施方式中,上述电子部件的处理方法包括:在将上述电子部件贴附于上述粘合片之后且自该粘合片剥离该电子部件之前,对该电子部件进行规定的处理。
在一个实施方式中,上述处理为研磨加工、切割加工、芯片接合、引线接合、蚀刻、蒸镀、模塑、电路形成、检查、产品检验、清洗、转印、排列、修复或装置表面的保护。
在一个实施方式中,包括:自上述粘合片剥离前述电子部件之后,将电子部件配置于其他片材。
发明的效果
根据本发明,可提供一种粘合片,其可良好地暂时固定小型电子部件(例如,尺寸为50μm□以下的芯片),且通过具备利用激光照射可产生气体的气体产生层,可使该小型电子部件良好地剥离。
附图说明
图1的(a)为本发明的一个实施方式的粘合片的示意截面图,(b)为本发明的另一实施方式的粘合片的示意截面图。
具体实施方式
A.粘合片的概要
图1的(a)为本发明的一个实施方式的粘合片的示意截面图。该实施方式的粘合片100具备气体产生层10。图1的(b)为本发明的另一实施方式的粘合片的示意截面图。该实施方式的粘合片200还具备在气体产生层10的至少单面配置的气体阻隔层20。如图1的(a)所示那样,粘合片100可以在气体产生层10的单面进一步具备基材30。另外,如图1的(b)所示那样,在具备气体产生层10和气体阻隔层20的情况下,粘合片200可以在气体产生层10的与气体阻隔层20相反的一侧进一步具备基材30。另外,粘合片可以在能够获得本发明效果的范围内进一步包含任意且适当的其它层。在一个实施方式中,上述粘合片可以进一步具备在气体产生层的与气体阻隔层相反的一侧配置的粘合剂层。粘合剂层的形态没有限定,可以为固化型的粘合剂层,也可以为压敏型的粘合剂层。虽未图示,但本发明的粘合片可以出于在至供于使用为止的期间保护粘合面的目的而在气体产生层或气体阻隔层的外侧设置有剥离衬垫。
气体产生层10通过激光照射而产生气体。更详细而言,气体产生层10为通过利用激光照射使其成分气体化而产生气体的层。作为激光,代表性而言使用UV激光。通过对粘合片(实质上为气体产生层)照射激光,粘合片的表面能够变形。作为激光,代表性而言使用UV激光。
在一个实施方式中,气体产生层和气体阻隔层具有粘合性。需要说明的是,本说明书中,“具有粘合性”是指:贴附于不锈钢板时的23℃下的粘合力为0.1N/20mm以上。
在具备气体阻隔层20的粘合片中,通过对粘合片(实质上为气体产生层)照射激光,从而气体阻隔层20的表面能够变形。在一个实施方式中,该变形起因于由气体产生层10产生的气体,在气体阻隔层20的与气体产生层10相反的一侧发生该变形。在一个实施方式中,气体阻隔层具有粘合性。
本发明的粘合片可以在粘合片表面(在图1的(a)所示形态中是气体产生层表面,在图1的(b)所示形态中是气体阻隔层)上贴附电子部件等被加工体而使用。本发明的粘合片具备气体产生层,通过激光照射而在微小范围局部地产生气体。因该气体的产生,而在粘合片的表面产生变形,其结果,在照射了激光的部分表现出剥离性。根据本发明,能如上操作来在微小的范围产生变形,因此,在对极其微细的小型电子部件进行加工时,也可使该小型电子部件良好地剥离。此外,即便在需要剥离的小型电子部件与不需要剥离的小型电子部件相邻地暂时固定的情况下,也可以在剥离对象的部位进行剥离,在剥离对象外的部位不进行剥离,即,可以仅使需要剥离的小型电子部件剥离,还可以防止小型电子部件的不必要的脱离。本发明的粘合片的剥离时的指向性优异,可仅在所期望的部位进行剥离,在防止破损且残胶较少的方面也是有利的。需要说明的是,所谓剥离时的指向性,是表示将小型电子部件等被粘物自该粘合片剥离、且对准某个相隔一定距离的场所射出时的位置精度的指标,若该指向性优异,则可防止剥离时被粘物向非预期的方向飞出。
粘合片的变形是指:在粘合片表面(在图1的(a)所示形态中是气体产生层表面,在图1的(b)所示形态中是气体阻隔层)的法线方向(厚度方向)和水平方向(与厚度方向正交的方向)产生的位移。粘合片的变形例如通过如下方式产生:通过使用波长355nm、光束直径约20μmφ的UV激光,在0.80mW功率、40kHz频率下进行脉冲扫描,由此自气体产生层产生气体。关于变形后的形状,例如对于脉冲扫描过的任意1点,在激光照射后24小时后,根据共焦激光显微镜或非接触型干涉显微镜(WYKO)等的测定来进行观测。其形状可为发泡(凸状)、贯通孔(凹凸状)、凹陷(凹状),通过这些变形,可产生剥离性。在要沿法线方向将电子部件有效地剥离时,优选激光照射前后的法线方向的位移变化较大,形成发泡形状者是尤其适合的。发泡(凸状)以未照射部的粘合片表面为基准,将最高点定义为垂直位移Y,将半峰全宽定义为水平位移X(直径)。关于激光照射后形成孔的贯通孔(凹凸)与凹陷(凹),将最高点与最低点的差定义为垂直位移Y,将孔的直径定义为水平位移X。通过对粘合片的激光照射而产生的粘合片的表面的水平位移优选为50μm以下,更优选为40μm以下,进一步优选为30μm以下。若为这样的范围,则对于较小的被粘物,可优选地进行仅期望部位的剥离。此外,在被粘物以较窄的间隔排列的情况下,也可期待同样的效果。该水平位移的下限例如为3μm(优选为4μm)。
本发明的粘合片的波长360nm的透光率优选为0%~40%,更优选为0%~35%,进一步优选为0.01%~30%,特别优选为0.02%~25%。另外,上述粘合片的波长380nm的透光率优选为10%~100%,更优选为12%~95%,进一步优选为15%~90%,特别优选为20%~85%。需要说明的是,粘合片的透光率是指粘合片的厚度方向的透光率,是将粘合片的构成层整层作为对象而测得的透光率。例如,通过使气体产生层含有规定的紫外线吸收剂,从而能够形成透光率如此调整后的粘合片。本发明中,通过将紫外线区域的光的波长设为上述范围,从而能够高效地吸收UV激光中使用的波长355nm的光,能够将光能转化成热能。另一方面,通过提高波长380nm的透过性,从而能够组合使用在波长350~380nm处具有吸收的光聚合引发剂,因此,在使用活性能量射线固化型粘合剂组合物时,通过活性能量射线照射(例如,波长380nm的紫外线照射),而能够使气体产生层固化,能够提高弹性模量。在这种粘合片中,在照射UV激光时能够抑制粘合剂的过度变形,能够仅使需要剥离的小型电子部件发生剥离,还能够防止小型电子部件的不需要的脱离。如上那样,如果确定波长360nm和波长380nm透射率,则能够将波长350nm~380nm的紫外线优选地用于固化反应,能够将气体产生层的弹性模量控制至最佳范围。
本发明的粘合片的波长500nm的透光率优选为70%~100%,更优选为75%~98%,进一步优选为80%~95%。如果为这样的范围,则在利用激光照射来剥离被粘物时,可得到能够隔着粘合片良好地视觉识别成为剥离对象的被粘物的粘合片。
本发明的粘合片的雾度值优选为70%以下,更优选为65%以下,进一步优选为50%以下。如果为这样的范围,则在利用激光照射来剥离被粘物时,能够在气体阻隔层的任意部位均产生变形部(例如凹凸部),且能够得到变形部(例如凹凸部)的形状偏差少的粘合片。粘合片的雾度值越低越优选,其下限例如为0.1%(优选为0%)。
将本发明的粘合片的粘合片表面(在图1的(a)所示形态中是气体产生层表面,在图1的(b)所示形态中是气体产生层)贴附于不锈钢板时的23℃下的初始粘合力优选为0.3N/20mm~15N/20mm,更优选为0.5N/20mm~10N/20mm。如果是这样的范围,则可得到能够良好地保持被粘物的粘合片。另外,能够通过低能量的激光照射而表现出剥离性,能够得到残胶少、剥离时的指向性优异的粘合片。粘合力按照JIS Z 0237:2000进行测定。具体而言,如下测定:通过2kg的辊往返1次而将粘合片贴附于不锈钢板(算术平均表面粗糙度Ra:40±25nm),在23℃下放置30分钟后,在剥离角度为180°、剥离速度(拉伸速度)为300mm/min的条件下,剥离粘合片并测定。粘合片的粘合力因激光照射而发生变化,但在本说明书中,“初始粘合力”是指照射激光之前的粘合力。另外,初始粘合力和下述粘合力可通过将气体产生层或气体阻隔层贴附于上述不锈钢板来测定。
粘合片的厚度优选为1μm~300μm,更优选为5μm~200μm。
在一个实施方式中,上述粘合片被用作被粘物(例如电部件)的载体片。例如,(1)将配置在其它固定材料上的多个超小型部件转印至上述粘合片上而进行接收,(2)其后,照射UV激光(例如,波长355nm的UV激光),将位于期望部位的超小型部件选择性地剥离,如此使用上述粘合片。
如上所述,本发明的粘合片通过激光照射而表现出良好的剥离性。此处,良好的剥离性是指:(1)能够以低能量进行剥离,(2)残胶少,(3)剥离时的指向性优异。如果能够以低能量进行剥离,则能够防止激光照射部位的劣化。如果残胶少,则能够防止后续工序的不良情况。如果剥离时的指向性优异,则能够防止不需要的芯片飞散。
B.气体产生层
气体产生层可以是能够吸收紫外线的层。代表性而言,气体产生层包含紫外线吸收剂。通过包含紫外线吸收剂,从而可形成能够吸收激光而进行气体化的气体产生层。
上述气体产生层截面的利用纳米压痕法得到的弹性模量(本说明书中,也简称为“气体产生层的利用纳米压痕法得到的弹性模量”)优选为0.1MPa~10000MPa,更优选为0.2MPa~1000MPa,特别优选为0.3MPa~800MPa。如果是这样的范围,则可防止由气体产生层产生的气体的不需要的脱除,通过激光照射而使粘合片(实质上为气体产生层)良好地发生变形。利用纳米压痕法得到的弹性模量是指:在负载时、卸载时连续测定将压头压入至试样(例如粘合面)时对压头施加的负载载荷和压入深度,由所得负载载荷-压入深度曲线求出的弹性模量。利用纳米压痕法得到的弹性模量如下来获得:对于通过将金刚石制的Berkovich型(三角锥型)探针垂直地按压于测定对象层的切出的截面而获得的位移-载荷滞回曲线,利用测定装置附带的软件(triboscan)进行数值处理,由此获得。本说明书中,所谓弹性模量,是使用纳米压痕仪(Hysitron Inc公司制造的Triboindenter TI-950),通过规定温度(25℃)下的单一压入法,在压入速度约500nm/sec、拔出速度约500nm/sec、压入深度约1500nm的测定条件下测得的弹性模量。需要说明的是,气体产生层的弹性模量可根据该层中包含的材料种类、构成材料的基础聚合物的结构、相应层中添加的添加剂的种类/量等来调整。
上述气体产生层的厚度优选为0.1μm~50μm,更优选为0.5μm~45μm,进一步优选为1μm~42μm,特别优选为2μm~40μm。如果是这样的范围,则可得到通过激光照射而能够形成更良好的变形部的粘合片。
上述气体产生层的利用纳米压痕法得到的弹性模量Er(gas)[单位:MPa]和厚度h(gas)[单位:μm]满足下述式(1)。
Log(Er(gas)×106)≥8.01×h(gas)-0.116···(1)
本发明中,通过以满足上述式(1)的方式构成气体产生层,从而防止由气体产生层中产生的气体导致的过度变形,因激光照射而使粘合片良好地变形。通过形成这种气体产生层,从而无需配置厚厚的阻隔层来作为防止过度变形的层,能够产生微小范围的表面变形。更具体而言,能够利用气体产生层单独进行表面变形,或者能够使气体阻隔层柔软地构成。
在一个实施方式中,利用纳米压痕法得到的弹性模量Er(gas)[单位:MPa]与厚度h(gas)[单位:μm]满足下述式(2)。在一个实施方式中,利用纳米压痕法得到的弹性模量Er(gas)[单位:MPa]与厚度h(gas)[单位:μm]满足下述式(3)。
Log(Er(gas)×106)≥7.66×h(gas)-0.092···(2)
Log(Er(gas)×106)≥7.52×h(gas)-0.081···(3)
如果是这样的范围,则上述效果变得更显著。
在一个实施方式中,利用纳米压痕法得到的弹性模量Er(gas)[单位:MPa]与厚度h(gas)[单位:μm]进一步满足下述式(4)。
Log(Er(gas)×106)≤47.675×h(gas)-0.519···(4)
上述气体产生层的气体化起始温度优选为150℃~500℃,更优选为170℃~450℃,进一步优选为190℃~420℃,尤其优选为200℃~400℃。若为这样的范围,则可获得可通过激光照射而形成更良好的变形部的粘合片。需要说明的是,本说明书中,所谓气体产生层的气体化起始温度,是指使粘合片升温时的根据EGA分析算出的气体产生开始温度。气体产生开始温度由达到根据EGA分析所得的EGA/MS图谱的最大气体产生峰的半值的温度定义。气体化起始温度越低,激光照射时开始产生气体的温度越低,在以更小功率进行激光照射时也产生充分的气体量。在一个实施方式中,气体产生层的气体化起始温度相当于紫外线吸收剂的气体化起始温度。
上述气体产生层的10%重量减少温度优选为150℃~500℃,更优选为170℃~450℃,进一步优选为200℃~400℃。若为这样的范围,则可获得可通过激光照射而形成更良好的变形部的粘合片。所谓气体产生层的10%重量减少温度,是指使粘合片升温时(例如,通过激光照射而升温时)的TGA分析中气体产生层的重量相对于升温前的重量而减少了10重量%(即,气体产生层的重量相对于升温前的重量而成为90%)的时刻的温度。
如上所述,气体产生层优选包含紫外线吸收剂。在一个实施方式中,上述气体产生层还包含活性能量射线固化型组合物(例如粘合剂)。在一个实施方式中,上述气体产生层包含粘结剂树脂。粘结剂树脂优选为活性能量射线固化型组合物(例如粘合剂)的固化物。在一个实施方式中,气体产生层包含丙烯酸系聚合物。
(紫外线吸收剂)
作为紫外线吸收剂,只要是吸收紫外线(例如波长360nm以下)的化合物,就可以使用任意且适当的紫外线吸收剂。作为紫外线吸收剂,例如可列举:苯并三唑系紫外线吸收剂、二苯甲酮系紫外线吸收剂、三嗪系紫外线吸收剂、水杨酸酯系紫外线吸收剂、氰基丙烯酸酯系紫外线吸收剂等。其中,优选为三嗪系紫外线吸收剂或苯并三唑系紫外线吸收剂,特别优选为三嗪系紫外线吸收剂。尤其是在使用丙烯酸系聚合物作为粘结剂树脂时,三嗪系紫外线吸收剂由于与丙烯酸系聚合物的相容性高而可优选使用。三嗪系紫外线吸收剂更优选由具有羟基的化合物构成,尤其优选由羟基苯基三嗪系化合物构成的紫外线吸收剂(羟基苯基三嗪系紫外线吸收剂)。
作为羟基苯基三嗪系紫外线吸收剂,例如可列举:2-(4,6-双(2,4-二甲基苯基)-1,3,5-三嗪-2-基)-5-羟基苯基与[(C10-C16(主要是C12-C13)烷氧基)甲基]环氧乙烷的反应产物(商品名“TINUVIN 400”,BASF公司制造)、2-[4,6-双(2,4-二甲基苯基)-1,3,5-三嗪-2-基]-5-[3-(十二烷氧基)-2-羟基丙氧基]苯酚、2-(2,4-二羟基苯基)-4,6-双-(2,4-二甲基苯基)-1,3,5-三嗪与缩水甘油酸(2-乙基己基)酯的反应产物(商品名“TINUVIN405”,BASF公司制造)、2,4-双(2-羟基-4-丁氧基苯基)-6-(2,4-二丁氧基苯基)-1,3,5-三嗪(商品名“TINUVIN 460”,BASF公司制造)、2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[(己基)氧基]苯酚(商品名“TINUVIN 1577”,BASF公司制造)、2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[2-(2-乙基己酰氧基)乙氧基]苯酚(商品名“Adekastab LA-46”,ADEKA公司制造)、2-(2-羟基-4-[1-辛氧基羰基乙氧基]苯基)-4,6-双(4-苯基苯基)-1,3,5-三嗪(商品名“TINUVIN479”,BASF公司制造)、BASF公司制造的商品名“TINUVIN 477”等。
作为苯并三唑系紫外线吸收剂(苯并三唑系化合物),例如可列举:2-(2-羟基-5-叔丁基苯基)-2H-苯并三唑(商品名“TINUVIN PS”,BASF公司制造)、苯丙酸与3-(2H-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羟基(C7-9侧链及直链烷基)的酯化合物(商品名“TINUVIN 384-2”,BASF公司制造)、3-[3-叔丁基-4-羟基-5-(5-氯-2H-苯并三唑-2-基)苯基]丙酸辛酯及3-[3-叔丁基-4-羟基-5-(5-氯-2H-苯并三唑-2-基)苯基]丙酸2-乙基己酯的混合物(商品名“TINUVIN109”,BASF公司制造)、2-(2H-苯并三唑-2-基)-4,6-双(1-甲基-1-苯基乙基)苯酚(商品名“TINUVIN 900”,BASF公司制造)、2-(2H-苯并三唑-2-基)-6-(1-甲基-1-苯基乙基)-4-(1,1,3,3-四甲基丁基)苯酚(商品名“TINUVIN 928”,BASF制造)、3-(3-(2H-苯并三唑-2-基)-5-叔丁基-4-羟基苯基)丙酸甲酯/聚乙二醇300的反应产物(商品名“TINUVIN 1130”,BASF公司制造)、2-(2H-苯并三唑-2-基)对甲酚(商品名“TINUVIN P”,BASF公司制造)、2-(2H-苯并三唑-2-基)-4,6-双(1-甲基-1-苯基乙基)苯酚(商品名“TINUVIN 234”,BASF公司制造)、2-[5-氯-2H-苯并三唑-2-基]-4-甲基-6-(叔丁基)苯酚(商品名“TINUVIN 326”,BASF公司制造)、2-(2H-苯并三唑-2-基)-4,6-二-叔戊基苯酚(商品名“TINUVIN 328”,BASF公司制造)、2-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)苯酚(商品名“TINUVIN 329”,BASF公司制造)、2,2'-亚甲基双[6-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)苯酚](商品名“TINUVIN 360”,BASF公司制造)、3-(3-(2H-苯并三唑-2-基)-5-叔丁基-4-羟基苯基)丙酸甲酯与聚乙二醇300的反应产物(商品名“TINUVIN 213”,BASF公司制造)、2-(2H-苯并三唑-2-基)-6-十二烷基-4-甲基苯酚(商品名“TINUVIN 571”,BASF公司制造)、2-[2-羟基-3-(3,4,5,6-四氢邻苯二甲酰亚胺-甲基)-5-甲基苯基]苯并三唑(商品名“Sumisorb 250”,住友化学株式会社制造)、2-(3-叔丁基-2-羟基-5-甲基苯基)-5-氯-2H-苯并三唑(商品名“SEESORB 703”,Shipro Kasei公司制造)、2-(2H-苯并三唑-2-基)-4-甲基-6-(3,4,5,6-四氢邻苯二甲酰亚胺基甲基)苯酚(商品名“SEESORB 706”,Shipro Kasei公司制造)、2-(4-苯甲酰氧基-2-羟基苯基)-5-氯-2H-苯并三唑(ShiproKasei公司制造的商品名“SEESORB 7012BA”)、2-叔丁基-6-(5-氯-2H-苯并三唑-2-基)-4-甲基苯酚(商品名“KEMISORB 73”,Chemipro Kasei公司制造)、2,2'-亚甲基双[6-(2H-苯并三唑-2-基)-4-叔辛基苯酚](商品名“Adekastab LA-31”,ADEKA株式会社制造)、2-(2H-苯并三唑-2-基)对纤维素(商品名“Adekastab LA-32”,ADEKA株式会社制造)、2-(5-氯-2H-苯并三唑-2-基)-6-叔丁基-4-甲基苯酚(商品名“Adekastab LA-36”,ADEKA株式会社制造)等。
上述紫外线吸收剂可以为染料或颜料。作为颜料,例如可列举:偶氮系、酞菁系、蒽醌系、色淀系、苝系、芘酮系、喹吖啶酮系、硫靛系、二噁嗪系、异吲哚啉酮系、喹酞酮系等颜料。作为染料,可列举:偶氮系、酞菁系、蒽醌系、羰基系、靛蓝系、醌亚胺系、次甲基系、喹啉系、硝基系等染料。
构成上述紫外线吸收剂的化合物的分子量优选为100~1500,更优选为200~1200,进一步优选为200~1000。如果为这样的范围,则可获得可通过激光照射而形成更良好的变形部的粘合片。
在一个实施方式中,上述紫外线吸收剂的最大吸收波长优选为360nm以下,更优选为355nm以下,进一步优选为340nm以下。如果使用这种紫外线吸收剂,则能够优选得到吸收紫外线而表现出良好的剥离性、且常态下的特性稳定性也优异的粘合片。
上述紫外线吸收剂的含有比例相对于气体产生层中的基础聚合物100重量份,优选为1重量份~50重量份,更优选为3重量份~40重量份。
(活性能量射线固化型组合物)
通过使用活性能量射线固化型组合物,从而能够形成弹性模量得以优选调整的气体产生层。
在一个实施方式中,作为活性能量射线固化型组合物,可使用包含成为母剂的基础聚合物以及能够与该基础聚合物键合的活性能量射线反应性化合物(单体或低聚物)的活性能量射线固化型组合物(A1)。在其它实施方式中,使用包含活性能量射线反应性聚合物作为基础聚合物的活性能量射线固化型组合物(A2)。上述基础聚合物优选具有能够与光聚合引发剂发生反应的官能团。作为该官能团,例如可列举羟基、羧基等。
作为上述组合物(A1)中使用的基础聚合物,例如可列举:天然橡胶、聚异丁烯橡胶、苯乙烯-丁二烯橡胶、苯乙烯-异戊二烯-苯乙烯嵌段共聚物橡胶、再生橡胶、丁基橡胶、聚异丁烯橡胶、腈橡胶(NBR)等橡胶系聚合物;有机硅系聚合物;丙烯酸系聚合物等。这些聚合物可以单独使用或组合使用两种以上。其中,优选为丙烯酸系聚合物。
作为丙烯酸系聚合物,可列举:(甲基)丙烯酸烷基酯、(甲基)丙烯酸环烷基酯、(甲基)丙烯酸芳基酯等含烃基的(甲基)丙烯酸酯的均聚物或共聚物;该含烃基的(甲基)丙烯酸酯与其它共聚性单体的共聚物等。作为(甲基)丙烯酸烷基酯,例如可列举:(甲基)丙烯酸的甲酯、乙酯、丙酯、异丙酯、丁酯、异丁酯、仲丁酯、叔丁酯、戊酯、异戊酯、己酯、庚酯、辛酯、2-乙基己酯、异辛酯、壬酯、癸酯、异癸酯、十一烷基酯、十二烷基酯即月桂酯、十三烷基酯、十四烷基酯、十六烷基酯、十八烷基酯和二十烷基酯。作为(甲基)丙烯酸环烷基酯,例如可列举:(甲基)丙烯酸的环戊酯和环己酯。作为(甲基)丙烯酸芳基酯,例如可列举:(甲基)丙烯酸苯酯和(甲基)丙烯酸苄酯。源自上述含烃基的(甲基)丙烯酸酯的结构单元的含有比例相对于基础聚合物100重量份优选为40重量份以上,更优选为60重量份以上。
作为上述其它共聚性单体,例如可列举:含羧基的单体、酸酐单体、含羟基的单体、含缩水甘油基的单体、含磺酸基的单体、含磷酸基的单体、丙烯酰胺和丙烯腈等含有官能团的单体等。作为含羧基的单体,例如可列举:丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、衣康酸、马来酸、富马酸和巴豆酸。作为酸酐单体,例如可列举:马来酸酐和衣康酸酐。作为含羟基的单体,例如可列举:(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、(甲基)丙烯酸4-羟基丁酯、(甲基)丙烯酸6-羟基己酯、(甲基)丙烯酸8-羟基辛酯、(甲基)丙烯酸10-羟基癸酯、(甲基)丙烯酸12-羟基月桂酯和(4-羟基甲基环己基)甲基(甲基)丙烯酸酯。作为含缩水甘油基的单体,例如可列举:(甲基)丙烯酸缩水甘油酯和(甲基)丙烯酸甲基缩水甘油酯。作为含磺酸基的单体,例如可列举:苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯酰胺-2-甲基丙磺酸、(甲基)丙烯酰胺丙磺酸、(甲基)丙烯酸磺基丙酯和(甲基)丙烯酰氧基萘磺酸。作为含磷酸基的单体,例如可列举:2-羟基乙基丙烯酰基磷酸酯。作为丙烯酰胺,例如可列举:N-丙烯酰基吗啉。它们可以单独使用1种,也可以组合使用2种以上。源自上述共聚性单体的结构单元的含有比例相对于基础聚合物100重量份,优选为60重量份以下,更优选为40重量份以下。
丙烯酸系聚合物为了在其聚合物骨架中形成交联结构,可以包含源自多官能性单体的结构单元。作为多官能性单体,例如可列举:己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、环氧(甲基)丙烯酸酯(即,聚(甲基)丙烯酸缩水甘油酯)、聚酯(甲基)丙烯酸酯和氨基甲酸酯(甲基)丙烯酸酯。它们可以单独使用1种,也可以组合使用2种以上。源自上述多官能性单体的结构单元的含有比例相对于基础聚合物100重量份,优选为40重量份以下,更优选为30重量份以下。
上述丙烯酸系聚合物的重均分子量优选为10万~300万,更优选为20万~200万。重均分子量利用GPC(溶剂:THF)进行测定。
作为上述组合物(A1)中可使用的上述活性能量射线反应性化合物,例如可列举:含有丙烯酰基、甲基丙烯酰基、乙烯基、烯丙基、乙炔基等具有聚合性碳-碳多重键的官能团的光反应性单体或光反应性低聚物。作为该光反应性单体的具体例,可列举三羟甲基丙烷三(甲基)丙烯酸酯、四羟甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇单羟基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯等(甲基)丙烯酸与多元醇的酯化物;多官能氨基甲酸酯(甲基)丙烯酸酯;环氧(甲基)丙烯酸酯;低聚酯(甲基)丙烯酸酯等。另外,可以使用甲基丙烯酰基异氰酸酯、2-甲基丙烯酰氧基乙基异氰酸酯(2-异氰酰基乙基甲基丙烯酸酯)、间异丙烯基-α,α-二甲基苄基异氰酸酯等单体。作为光反应性低聚物的具体例,可列举上述单体的二聚物~五聚物等。光反应性低聚物的分子量优选为100~3000。
另外,作为上述活性能量射线反应性化合物,可以使用环氧化丁二烯、甲基丙烯酸缩水甘油酯、丙烯酰胺、乙烯基硅氧烷等单体;或者由该单体构成的低聚物。
进而,作为上述活性能量射线反应性化合物,可使用鎓盐等有机盐类与分子内具有多个杂环的化合物的混合物。该混合物通过活性能量射线(例如,紫外线、电子束)的照射,有机盐会裂解而生成离子,其成为起始种而引发杂环的开环反应,从而可形成三维网状结构。作为上述有机盐类,例如可列举:碘鎓盐、鏻盐、锑盐、锍盐、硼酸盐等。作为上述分子内具有多个杂环的化合物中的杂环,可列举:环氧乙烷、氧杂环丁烷、氧杂环戊烷、环硫乙烷、氮丙啶等。
上述组合物(A1)中,活性能量射线反应性化合物的含有比例相对于基础聚合物100重量份,优选为0.1重量份~500重量份,更优选为5重量份~300重量份,进一步优选为40重量份~150重量份。
作为上述组合物(A2)中包含的活性能量射线反应性聚合物(基础聚合物),例如可列举:含有丙烯酰基、甲基丙烯酰基、乙烯基、烯丙基、乙炔基等具有碳-碳多重键的官能团的聚合物。作为活性能量射线反应性聚合物的具体例,可列举:由多官能(甲基)丙烯酸酯构成的聚合物;光阳离子聚合型聚合物;聚肉桂酸乙烯酯等含有肉桂酰基的聚合物;经重氮化的氨基酚醛清漆树脂;聚丙烯酰胺等。
在一个实施方式中,可以使用在上述丙烯酸系聚合物的侧链、主链和/或主链末端导入活性能量射线聚合性的碳-碳多重键而构成的活性能量射线反应性聚合物。作为向丙烯酸系聚合物中导入辐射线聚合性碳-碳双键的方法,例如可列举如下方法:使包含具有规定官能团(第一官能团)的单体的原料单体进行共聚而得到丙烯酸系聚合物后,使具有能够与第一官能团之间发生反应而键合的规定官能团(第二官能团)和辐射线聚合性碳-碳双键的化合物在维持碳-碳双键的辐射线聚合性的状态下与丙烯酸系聚合物发生缩合反应或加成反应。
作为第一官能团与第二官能团的组合,例如可列举:羧基与环氧基、环氧基与羧基、羧基与氮丙啶基、氮丙啶基与羧基、羟基与异氰酸酯基、异氰酸酯基与羟基。在这些组合之中,从反应追踪容易度的观点出发,优选为羟基与异氰酸酯基的组合、异氰酸酯基与羟基的组合。另外,制作具有高反应性的异氰酸酯基的聚合物的技术难度高时,从丙烯酸系聚合物的制作或获取容易度的观点出发,更优选丙烯酸系聚合物侧的上述第一官能团为羟基且上述第二官能团为异氰酸酯基的情况。此时,作为兼具辐射线聚合性碳-碳双键和属于第二官能团的异氰酸酯基的异氰酸酯化合物,例如可列举:甲基丙烯酰基异氰酸酯、2-甲基丙烯酰氧基乙基异氰酸酯和间异丙烯基-α,α-二甲基苄基异氰酸酯。另外,作为具有第一官能团的丙烯酸系聚合物,优选包含源自上述含羟基的单体的结构单元,还优选包含源自2-羟基乙基乙烯基醚、4-羟基丁基乙烯基醚、二乙二醇单乙烯基醚等醚系化合物的结构单元。
上述组合物(A2)可以进一步包含上述活性能量射线反应性化合物(单体或低聚物)。
上述活性能量射线固化型组合物可以包含光聚合引发剂。
作为光聚合引发剂,可以使用任意且适当的引发剂。作为光聚合引发剂,例如可列举:4-(2-羟基乙氧基)苯基(2-羟基-2-丙基)酮、α-羟基-α,α’-二甲基苯乙酮、2-甲基-2-羟基苯丙酮、1-羟基环己基苯基酮等α-酮醇系化合物;甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、2-甲基-1-[4-(甲基硫基)-苯基]-2-吗啉基丙烷-1等苯乙酮系化合物;苯偶姻乙基醚、苯偶姻异丙基醚、茴香偶姻甲基醚等苯偶姻醚系化合物;苯偶酰二甲基缩酮等缩酮系化合物;2-萘磺酰氯等芳香族磺酰氯系化合物;1-苯酮-1,1-丙二酮-2-(邻乙氧基羰基)肟等光活性肟系化合物;二苯甲酮、苯甲酰基苯甲酸、3,3’-二甲基-4-甲氧基二苯甲酮等二苯甲酮系化合物;噻吨酮、2-氯噻吨酮、2-甲基噻吨酮、2,4-二甲基噻吨酮、异丙基噻吨酮、2,4-二氯噻吨酮、2,4-二乙基噻吨酮、2,4-二异丙基噻吨酮等噻吨酮系化合物;樟脑醌;卤代酮;酰基氧化膦;酰基膦酸酯等。光聚合引发剂的用量可设定成任意且适当的量。
在一个实施方式中,可使用波长365nm的吸光系数为10ml/g·cm~10000ml/g·cm(优选为80ml/g·cm~8000ml/g·cm、更优选为100ml/g·cm~5000ml/g·cm)的光聚合引发剂。本发明中,由于以粘合片的波长360nm的透光率成为0%~35%的方式构成气体产生层,因此可采用在中波长(例如360nm~380nm)区域内的反应性高的光聚合引发剂。包含这种光聚合引发剂的气体产生层在不应该固化的状况下,例如在保管时、在UV截止灯下使用时等,特性不易变化,在这一点上是有利的。需要说明的是,本说明书中,吸光系数是指甲醇中的吸光系数。吸光系数通过制备光聚合引发剂的甲醇溶液,并使用紫外可见近红外分光光度计(商品名“V-570”、日本分光公司制)来测定。
在一个实施方式中,上述光聚合引发剂的波长405nm的吸光系数为10ml/g·cm以下,更优选为8ml/g·cm以下。
作为上述光聚合引发剂,可以使用市售品。例如,作为光聚合引发剂,可列举:BASF公司制的商品名“Irgacure 651”、“Irgacure 184”、“Irgacure 1173”、“Irgacure 500”、“Irgacure 2959”、“Irgacure 127”、“Irgacure 754”、“Irgacure MBF”、“Irgacure 907”等。
上述光聚合引发剂的含有比例相对于粘合剂的基础聚合物100重量份,优选为0.1重量份~20重量份,更优选为0.5重量份~15重量份。
上述活性能量射线固化型组合物优选包含交联剂。作为交联剂,例如可列举:异氰酸酯系交联剂、环氧系交联剂、噁唑啉系交联剂、氮丙啶系交联剂、三聚氰胺系交联剂、过氧化物系交联剂、脲系交联剂、金属醇盐系交联剂、金属螯合物系交联剂、金属盐系交联剂、碳二亚胺系交联剂、胺系交联剂等。
上述交联剂的含有比例相对于上述活性能量射线固化型组合物中的基础聚合物100重量份,优选为0.1重量份~15重量份,更优选为0.2重量份~12重量份。
在一个实施方式中,优选使用异氰酸酯系交联剂。异氰酸酯系交联剂从能够与多种官能团发生反应的观点出发是优选的。作为上述异氰酸酯系交联剂的具体例,可列举亚丁基二异氰酸酯、六亚甲基二异氰酸酯等低级脂肪族多异氰酸酯类;亚环戊基二异氰酸酯、亚环己基二异氰酸酯、异佛尔酮二异氰酸酯等脂环族异氰酸酯类;2,4-甲苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯等芳香族异氰酸酯类;三羟甲基丙烷/甲苯二异氰酸酯三聚物加成物(日本聚氨酯工业公司制、商品名“CORONATE L”)、三羟甲基丙烷/六亚甲基二异氰酸酯三聚物加成物(日本聚氨酯工业公司制、商品名“CORONATEHL”)、六亚甲基二异氰酸酯的异氰脲酸酯体(日本聚氨酯工业公司制、商品名“CORONATEHX”)等异氰酸酯加成物等。优选使用具有3个以上异氰酸酯基的交联剂。
活性能量射线固化型组合物可根据需要而进一步包含任意且适当的添加剂。作为添加剂,例如可列举:活性能量射线聚合促进剂、自由基捕捉剂、增粘剂、增塑剂(例如偏苯三甲酸酯系增塑剂、均苯四甲酸酯系增塑剂等)、颜料、染料、填充剂、防老剂、导电材料、抗静电剂、紫外线吸收剂、光稳定剂、剥离调节剂、软化剂、表面活性剂、阻燃剂、抗氧化剂等。
C.气体阻隔层
上述气体阻隔层的利用纳米压痕法得到的弹性模量优选为0.1MPa~100MPa,更优选为0.2MPa~50MPa,进一步优选为0.3MPa~35MPa。
上述气体阻隔层的厚度优选为0.1μm~50μm,更优选为0.2μm~45μm,进一步优选为0.3μm~40μm。本发明中,即便具有薄且柔软的气体阻隔层,也能够利用激光照射而有效地发生表面变形。
上述气体阻隔层可包含任意且适当的粘合剂。作为上述气体阻隔层中包含的粘合剂A,优选使用压敏粘合剂A。作为粘合剂A,例如可列举:丙烯酸系粘合剂、橡胶系粘合剂、乙烯基烷基醚系粘合剂、有机硅系粘合剂、聚酯系粘合剂、聚酰胺系粘合剂、氨基甲酸酯系粘合剂、苯乙烯-二烯嵌段共聚物系粘合剂等。其中优选为丙烯酸系粘合剂或橡胶系粘合剂,更优选为丙烯酸系粘合剂。需要说明的是,上述粘合剂可单独使用或组合2种以上而使用。
作为上述丙烯酸系粘合剂,例如可列举将使用(甲基)丙烯酸烷基酯的1种或2种以上作为单体成分的丙烯酸系聚合物(均聚物或共聚物)作为基础聚合物的丙烯酸系粘合剂等。作为(甲基)丙烯酸烷基酯的具体例,可列举:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸异壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯等(甲基)丙烯酸C1-20烷基酯。其中,可优选使用具有碳数为4~18的直链状或支链状的烷基的(甲基)丙烯酸烷基酯。
上述丙烯酸系聚合物也可以出于内聚力、耐热性、交联性等的改性的目的,根据需要含有对应于可与上述(甲基)丙烯酸烷基酯共聚的其他单体成分的单元。作为这样的单体成分,例如可列举:丙烯酸、甲基丙烯酸、丙烯酸羧乙酯、丙烯酸羧戊酯、衣康酸、马来酸、富马酸、巴豆酸等含羧基的单体;马来酸酐、衣康酸酐等酸酐单体;(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸羟丁酯、(甲基)丙烯酸羟己酯、(甲基)丙烯酸羟辛酯、(甲基)丙烯酸羟癸酯、(甲基)丙烯酸羟基月桂酯、甲基丙烯酸(4-羟甲基环己基)甲酯等含羟基的单体;苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯酰胺-2-甲基丙磺酸、(甲基)丙烯酰胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯酰氧基萘磺酸等含磺酸基的单体;(甲基)丙烯酰胺、N,N-二甲基(甲基)丙烯酰胺、N-丁基(甲基)丙烯酰胺、N-羟甲基(甲基)丙烯酰胺、N-羟甲基丙烷(甲基)丙烯酰胺等(N-取代)酰胺系单体;(甲基)丙烯酸氨基乙酯、(甲基)丙烯酸N,N-二甲基氨基乙酯、(甲基)丙烯酸叔丁基氨基乙酯等(甲基)丙烯酸氨基烷基酯系单体;(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等(甲基)丙烯酸烷氧基烷基酯系单体;N-环己基马来酰亚胺、N-异丙基马来酰亚胺、N-月桂基马来酰亚胺、N-苯基马来酰亚胺等马来酰亚胺系单体;N-甲基衣康酰亚胺、N-乙基衣康酰亚胺、N-丁基衣康酰亚胺、N-辛基衣康酰亚胺、N-2-乙基己基衣康酰亚胺、N-环己基衣康酰亚胺、N-月桂基衣康酰亚胺等衣康酰亚胺系单体;N-(甲基)丙烯酰氧基亚甲基琥珀酰亚胺、N-(甲基)丙烯酰基-6-氧基六亚甲基琥珀酰亚胺、N-(甲基)丙烯酰基-8-氧基八亚甲基琥珀酰亚胺等琥珀酰亚胺系单体;乙酸乙烯酯、丙酸乙烯酯、N-乙烯基吡咯烷酮、甲基乙烯基吡咯烷酮、乙烯基吡啶、乙烯基哌啶酮、乙烯基嘧啶、乙烯基哌嗪、乙烯基吡嗪、乙烯基吡咯、乙烯基咪唑、乙烯基噁唑、乙烯基吗啉、N-乙烯基羧酸酰胺类、苯乙烯、α-甲基苯乙烯、N-乙烯基己内酰胺等乙烯基系单体;丙烯腈、甲基丙烯腈等氰基丙烯酸酯单体;(甲基)丙烯酸缩水甘油酯等含环氧基的丙烯酸系单体;(甲基)丙烯酸聚乙二醇酯、(甲基)丙烯酸聚丙二醇酯、(甲基)丙烯酸甲氧基乙二醇酯、(甲基)丙烯酸甲氧基聚丙二醇酯等二醇系丙烯酸酯单体;(甲基)丙烯酸四氢糠酯、氟(甲基)丙烯酸酯、有机硅(甲基)丙烯酸酯等具有杂环、卤素原子、硅原子等的丙烯酸酯系单体;己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、环氧丙烯酸酯、聚酯丙烯酸酯、氨基甲酸酯丙烯酸酯等多官能单体;异戊二烯、丁二烯、异丁烯等烯烃系单体;乙烯醚等乙烯醚系单体等。这些单体成分可单独使用或组合2种以上而使用。
作为上述橡胶系粘合剂,例如可列举将如下物质作为基础聚合物的橡胶系粘合剂:天然橡胶;聚异戊二烯橡胶、苯乙烯-丁二烯(SB)橡胶、苯乙烯-异戊二烯(SI)橡胶、苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS)橡胶、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)橡胶、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS)橡胶、苯乙烯-乙烯-丙烯-苯乙烯嵌段共聚物(SEPS)橡胶、苯乙烯-乙烯-丙烯嵌段共聚物(SEP)橡胶、再生橡胶、丁基橡胶、聚异丁烯、它们的改性体等合成橡胶等。
上述粘合剂A可根据需要含有任意适当的添加剂。作为该添加剂,例如可列举:交联剂、增粘剂(例如,松香系增粘剂、萜烯系增粘剂、烃系增粘剂等)、增塑剂(例如,偏苯三甲酸酯系增塑剂、均苯四甲酸酯系增塑剂)、颜料、染料、抗老化剂、导电材料、抗静电剂、光稳定剂、剥离调整剂、软化剂、表面活性剂、阻燃剂、抗氧化剂等。
作为上述交联剂,例如可列举:异氰酸酯系交联剂、环氧系交联剂、三聚氰胺系交联剂、过氧化物系交联剂、以及脲系交联剂、金属烷氧化物系交联剂、金属螯合物系交联剂、金属盐系交联剂、碳二亚胺系交联剂、噁唑啉系交联剂、氮丙啶系交联剂、胺系交联剂等。其中,优选为异氰酸酯系交联剂或环氧系交联剂。
作为上述异氰酸酯系交联剂的具体例,可列举:亚丁基二异氰酸酯、六亚甲基二异氰酸酯等低级脂肪族多异氰酸酯类;亚环戊基二异氰酸酯、亚环己基二异氰酸酯、异佛尔酮二异氰酸酯等脂环族异氰酸酯类;2,4-甲苯二异氰酸酯、4,4'-二苯甲烷二异氰酸酯、苯二甲基二异氰酸酯等芳香族异氰酸酯类;三羟甲基丙烷/甲苯二异氰酸酯三聚物加成物(Nippon Polyurethane Industry公司制造,商品名“Coronate L”)、三羟甲基丙烷/六亚甲基二异氰酸酯三聚物加成物(Nippon Polyurethane Industry公司制造,商品名“CoronateHL”)、六亚甲基二异氰酸酯的异氰脲酸酯体(Nippon Polyurethane Industry公司制造,商品名“Coronate HX”)等异氰酸酯加成物等。异氰酸酯系交联剂的含量可根据所需的粘合力而设定为任意适当的量,相对于基础聚合物100重量份,代表性而言为0.1重量份~20重量份,更优选为0.5重量份~10重量份。
作为上述环氧系交联剂,例如可列举:N,N,N',N'-四缩水甘油基间苯二甲胺、二缩水甘油基苯胺、1,3-双(N,N-缩水甘油基氨基甲基)环己烷(三菱瓦斯化学公司制造,商品名“Tetrad C”)、1,6-己二醇二缩水甘油醚(共荣社化学公司制造,商品名“Epolight 1600”)、新戊二醇二缩水甘油醚(共荣社化学公司制造,商品名“Epolight 1500NP”)、乙二醇二缩水甘油醚(共荣社化学公司制造,商品名“Epolight 40E”)、丙二醇二缩水甘油醚(共荣社化学公司制造,商品名“Epolight 70P”)、聚乙二醇二缩水甘油醚(日本油脂公司制造,商品名“EPIOL E-400”)、聚丙二醇二缩水甘油醚(日本油脂公司制造,商品名“EPIOL P-200”)、山梨糖醇多缩水甘油醚(Nagase chemteX公司制造,商品名“Denacol EX-611”)、甘油多缩水甘油醚(Nagase chemteX公司制造,商品名“Denacol EX-314”)、季戊四醇多缩水甘油醚、聚甘油多缩水甘油醚(Nagase chemteX公司制造,商品名“Denacol EX-512”)、山梨糖醇酐多缩水甘油醚、三羟甲基丙烷多缩水甘油醚、己二酸二缩水甘油酯、邻苯二甲酸二缩水甘油酯、三(2-羟乙基)异氰脲酸三缩水甘油酯、间苯二酚二缩水甘油醚、双酚-S-二缩水甘油醚、分子内具有2个以上环氧基的环氧系树脂等。环氧系交联剂的含量可根据所需的粘合力而设定为任意适当的量,相对于基础聚合物100重量份,代表性而言为0.01重量份~10重量份,更优选为0.03重量份~5重量份。
D.粘合剂层
作为构成在上述基材的与气体产生层相反的一侧配置的粘合剂层的粘合剂,只要能够获得本发明的效果,就可以使用任意且适当的粘合剂。作为上述粘合剂,例如可列举:丙烯酸系粘合剂、有机硅系粘合剂、乙烯基烷基醚系粘合剂、聚酯系粘合剂、聚酰胺系粘合剂、氨基甲酸酯系粘合剂、氟系粘合剂、苯乙烯-二烯嵌段共聚物系粘合剂、活性能量射线固化型粘合剂等。其中,优选为丙烯酸系粘合剂、橡胶系粘合剂或有机硅系粘合剂,更优选为丙烯酸系粘合剂。
将上述粘合片的粘合剂层贴附于聚对苯二甲酸乙二醇酯薄膜时的23℃下的粘合力优选为0.01N/20mm~15N/20mm,更优选为0.05N/20mm~10N/20mm。
上述粘合剂层的波长355nm的透光率优选为70%以上,更优选为80%以上,进一步优选为90%以上,特别优选为95%以上。上述粘合剂层的355nm的透光率的上限例如为98%(优选为99%)。
E.基材
上述基材可以由任意且适当的树脂构成。作为该树脂,例如可列举:聚乙烯系树脂、聚丙烯系树脂、聚丁烯系树脂、聚甲基戊烯系树脂等聚烯烃系树脂;聚氨酯系树脂、聚酯系树脂、聚酰亚胺系树脂、聚醚酮系树脂、聚苯乙烯系树脂、聚氯乙烯系树脂、聚偏二氯乙烯系树脂、氟系树脂、硅系树脂、纤维素系树脂、离聚物树脂等。其中,优选为聚烯烃系树脂。
上述基材的厚度优选为2μm~300μm,更优选为2μm~100μm,进一步优选为2μm~50μm。
基材的波长355nm的透光率优选为70%以上,更优选为80%以上,进一步优选为90%以上,特别优选为95%以上。基材的总光线透射率的上限例如为98%(优选为99%)。
F.粘合片的制造方法
本发明的粘合片可通过任意且适当的方法而制造。本发明的粘合片可通过例如在规定的基材上直接涂布(涂覆、固化)包含活性能量射线固化型组合物和紫外线吸收剂的气体产生层形成用组合物而形成气体产生层来获得。另外,粘合片具备气体阻隔层时,可通过在该气体产生层上涂布包含粘合剂A的气体阻隔层形成用组合物来获得粘合片。另外,也可以在分别形成各层后,进行贴合来形成粘合片。
作为上述组合物的涂布方法,可采用任意适当的涂布方法。例如,可在涂布后进行干燥而形成各层。作为涂布方法,例如可列举使用多层涂布机(multi coater)、模涂布机、凹版涂布机、涂抹器等的涂布方法。作为干燥方法,例如可列举:自然干燥、加热干燥等。进行加热干燥的情况下的加热温度可根据成为干燥对象的物质的特性而设定为任意适当的温度。此外,可根据各层的形态而进行活性能量射线照射(例如,紫外线照射)。
G.电子部件的加工方法
本发明的电子部件的处理方法包括:将电子部件贴附于上述粘合片;及对该粘合片照射激光,自该粘合片剥离电子部件。作为电子部件,例如可列举:半导体芯片、LED芯片、MLCC等。
上述电子部件的剥离可选择位置地进行。具体而言,将多个电子部件贴附、固定于粘合片,能以将电子部件的一部分剥离、其他电子部件仍被固定的方式进行电子部件的剥离。
在一个实施方式中,本发明的电子部件的处理方法包括:在将电子部件贴附于粘合片后且自粘合片剥离电子部件前,对该电子部件进行规定的处理。上述处理并无特别限定,例如可列举:研磨加工、切割加工、芯片接合、引线接合、蚀刻、蒸镀、模塑、电路形成、检查、产品检验、清洗、转印、排列、修复、装置表面的保护等处理。
上述电子部件的尺寸(贴附面的面积)例如为1μm2~250000μm2。在一个实施方式中,可将电子部件的尺寸(贴附面的面积)为1μm2~6400μm2的电子部件供于处理。在其他实施方式中,可将电子部件的尺寸(贴附面的面积)为1μm2~2500μm2的电子部件供于处理。
在一个实施方式中,如上所述可将多个电子部件配置于粘合片上。电子部件的间隔例如为1μm~500μm。本发明在可缩小间隔地暂时固定被处理物的方面是有利的。
作为激光,例如可使用UV激光。激光的照射功率例如为1μJ~1000μJ。UV激光的波长例如为240nm~380nm。
在一个实施方式中,上述电子部件的处理方法包括:在电子部件剥离后,将该电子部件配置于其他片材(例如,粘合片、基板等)。
实施例
以下,通过实施例来具体说明本发明,但本发明并不受这些实施例的限定。实施例中的试验和评价方法如下所述。另外,只要没有明确记载,则“份”和“%”是重量基准。
(1)初始粘合力
将粘合片的气体阻隔层(实施例17中的气体产生层)贴附于SUS304BA,利用基于JIS Z 0237:2000的方法(贴合条件:2kg辊往返1次、拉伸速度:300mm/min、剥离角度:180°、测定温度:23℃),测定对于该粘合片而言的粘合力。另外,将粘合片的气体阻隔层(实施例17中的气体产生层)贴附于不锈钢板等支承体来进行固定,将在基材的与气体产生层相反的一侧配置的粘合剂层贴附于聚对苯二甲酸乙二醇酯薄膜(东丽公司制、商品名“LumirrorS10”、厚度:25μm),利用基于JIS Z 0237:2000的方法(贴合条件:2kg辊往返1次、拉伸速度:300mm/min、剥离角度:180°、测定温度:23℃)来测定粘合剂层的粘合力。
(2)透光率
将粘合片置于分光光度计(商品名“UV-VIS紫外可见分光光度计SolidSpec3700”、岛津制作所制),使得入射光朝着样品的气体阻隔层侧垂直入射,测定300nm~800nm的波长区域的透光率。抽取所得透射光谱的360nm、380nm和500nm的波长处的透射率。
(3-1)粘合片的表面形状变化
在粘合片的粘合剂层侧贴合玻璃板(松波硝子公司制、大型载玻片S9112(标准大型白缘磨No.2)),得到测定样品。使用波长355nm、光束直径约为20μmφ的UV激光,以0.80mW的功率、40kHz的频率从测定样品的玻璃板侧进行脉冲扫描,使气体产生层产生气体。观察因这种操作而产生的粘合片表面(气体阻隔层表面、实施例17中的气体产生层表面)的形状变化。
(3-2)粘合片的表面形状变化(剥离性、剥离的位置选择性)
在粘合片的粘合剂层侧贴合玻璃板(松波硝子公司制、大型载玻片S9112(标准大型白缘磨No.2)),得到测定样品。使用波长355nm、光束直径约为20μmφ的UV激光,以0.80mW的功率、40kHz的频率从测定样品的玻璃板侧进行脉冲扫描,使气体产生层产生气体。对于与脉冲扫描过的任意1点对应的气体阻隔层表面(实施例17中的气体产生层表面),在激光照射后1分钟后,利用共焦激光显微镜进行观察,测定垂直位移Y和水平位移X(直径;半峰全宽)。
在位移Y为1μm以上的情况下,剥离性优异(表中,〇);在位移Y为0.6μm以上且小于1μm的情况下,剥离性良好(表中,△);在位移Y小于0.6μm的情况下,剥离性不充分(表中,×)。在位移X为50μm以下的情况下,剥离的位置选择性优异(表中,〇);在位移X超过50μm的情况下,剥离的位置选择性不充分(表中,×)。
(4)雾度值
使用雾度计(商品名“HAZE METER HM-150”、村上色彩技术研究所制),测定粘合片的雾度值。
(5)10%重量减少温度
关于紫外线吸收剂,测定10%重量减少温度。
使用差热分析装置(TA Instruments公司制、商品名“Discovery TGA”),对于粘合片,升温温度设为10℃/分钟,在N2气氛下,流量设为25ml/分钟,测定重量减少10%时的温度。
(6)弹性模量
使用纳米压痕仪(Hysitron Inc制、Triboindenter TI-950),利用规定温度(25℃)下的单一压痕法,在压痕速度约为500nm/sec、拔出速度约为500nm/sec、压入深度约为1500nm的测定条件下,测定弹性模量。
[制造例1]丙烯酸类聚合物I的制造
向乙酸乙酯中添加丙烯酸2-乙基己酯95重量份、丙烯酸5重量份、作为聚合引发剂的过氧化苯甲酰0.15重量份后,加热至70℃,得到丙烯酸系共聚物(丙烯酸类聚合物I)的乙酸乙酯溶液。
[制造例2]丙烯酸类聚合物II的制造
向甲苯中添加丙烯酸2-乙基己酯100重量份、丙烯酸2-羟基乙酯12.6重量份、作为聚合引发剂的过氧化苯甲酰0.25重量份后,在氮气气流下以60℃进行聚合反应,向其中添加甲基丙烯酰氧基乙基异氰酸酯13.5份,使其进行加成反应,由此得到具有碳-碳双键的丙烯酸系共聚物(丙烯酸类聚合物II)的甲苯溶液。
[实施例1]
(气体阻隔层形成用粘合剂A(1)的制备)
向包含100重量份丙烯酸系聚合物I的丙烯酸系聚合物的乙酸乙酯溶液I中添加环氧系交联剂(三菱瓦斯公司制、商品名“TETRAD-C”)1重量份、异氰酸酯交联剂(日本聚氨酯公司制、商品名“CORONATE L”)3重量份,制备气体阻隔层形成用粘合剂A(1)。
(气体产生层形成用组合物的制备)
向包含100重量份丙烯酸系聚合物II的丙烯酸系聚合物的甲苯溶液I中添加异氰酸酯系交联剂(日本聚氨酯公司制、商品名“CORONATE L”)0.2重量份、光聚合引发剂(BASF公司制、商品名“Irgacure127”)3重量份和紫外线吸收剂(BASF公司制、商品名“Tinuvin400”)20重量份,制备气体产生层形成用组合物(1)。
(粘合剂(2)的制备)
向包含100重量份丙烯酸系聚合物I的丙烯酸系聚合物的乙酸乙酯溶液I中添加环氧系交联剂(三菱瓦斯公司制、商品名“TETRAD-C”)2重量份,制备粘合剂(2)。
(粘合片)
在聚对苯二甲酸乙二醇酯薄膜(东丽公司制、商品名“Lumirror S10”、厚度:50μm)的一个面上,以溶剂挥发(干燥)后的厚度成为10μm的方式涂布粘合剂(2),形成粘合剂层。
接着,在上述聚对苯二甲酸乙二醇酯薄膜(东丽公司制、商品名“LumirrorS10”、厚度:50μm)的另一个面上,以溶剂挥发(干燥)后的厚度成为10μm的方式涂布气体产生层形成用组合物(1),形成气体产生层的前体层。
接着,在带有机硅脱模剂处理面的聚对苯二甲酸乙二醇酯薄膜(东丽公司制、商品名“Cerapeel”、厚度:38μm)上,以溶剂挥发(干燥)后的厚度成为10μm的方式,涂布气体阻隔层形成用粘合剂A(1),形成气体阻隔层。
接着,将气体产生层的前体层与气体阻隔层进行层叠,得到被带有机硅脱模剂处理面的聚对苯二甲酸乙二醇酯薄膜和聚对苯二甲酸乙二醇酯薄膜夹持的粘合片前体(气体阻隔层/气体产生层/基材)。隔着该粘合片前体的气体阻隔层侧的带有机硅脱模剂处理面的聚对苯二甲酸乙二醇酯薄膜,照射500mJ/cm2的紫外线,得到粘合片。上述紫外线照射通过使用紫外线照射装置(日东精机公司制、商品名“UM-810”),对气体产生层照射高压汞灯的紫外线(特性波长:365nm、累积光量:500mJ/cm2、照射能量:70W/cm2、照射时间:7.1秒)来进行。
将所得粘合片供于上述评价(1)~(6)。将结果示于表1。
[实施例2~16、比较例1~5]
除了如表1那样地设定气体阻隔层的厚度、气体产生层的厚度、紫外线吸收剂的配混量、交联剂的配混量之外,与实施例1同样操作,得到粘合片。将所得粘合片供于上述评价(1)~(6)。将结果示于表1~4。需要说明的是,实施例10~13和17、以及比较例3~5不对气体产生层照射紫外线地形成该气体产生层。
[实施例17]
与实施例1同样操作,制备气体产生层形成用组合物(1)。
与实施例1同样操作,制备粘合剂(2)。
在聚对苯二甲酸乙二醇酯薄膜(东丽公司制、商品名“Lumirror S10”、厚度:50μm)的一个面上,以溶剂挥发(干燥)后的厚度成为10μm的方式涂布粘合剂(2),形成粘合剂层。在聚对苯二甲酸乙二醇酯薄膜(东丽公司制、商品名“Lumirror S10”、厚度:50μm)的另一个面上,以溶剂挥发(干燥)后的厚度成为10μm的方式涂布气体产生层形成用组合物(1),形成气体产生层的前体层。
将如此操作而得到的粘合片供于上述评价(1)~(6)。将结果示于表3。
[表1]
[表2]
[表3]
[表4]
附图标记说明
10 气体产生层
20 气体阻隔层
100、200 粘合片
Claims (19)
1.一种粘合片,其具备通过激光照射而产生气体的气体产生层,
该气体产生层的利用纳米压痕法得到的弹性模量Er(gas)[单位:MPa]与厚度h(gas)[单位:μm]满足下述式(1):
Log(Er(gas)×106)≥8.01×h(gas)-0.116···(1)。
2.根据权利要求1所述的粘合片,其中,波长360nm的透光率为0%~40%。
3.根据权利要求1或2所述的粘合片,其中,波长380nm的透光率为10%~100%。
4.根据权利要求1至3中任一项所述的粘合片,其中,所述气体产生层含有紫外线吸收剂,
该紫外线吸收剂的最大吸收波长为360nm以下。
5.根据权利要求1至4中任一项所述的粘合片,其中,所述气体产生层为活性能量射线固化型组合物的固化物。
6.根据权利要求1至5中任一项所述的粘合片,其中,所述气体产生层含有丙烯酸系聚合物。
7.根据权利要求1至6中任一项所述的粘合片,其中,在所述气体产生层的至少单侧具备气体阻隔层,
该气体阻隔层的利用纳米压痕法得到的弹性模量为0.1MPa~100MPa。
8.根据权利要求7所述的粘合片,其中,所述气体阻隔层的厚度为0.1μm~50μm。
9.根据权利要求1至8中任一项所述的粘合片,其中,所述阻隔层表现出粘合性。
10.根据权利要求1至9中任一项所述的粘合片,其中,波长500nm的透光率为70%~100%。
11.根据权利要求1至10中任一项所述的粘合片,其中,雾度值为50%以下。
12.根据权利要求1至11中任一项所述的粘合片,其中,所述粘合片的表面通过激光照射而变形。
13.根据权利要求12所述的粘合片,其中,所述粘合片的表面通过激光照射而变形为凸状。
14.根据权利要求12或13所述的粘合片,其中,通过对所述粘合片的激光照射而产生的该粘合片表面的水平位移为50μm以下。
15.一种电子部件的处理方法,其包括:将电子部件贴附于权利要求1至14中任一项所述的粘合片上;及对该粘合片照射激光而自该粘合片剥离该电子部件。
16.根据权利要求15所述的电子部件的处理方法,其中,所述电子部件的剥离选择位置地进行。
17.根据权利要求15或16所述的电子部件的处理方法,其包括:
在将所述电子部件贴附于所述粘合片之后且自该粘合片剥离该电子部件之前,
对该电子部件进行规定的处理。
18.根据权利要求17所述的电子部件的处理方法,其中,所述处理为研磨加工、切割加工、芯片接合、引线接合、蚀刻、蒸镀、模塑、电路形成、检查、产品检验、清洗、转印、排列、修复或装置表面的保护。
19.根据权利要求15至18中任一项所述的电子部件的处理方法,其包括:自所述粘合片剥离所述电子部件之后,将电子部件配置于其他片材。
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JP3594853B2 (ja) | 1999-11-08 | 2004-12-02 | 日東電工株式会社 | 加熱剥離型粘着シート |
JP2003342540A (ja) * | 2002-05-28 | 2003-12-03 | Asahi Kasei Corp | 半導体加工用粘着シート |
JP2004186200A (ja) * | 2002-11-29 | 2004-07-02 | Sekisui Chem Co Ltd | 半導体チップの製造方法 |
JP2005097507A (ja) * | 2003-09-02 | 2005-04-14 | Sekisui Chem Co Ltd | 粘着テープ |
JP2010129699A (ja) * | 2008-11-26 | 2010-06-10 | Nitto Denko Corp | ダイシング・ダイボンドフィルム及び半導体装置の製造方法 |
JP2010202833A (ja) * | 2009-03-05 | 2010-09-16 | Sekisui Chem Co Ltd | 電子部品加工用粘着テープ |
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JP7019333B2 (ja) * | 2017-04-17 | 2022-02-15 | 日東電工株式会社 | ダイシングダイボンドフィルム |
JP7088736B2 (ja) * | 2017-10-06 | 2022-06-21 | 積水化学工業株式会社 | 表面保護フィルム |
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JPWO2021131518A1 (ja) | 2021-12-23 |
US20220372349A1 (en) | 2022-11-24 |
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