JP2016094334A - Heat resistant aluminum hydroxide particle and manufacturing method therefor, resin composition, prepreg and laminate - Google Patents
Heat resistant aluminum hydroxide particle and manufacturing method therefor, resin composition, prepreg and laminate Download PDFInfo
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- aluminum hydroxide
- hydroxide particles
- fluorine
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- resistant aluminum
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- 239000002245 particle Substances 0.000 title claims abstract description 102
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 title claims abstract description 99
- 239000011342 resin composition Substances 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 50
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 50
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 31
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 27
- 230000018044 dehydration Effects 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 239000011888 foil Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 31
- 239000012298 atmosphere Substances 0.000 abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- -1 fluorine ions Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 125000001153 fluoro group Chemical group F* 0.000 description 8
- 229910000679 solder Inorganic materials 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 2
- 229910017944 Ag—Cu Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- 229910020816 Sn Pb Inorganic materials 0.000 description 2
- 229910020888 Sn-Cu Inorganic materials 0.000 description 2
- 229910020922 Sn-Pb Inorganic materials 0.000 description 2
- 229910019204 Sn—Cu Inorganic materials 0.000 description 2
- 229910008783 Sn—Pb Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000019000 fluorine Nutrition 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
本発明は、主に、プリント配線板基材を作製する際に用いられる耐熱性水酸化アルミニウム粒子及びその製造方法、樹脂組成物、プリプレグ、積層板に関する。 The present invention mainly relates to heat-resistant aluminum hydroxide particles used for producing a printed wiring board substrate, a method for producing the same, a resin composition, a prepreg, and a laminate.
プリント配線板用基材等の樹脂組成物の難燃性を確保するために、従来はハロゲン系の難燃材が使用されていた。しかし、近年、環境問題への関心の高まりとともにダイオキシン等の有害物質を発生しない水酸化アルミニウム、水酸化マグネシウム等の金属水酸化物を難燃性フィラーとして充填したものが増えている。 Conventionally, halogen-based flame retardants have been used in order to ensure the flame retardancy of resin compositions such as printed wiring board substrates. However, in recent years, with increasing interest in environmental problems, there has been an increase in those filled with metal hydroxides such as aluminum hydroxide and magnesium hydroxide that do not generate harmful substances such as dioxins as flame retardant fillers.
特に水酸化アルミニウムは含水量が多く、難燃効果が大きいだけでなく、耐酸性や耐アルカリ性等の耐薬品性に優れるため、難燃性フィラーとして広く使用されている。この水酸化アルミニウムは２００℃以上で吸熱を伴って脱水反応を起こし、χ−アルミナに変化する。この吸熱反応により樹脂組成物の温度上昇を抑制し、発生した水蒸気により可燃性のガスを希釈することにより燃焼が抑制される。 In particular, aluminum hydroxide is widely used as a flame retardant filler because it has a high water content and a large flame retardant effect, as well as excellent chemical resistance such as acid resistance and alkali resistance. This aluminum hydroxide undergoes a dehydration reaction with endotherm at 200 ° C. or higher, and changes to χ-alumina. By this endothermic reaction, the temperature rise of the resin composition is suppressed, and combustion is suppressed by diluting the combustible gas with the generated water vapor.
一方、プリント配線板用基材には、はんだにより電子部品が実装されるために、はんだ溶融温度以上の耐熱性が要求される。はんだには従来Ｓｎ−Ｐｂ系はんだが使用されていたが、鉛の毒性の問題からＳｎ−Ｃｕ系、Ｓｎ−Ａｇ−Ｃｕ系等の鉛フリーはんだへの転換が進んでいる。これらの材料の融点は、従来のＳｎ−Ｐｂ系はんだの１８３℃に対してＳｎ−Ｃｕ系、Ｓｎ−Ａｇ−Ｃｕ系等の鉛フリーはんだでは２２０℃付近であり、約４０℃上昇している。このため従来の水酸化アルミニウム使用すると、実装時の加熱により水酸化アルミニウムが脱水反応を起こし、生じた水蒸気により基材に膨れが生じるという問題が生じる。
このような問題を解決するために、種々の熱分解温度を向上させた耐熱性水酸化アルミニウムの製造方法が提案されている。（例えば、特許文献１〜３参照）
On the other hand, the printed wiring board base material is required to have heat resistance equal to or higher than the solder melting temperature because electronic components are mounted by solder. Conventionally, Sn—Pb solder has been used as the solder, but due to the toxicity of lead, conversion to lead-free solders such as Sn—Cu and Sn—Ag—Cu is progressing. The melting point of these materials is about 220 ° C. for lead-free solders such as Sn—Cu type and Sn—Ag—Cu type, which is about 40 ° C., higher than 183 ° C. of conventional Sn—Pb type solder. . Therefore, when conventional aluminum hydroxide is used, there arises a problem that the aluminum hydroxide causes a dehydration reaction due to heating during mounting, and the base material is swollen by the generated water vapor.
In order to solve such problems, methods for producing heat-resistant aluminum hydroxide with various pyrolysis temperatures improved have been proposed. (For example, see Patent Documents 1 to 3)
しかしながら、特許文献１のように水酸化アルミニウム粒子を大気下で加熱処理し、水酸化アルミニウムを化学式Ａｌ２Ｏ３・３Ｈ２Ｏで表したときに、含水量の３モルを１．８〜２．７モルまで減らした場合には、放出可能な水分量が減るため難燃性が低下するという問題が生じる。 However, when aluminum hydroxide particles are heat-treated in the atmosphere as in Patent Document 1 and the aluminum hydroxide is represented by the chemical formula Al 2 O 3 .3H 2 O, 3 mol of water content is 1.8-2. When the amount is reduced to 7 mol, the amount of water that can be released decreases, resulting in a problem that flame retardancy is reduced.
特許文献２のように水酸化アルミニウム粒子を１７０℃程度で水熱処理し、一部をベーマイトに転換した場合には、ベーマイトに転換する温度が低いため、未反応の水酸化アルミニウムには１７０℃程度の熱履歴しか付与されておらず、充分な高耐熱化ができない。 When the aluminum hydroxide particles are hydrothermally treated at about 170 ° C. and partially converted to boehmite as in Patent Document 2, the temperature of conversion to boehmite is low, so unreacted aluminum hydroxide is about 170 ° C. Only a heat history is given, and sufficient heat resistance cannot be achieved.
特許文献３のように水酸化アルミニウム粒子にベーマイト化を遅延させる反応遅延剤を混合し、水熱処理した場合には２５０℃程度までの熱処理が可能になり、高耐熱化が可能になる。しかし、高耐圧の反応設備が必要になる他、樹脂と混合した場合に添加した反応遅延剤による特性低下が発生する可能性がある。 When a reaction retarder that delays the formation of boehmite is mixed with aluminum hydroxide particles as in Patent Document 3, heat treatment up to about 250 ° C. is possible, and heat resistance can be increased. However, in addition to the need for a high pressure resistant reaction facility, there is a possibility that characteristic deterioration due to a reaction retarder added when mixed with a resin may occur.
以上のように、鉛フリーはんだに対応可能なプリント配線板基材には耐熱性と難燃性、即ち高い脱水開始温度と充分な脱水量を示す水酸化アルミニウム粒子が求められていた。
本発明の目的は、従来の水酸化アルミニウムでは達成が困難な高い脱水開始温度と充分な脱水量を併せ持つ耐熱性水酸化アルミニウム粒子及びその製造方法、並びに当該耐熱性水酸化アルミニウム粒子を含有する樹脂組成物、プリプレグ、積層板を提供するものである。
As described above, printed wiring board substrates that can be used for lead-free solder have been required to have aluminum hydroxide particles exhibiting heat resistance and flame retardancy, that is, a high dehydration start temperature and a sufficient dehydration amount.
An object of the present invention is to provide a heat-resistant aluminum hydroxide particle having a high dehydration start temperature and a sufficient amount of dehydration, which are difficult to achieve with conventional aluminum hydroxide, a method for producing the same, and a resin containing the heat-resistant aluminum hydroxide particles A composition, a prepreg, and a laminate are provided.
上記目的は、下記本発明により達成される。すなわち、本発明は下記の通りである。
［１］ 水酸化アルミニウム粒子を、フッ素を含有するガス雰囲気で２００℃〜２７０℃の加熱処理を行い、前記水酸化アルミニウム粒子の水酸基の一部をフッ素に置換した耐熱性水酸化アルミニウム粒子。
［２］ 水酸化アルミニウム粒子を、フッ素イオンを含む溶液で処理し、前記水酸化アルミニウム粒子の水酸基の一部をフッ素に置換した後、２００℃〜２７０℃の加熱処理を施した耐熱性水酸化アルミニウム粒子。
The above object is achieved by the present invention described below. That is, the present invention is as follows.
[1] Heat-resistant aluminum hydroxide particles obtained by subjecting aluminum hydroxide particles to a heat treatment at 200 ° C. to 270 ° C. in a gas atmosphere containing fluorine, and substituting some of the hydroxyl groups of the aluminum hydroxide particles with fluorine.
[2] Heat-resistant hydroxylation in which aluminum hydroxide particles are treated with a solution containing fluorine ions, and a part of the hydroxyl groups of the aluminum hydroxide particles are replaced with fluorine, followed by heat treatment at 200 ° C to 270 ° C. Aluminum particles.
［３］ 水酸化アルミニウム粒子表面に存在するフッ素の比率が１〜２０ａｔ％であり、熱分解開始温度が２６０℃以上、脱水量が３２質量％以上である［１］又は［２］に記載の耐熱性水酸化アルミニウム粒子。
［４］ Ｎａ２Ｏ濃度が０．３質量％以下であり、平均粒径が０．５〜５μｍである［１］〜［３］のいずれかに記載の耐熱性水酸化アルミニウム粒子。
[3] The ratio of fluorine present on the surface of the aluminum hydroxide particles is 1 to 20 at%, the thermal decomposition starting temperature is 260 ° C. or higher, and the dehydration amount is 32 mass% or higher. Heat resistant aluminum hydroxide particles.
[4] The heat-resistant aluminum hydroxide particles according to any one of [1] to [3], wherein the Na 2 O concentration is 0.3% by mass or less and the average particle size is 0.5 to 5 μm.
［５］ 水酸化アルミニウム粒子を、フッ素含有ガスの存在下で２００℃〜２７０℃の加熱処理を行い、水酸化アルミニウム粒子の水酸基の一部をフッ素に置換した耐熱性水酸化アルミニウム粒子の製造方法。
［６］ 水酸化アルミニウム粒子を、フッ素イオンを含む溶液で処理し、水酸化アルミニウム粒子の水酸基の一部をフッ素に置換した後、２００℃〜２７０℃の加熱処理を施す耐熱性水酸化アルミニウム粒子の製造方法。
[5] A method for producing heat-resistant aluminum hydroxide particles, wherein the aluminum hydroxide particles are subjected to a heat treatment at 200 ° C. to 270 ° C. in the presence of a fluorine-containing gas, and a part of the hydroxyl groups of the aluminum hydroxide particles are replaced with fluorine. .
[6] Heat-resistant aluminum hydroxide particles in which aluminum hydroxide particles are treated with a solution containing fluorine ions, and a portion of the hydroxyl groups of the aluminum hydroxide particles are replaced with fluorine, followed by heat treatment at 200 ° C to 270 ° C. Manufacturing method.
［７］ 前記フッ素含有ガスのフッ素源がフッ化アンモニウムであり、２００℃〜２７０℃の加熱処理前に、水酸化アルミニウム粒子とフッ化アンモニウムとを混合する［５］又は［６］に記載の耐熱性水酸化アルミニウム粒子の製造方法。 [7] The fluorine source of the fluorine-containing gas is ammonium fluoride, and aluminum hydroxide particles and ammonium fluoride are mixed before heat treatment at 200 ° C. to 270 ° C. [5] or [6] A method for producing heat-resistant aluminum hydroxide particles.
［８］ 上記［１］〜［４］のいずれかに記載の耐熱性水酸化アルミニウム粒子を含む樹脂組成物。
［９］ 基材に上記［８］に記載の樹脂組成物が含浸、乾燥されてなるプリプレグ。
［１０］ 上記［９］に記載のプリプレグの硬化物の少なくとも一方の面に導体層を有する積層板。
[8] A resin composition comprising the heat-resistant aluminum hydroxide particles according to any one of [1] to [4].
[9] A prepreg obtained by impregnating the substrate with the resin composition according to [8] and drying.
[10] A laminate having a conductor layer on at least one surface of the cured product of the prepreg according to [9].
本発明によれば、従来の水酸化アルミニウムでは達成が困難な高い脱水開始温度と充分な脱水量を併せ持つ耐熱性水酸化アルミニウム粒子及びその製造方法、並びに当該耐熱性水酸化アルミニウム粒子を含有する樹脂組成物、プリプレグ、積層板を提供することができる。
当該本発明により、耐熱性が高く、製造プロセスマージンが広く、難燃特性に優れるプリント配線板用基材の製造が可能になる。
According to the present invention, heat-resistant aluminum hydroxide particles having a high dehydration start temperature and a sufficient amount of dehydration that are difficult to achieve with conventional aluminum hydroxide, a method for producing the same, and a resin containing the heat-resistant aluminum hydroxide particles Compositions, prepregs, and laminates can be provided.
According to the present invention, it is possible to manufacture a substrate for a printed wiring board having high heat resistance, a wide manufacturing process margin, and excellent flame retardancy.
［耐熱性水酸化アルミニウム粒子及びその製造方法］
以下、本発明を詳細に説明する。
無機物の熱分解は一般に活性化エネルギーの低い表面や、粒界の結晶転移やその他の欠陥部分から始まるとされる。そこで耐熱性を向上させるためには活性化エネルギーの低い箇所を、より安定な他の材料に変えることや、予め熱分解させ安定化することが有効である。水酸化アルミニウム粒子においては大気下での熱分解によりχ−アルミナに変化させる。活性化エネルギーの低い箇所を安定な脱水物に変えることにより、熱分解開始温度が上昇する。
[Heat-resistant aluminum hydroxide particles and production method thereof]
Hereinafter, the present invention will be described in detail.
In general, thermal decomposition of inorganic substances is considered to start from a surface with a low activation energy, a crystal transition at a grain boundary, and other defective portions. Therefore, in order to improve the heat resistance, it is effective to change the portion having a low activation energy to another more stable material, or to thermally decompose and stabilize in advance. Aluminum hydroxide particles are converted to χ-alumina by thermal decomposition in the atmosphere. By changing the portion with low activation energy into a stable dehydrated product, the thermal decomposition starting temperature increases.
一方、熱分解により生じるχ−アルミナは別名活性アルミナと呼ばれ、比表面積が大きく、吸湿性の大きい材料である。このためプリント配線板基材用フィラーとして充填した場合、吸着により表面に保持している水分量が増加するため、リフロー温度である２６０℃付近までの加熱によって生じる水分量を増やす作用がある。 On the other hand, χ-alumina produced by thermal decomposition is also called activated alumina, which is a material having a large specific surface area and a high hygroscopic property. For this reason, when it fills as a filler for printed wiring board base materials, since the moisture content currently hold | maintained on the surface by adsorption | suction increases, there exists an effect | action which increases the moisture content produced by the heating to 260 degreeC which is reflow temperature.
本発明はこの問題点に鑑みなされた。すなわち、水酸化アルミニウム粒子の耐熱性を向上させるために水酸化アルミニウムの表面の水酸基を、より熱分解温度の高いフッ素と置換するために、所定の加熱処理を行う（本発明の第１の態様）又は所定の液相での処理及び加熱処理を行う（本発明の第２の態様）ことによって、耐熱性に優れ吸湿性の低い水酸化アルミニウム粒子の提供を可能とするものである。以下、本発明の第１の態様及び第２の態様について説明する。なお、第１の態様及び第２の態様を合わせて「本発明」ということがある。 The present invention has been made in view of this problem. That is, in order to improve the heat resistance of the aluminum hydroxide particles, a predetermined heat treatment is performed in order to replace the hydroxyl group on the surface of the aluminum hydroxide with fluorine having a higher thermal decomposition temperature (first aspect of the present invention). Or by performing a treatment in a predetermined liquid phase and a heat treatment (second aspect of the present invention), it is possible to provide aluminum hydroxide particles having excellent heat resistance and low hygroscopicity. Hereinafter, the first aspect and the second aspect of the present invention will be described. The first aspect and the second aspect may be collectively referred to as “the present invention”.
（本発明の第１の態様）
本発明の第１の態様は、水酸化アルミニウム粒子を、フッ素を含有するガス雰囲気で２００℃〜２７０℃の加熱処理を行い、前記水酸化アルミニウム粒子の水酸基の一部をフッ素に置換した耐熱性水酸化アルミニウム粒子である。
(First aspect of the present invention)
The first aspect of the present invention is a heat resistance in which aluminum hydroxide particles are subjected to a heat treatment at 200 ° C. to 270 ° C. in a fluorine-containing gas atmosphere, and a part of the hydroxyl groups of the aluminum hydroxide particles are substituted with fluorine. Aluminum hydroxide particles.
フッ素を含有するガス雰囲気（気相）で処理を行う場合には、フッ化水素酸ガス、フッ素ガス、又はフッ化アンモニウムの加熱分解ガス等のフッ素を含むガス雰囲気で加熱処理を施すことにより、水酸化アルミニウムの水酸基をフッ素と置換する。 When the treatment is performed in a gas atmosphere (vapor phase) containing fluorine, by performing the heat treatment in a gas atmosphere containing fluorine such as hydrofluoric acid gas, fluorine gas, or heat decomposition gas of ammonium fluoride, The hydroxyl group of aluminum hydroxide is replaced with fluorine.
気相での処理ではフッ素との置換処理と熱処理とを同時に行うことができる。フッ化水素酸ガス又はフッ素ガスを使用する場合には加熱雰囲気中にこれらのガスを導入することにより、また、フッ化アンモニウムを使用する場合には、水酸化アルミニウム粒子にフッ化アンモニウムを添加した容器を加熱することにより、フッ化アンモニウムが分解、昇華してフッ素を含むガス雰囲気を作ることができる。 In the treatment in the gas phase, the substitution treatment with fluorine and the heat treatment can be performed simultaneously. When hydrofluoric acid gas or fluorine gas is used, these gases are introduced into the heating atmosphere. When ammonium fluoride is used, ammonium fluoride is added to the aluminum hydroxide particles. By heating the container, the ammonium fluoride can be decomposed and sublimated to create a gas atmosphere containing fluorine.
処理温度が２７０℃以下であるとχ−アルミナの生成速度が大きくなるのを防ぎ、脱水量の制御を容易にすることができる。また、２００℃以上であると実用的な処理時間では熱分解開始温度の上昇させることができる。処理温度は、２１０℃〜２６０℃であることが好ましい。
処理時間は例えば０．１〜１０時間であることが好ましく、０．５〜５時間であることがより好ましい。
When the treatment temperature is 270 ° C. or less, the generation rate of χ-alumina can be prevented from increasing, and the amount of dehydration can be easily controlled. Moreover, if it is 200 ° C. or higher, the thermal decomposition starting temperature can be increased in a practical treatment time. The treatment temperature is preferably 210 ° C to 260 ° C.
The treatment time is preferably 0.1 to 10 hours, for example, and more preferably 0.5 to 5 hours.
（本発明の第２の態様）
本発明の第２の態様は、水酸化アルミニウム粒子を、フッ素イオンを含む溶液で処理し、前記水酸化アルミニウム粒子の水酸基の一部をフッ素に置換した後、２００℃〜２７０℃の加熱処理を施した耐熱性水酸化アルミニウム粒子である。
(Second aspect of the present invention)
In the second aspect of the present invention, the aluminum hydroxide particles are treated with a solution containing fluorine ions, and a part of the hydroxyl groups of the aluminum hydroxide particles are replaced with fluorine, and then heat treatment is performed at 200 ° C. to 270 ° C. Heat-resistant aluminum hydroxide particles applied.
フッ素イオンを含む溶液で処理（液相での処理）を行う場合には、フッ素イオンを含む溶液に水酸化アルミニウムを浸漬・攪拌すればよい。フッ素を含む溶液はフッ酸又はフッ化ナトリウム、フッ化カリウム等のフッ素のアルカリ金属塩、フッ化マグネシウム、フッ化カルシウム等のフッ素のアルカリ土類金属塩、フッ化アンモニウム、フッ化アルミニウム等のフッ化物塩を１種又は複数含む溶液が使用できる。なかでも水への溶解度が大きく、３００℃以下の焼成で揮発し、不純物イオンを増加させることのないフッ酸、フッ化アンモニウムが好ましい。 When processing with a solution containing fluorine ions (processing in a liquid phase), aluminum hydroxide may be immersed and stirred in a solution containing fluorine ions. Fluorine-containing solutions include fluorine alkali metal salts such as hydrofluoric acid, sodium fluoride, and potassium fluoride, fluorine alkaline earth metal salts such as magnesium fluoride and calcium fluoride, ammonium fluoride, aluminum fluoride, and other fluorides. Solutions containing one or more chloride salts can be used. Of these, hydrofluoric acid and ammonium fluoride, which have a high solubility in water, volatilize by firing at 300 ° C. or lower and do not increase impurity ions, are preferable.
浸漬する時間は１０分から１時間程度であり、浸漬する温度は室温付近から水の沸騰する１００未満で行うことが好ましいが特に制限はない。フッ化物イオンの濃度は水酸化アルミニウムの処理量と溶液の量とから適宜選定するが、実用的な範囲は０．０１ｍｏｌ／リットルから１０ｍｏｌ／リットルである。 The immersion time is about 10 minutes to 1 hour, and the immersion temperature is preferably less than 100 where water is boiled from around room temperature, but there is no particular limitation. The concentration of fluoride ions is appropriately selected from the amount of aluminum hydroxide treated and the amount of solution, but the practical range is 0.01 mol / liter to 10 mol / liter.
液相で置換処理を行った後、水酸化アルミニウム粒子はろ過や遠心分離により水を除去し、ついで乾燥処理を行い、続いて加熱処理を行う。加熱処理は２００℃〜２７０℃の温度範囲で行うことが好ましく、２１０℃〜２６０℃温度範囲で行うことがより好ましい。
処理温度が２７０℃以下であるとχ−アルミナの生成速度が大きくなるのを防ぎ、脱水量の制御を容易にすることができる。また、２００℃以上であると実用的な処理時間では熱分解開始温度の上昇させることができる。
処理時間は例えば０．１〜１０時間であることが好ましく、０．２〜５時間である。処理雰囲気は大気雰囲気、窒素雰囲気等、特に制限はないが、大気雰囲気で行うことが実用的である。
After the substitution treatment is performed in the liquid phase, the aluminum hydroxide particles are removed by filtration or centrifugation, followed by a drying treatment, followed by a heating treatment. The heat treatment is preferably performed in a temperature range of 200 ° C. to 270 ° C., and more preferably performed in a temperature range of 210 ° C. to 260 ° C.
When the treatment temperature is 270 ° C. or less, the generation rate of χ-alumina can be prevented from increasing, and the amount of dehydration can be easily controlled. Moreover, if it is 200 ° C. or higher, the thermal decomposition starting temperature can be increased in a practical treatment time.
The treatment time is preferably 0.1 to 10 hours, for example, and 0.2 to 5 hours. The treatment atmosphere is not particularly limited, such as an air atmosphere or a nitrogen atmosphere, but it is practical to carry out the treatment in an air atmosphere.
本発明において加熱処理を行うことで、水酸化アルミニウムの表面活性化エネルギーの低い表面や、粒界の結晶転移やその他の欠陥部分から分解脱水反応が起こり、水酸化アルミニウムからχ−アルミナに変化する。熱分解開始温度の低い部分が予め除去されることにより、熱分解開始温度が上昇する。本発明でのフッ素の作用は明確ではないが、フッ化アルミニウムは水酸化アルミニウムに比べて熱分解温度が高いことから、粒子表面に存在するフッ素が、χ−アルミナへの変化速度を遅くしているものと推定される。 By performing the heat treatment in the present invention, the decomposition and dehydration reaction occurs from the surface of aluminum hydroxide having a low surface activation energy, crystal transition at the grain boundary, and other defective portions, and changes from aluminum hydroxide to χ-alumina. . By removing a part having a low thermal decomposition start temperature in advance, the thermal decomposition start temperature is increased. Although the action of fluorine in the present invention is not clear, since aluminum fluoride has a higher thermal decomposition temperature than aluminum hydroxide, fluorine present on the particle surface slows the rate of change to χ-alumina. It is estimated that
フッ素の置換量は水酸化アルミニウム粒子表面に存在するフッ素の比率が１〜２０ａｔ％であり、３〜１５ａｔ％であることが好ましい。置換量が１ａｔ％より少ないと熱分解開始温度上昇効果が小さく、２０ａｔ％を超えると分解放出される水の量が減るので難燃作用が低下する。フッ素置換量の定量にはＸＰＳ（Ｘ−ｒａｙ Ｐｈｏｔｏｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ Ｘ線光電子分光装置）で行う。ＸＰＳは一般に物質の表層１０ｎｍ以内の極表層の元素分析が可能であり、検出されるアルミニウム、酸素、フッ素、炭素の分光スペクトルから元素の存在比率を算出できる。 The fluorine substitution amount is such that the ratio of fluorine present on the surface of the aluminum hydroxide particles is 1 to 20 at%, and preferably 3 to 15 at%. When the amount of substitution is less than 1 at%, the effect of increasing the thermal decomposition start temperature is small, and when it exceeds 20 at%, the amount of water decomposed and released is reduced and the flame retarding action is lowered. Quantification of the fluorine substitution amount is performed by XPS (X-ray Photoelectron Spectroscopy X-ray photoelectron spectrometer). XPS generally enables elemental analysis of the extreme surface layer within 10 nm of the surface layer of a substance, and the element abundance ratio can be calculated from the detected spectrum of aluminum, oxygen, fluorine, and carbon.
また、熱分解開始温度は２６０℃以上であることが好ましく、２６５〜３００℃であることがより好ましい。また、８００℃まで加熱した後の脱水量が３２質量％以上であることが好ましく、３２．５〜３４．６質量％であることがより好ましい。熱分解開始温度は２６０℃以上であるとＬＳＩの実装工程などの熱処理時に、熱分解による水蒸気の発生が無い、安定な樹脂組成物を提供することができる。脱水量が３２質量％以上であると熱分解時に発生する水蒸気量が多く、難燃効果を高めることができる。 Moreover, it is preferable that thermal decomposition start temperature is 260 degreeC or more, and it is more preferable that it is 265-300 degreeC. Moreover, it is preferable that the dehydration amount after heating to 800 degreeC is 32 mass% or more, and it is more preferable that it is 32.5-34.6 mass%. When the thermal decomposition starting temperature is 260 ° C. or higher, it is possible to provide a stable resin composition that does not generate water vapor due to thermal decomposition during heat treatment such as an LSI mounting process. When the amount of dehydration is 32% by mass or more, the amount of water vapor generated during thermal decomposition is large, and the flame retarding effect can be enhanced.
本発明に使用される水酸化アルミニウム粒子は、工業的に量産されているギブサイト型の水酸化アルミニウム粒子である。化学式はＡｌ（ＯＨ）３又はＡｌ２Ｏ３・３Ｈ２Ｏで表され、理論値で３４．６４質量％の水を含有する。 The aluminum hydroxide particles used in the present invention are gibbsite type aluminum hydroxide particles that are mass-produced industrially. The chemical formula is represented by Al (OH) 3 or Al 2 O 3 .3H 2 O, and contains 34.64% by mass of water in theory.
水酸化アルミニウム粒子は一般に、高温のアルミン酸ナトリウム溶液に種結晶を添加した後、液温を低下させて過飽和溶液にすることにより、種結晶上に水酸化アルミニウム粒子として析出させることにより製造される。このため、一定量のナトリウムを不純物として含む。熱分解開始温度は不純物濃度の影響を受け、Ｎａ２Ｏ濃度が低いほど高くなることが知られている。このため本発明に使用される水酸化アルミニウム粒子にはＮａ２Ｏ濃度が０．３ｗｔ％以下、好ましくは０．１ｗｔ％以下のものを使用する。 Aluminum hydroxide particles are generally produced by adding seed crystals to a hot sodium aluminate solution and then precipitating them as aluminum hydroxide particles on the seed crystals by lowering the liquid temperature to form a supersaturated solution. . For this reason, a certain amount of sodium is contained as an impurity. It is known that the thermal decomposition start temperature is affected by the impurity concentration and becomes higher as the Na 2 O concentration is lower. For this reason, the aluminum hydroxide particles used in the present invention have a Na 2 O concentration of 0.3 wt% or less, preferably 0.1 wt% or less.
また、本発明に使用される水酸化アルミニウム粒子の平均粒径は０．３μｍ〜５μｍであることが好ましく、１〜４μｍであることがより好ましい。
平均粒径が０．３μｍ以上であると凝集を防止することができ、樹脂組成物中へ均一に混合分散すること容易になる。また、平均粒径が５μｍ以下であると樹脂組成物の電気的な特性を良好な状態に維持することができる。
Moreover, it is preferable that the average particle diameter of the aluminum hydroxide particle used for this invention is 0.3 micrometer-5 micrometers, and it is more preferable that it is 1-4 micrometers.
Aggregation can be prevented when the average particle size is 0.3 μm or more, and uniform mixing and dispersion in the resin composition is facilitated. Further, when the average particle size is 5 μm or less, the electrical characteristics of the resin composition can be maintained in a good state.
［樹脂組成物］
本発明の樹脂組成物は、耐熱性水酸化アルミニウム粒子を含む。水酸化アルミニウムの粒子を添加することにより、樹脂組成物の難燃性を向上させることができる。従って本発明による耐熱性水酸化アルミニウム粒子を樹脂に添加することにより、耐熱性および難燃性の高い樹脂組成物を得ることができる。耐熱性水酸化アルミニウム粒子は、樹脂成分１００質量部に対し、５〜６０質量部とすることが好ましく、１０〜５０質量部とすることがより好ましい。
[Resin composition]
The resin composition of the present invention contains heat-resistant aluminum hydroxide particles. By adding aluminum hydroxide particles, the flame retardancy of the resin composition can be improved. Therefore, a resin composition having high heat resistance and flame retardancy can be obtained by adding the heat-resistant aluminum hydroxide particles according to the present invention to the resin. The heat-resistant aluminum hydroxide particles are preferably 5 to 60 parts by mass, and more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the resin component.
本発明に用いる樹脂は特に限定されず、例えばエポキシ樹脂、ポリイミド樹脂、ビスマレイミド−トリアジン樹脂、フェノール樹脂、メラミン樹脂、これら樹脂の変性物等が用いられる。また、これらの樹脂は２種類以上を併用してもよく、必要に応じて各種硬化剤、硬化促進剤等を使用し、これらを溶剤溶液として配合してもかまわない。 The resin used in the present invention is not particularly limited, and for example, epoxy resin, polyimide resin, bismaleimide-triazine resin, phenol resin, melamine resin, modified products of these resins, and the like are used. Two or more kinds of these resins may be used in combination, and various curing agents, curing accelerators and the like may be used as necessary, and these may be blended as a solvent solution.
［プリプレグ］
本発明のプリプレグは、本発明の樹脂組成物が含浸、乾燥されてなる。具体的には、本発明の樹脂組成物を含むワニスを基材に含浸させ、例えば８０℃〜２００℃の範囲で乾燥させてなるものである。基材としては、金属箔張り積層板や多層印刷配線板を製造する際に用いられるものであれば特に制限されないが、織布や不織布等の繊維基材が用いられる。
[Prepreg]
The prepreg of the present invention is formed by impregnating and drying the resin composition of the present invention. Specifically, the substrate is impregnated with a varnish containing the resin composition of the present invention and dried, for example, in the range of 80 ° C to 200 ° C. Although it will not restrict | limit especially if it is used when manufacturing a metal foil clad laminated board and a multilayer printed wiring board as a base material, Fiber base materials, such as a woven fabric and a nonwoven fabric, are used.
繊維基材としては、例えばガラス、アルミナ、シリカアルミナガラス、シリカガラス、チラノ、炭化ケイ素、窒化ケイ素、ジルコニア等の無機繊維やアラミド、ポリエーテルエーテルケトン、ポリエーテルイミド、ポリエーテルサルフォン、カーボン、セルロース等の有機繊維等及びこれらの混抄系が挙げられる。これらのなかでも、ガラス繊維の織布が好ましく用いられる。ガラス織布の種類は特に指定はなく、厚さ２０μｍ〜２００μｍまでのものを、目的のプリプレグ又は積層板の厚さに合わせて使用することができる。 Examples of the fiber substrate include inorganic fibers such as glass, alumina, silica alumina glass, silica glass, tyrano, silicon carbide, silicon nitride, zirconia, aramid, polyetheretherketone, polyetherimide, polyethersulfone, carbon, Examples thereof include organic fibers such as cellulose and mixed papers thereof. Among these, a glass fiber woven fabric is preferably used. The type of the glass woven fabric is not particularly specified, and those having a thickness of 20 μm to 200 μm can be used according to the thickness of the target prepreg or laminate.
樹脂にワニスを含浸させる方法としては、特に制限されず、例えば、ウェット方式やドライ方式等の樹脂液に基材を含浸させる方法、基材に樹脂組成物を塗布する方法等が挙げられる。 The method of impregnating the resin with the varnish is not particularly limited, and examples thereof include a method of impregnating the substrate with a resin liquid such as a wet method and a dry method, a method of applying a resin composition to the substrate, and the like.
［積層板］
上記により得られたプリプレグを少なくとも１枚以上重ね、加熱加圧成形することにより積層板が得られる。加熱温度は１５０℃〜２５０℃であることが好ましく、１７０℃〜２００℃であることがより好ましい。圧力は１．０ＭＰａ〜８．０ＭＰａであることが好ましく、２．０ＭＰａ〜６．０ＭＰａであることが好ましい。加熱加圧条件は、プリプレグ特性や、プレス機の能力、目的積層板の厚み等により適宜決定する。
[Laminated board]
A laminated board can be obtained by stacking at least one prepreg obtained as described above and heating and pressing. The heating temperature is preferably 150 ° C. to 250 ° C., and more preferably 170 ° C. to 200 ° C. The pressure is preferably 1.0 MPa to 8.0 MPa, and preferably 2.0 MPa to 6.0 MPa. The heating and pressing conditions are appropriately determined depending on the prepreg characteristics, the capacity of the press, the thickness of the target laminate, and the like.
また、プリプレグを少なくとも１枚以上重ねて、その片側又は両側に金属箔を配して、加熱加圧成形してプリント配線板用基材を製造することができる。金属箔としては主に銅箔やアルミ箔を用いるが、他の金属箔を用いてもよい。金属箔の厚みは通常３〜２００μｍである。これらのプリント配線板用基材を使用し、回路加工してプリント配線板が得られる。 Moreover, the base material for printed wiring boards can be manufactured by stacking at least one prepreg, placing a metal foil on one side or both sides thereof, and heating and pressing. As the metal foil, copper foil or aluminum foil is mainly used, but other metal foil may be used. The thickness of the metal foil is usually 3 to 200 μm. Using these printed wiring board base materials, a printed wiring board can be obtained by circuit processing.
以下、本発明の実施例について説明する。本発明は、これらの実施例によって限定されるものではない。
なお、本発明の実施例および比較例の水酸化アルミニウム粒子の平均粒径、加熱重量減少量、熱分解開始温度、表面フッ素含有量は以下の方法で測定した。
Examples of the present invention will be described below. The present invention is not limited by these examples.
In addition, the average particle diameter of the aluminum hydroxide particle of the Example and comparative example of this invention, the amount of heating weight reduction | decrease, the thermal decomposition start temperature, and surface fluorine content were measured with the following method.
平均粒径：
水酸化アルミニウム粒子の平均粒径は日機装株式会社製レーザー散乱粒度分布計ＭＴ３０００で水を分散液にして測定した。
Average particle size:
The average particle size of the aluminum hydroxide particles was measured using Nikkiso Co., Ltd. Laser Scattering Particle Size Distribution Meter MT3000 as a dispersion.
加熱重量減少量：
水酸化アルミニウム粒子の加熱重量減少量は、マックサイエンス株式会社製の示差熱−重量分析装置（ＴＧ−ＤＴＡ２０００）で昇温速度１０℃／分、空気流量５０ｍｌ／分で８００℃まで測定し、１１０℃を基準に８００℃までにおける重量減少量から算出した。
Heat weight loss:
The amount of heating weight reduction of the aluminum hydroxide particles was measured up to 800 ° C. at a heating rate of 10 ° C./min and an air flow rate of 50 ml / min with a differential heat-gravimetric analyzer (TG-DTA2000) manufactured by Mac Science Co., Ltd. It calculated from the weight loss amount up to 800 ° C. based on ° C.
熱分解開始温度：
水酸化アルミニウム粒子の熱分解開始温度はマックサイエンス株式会社製の示差熱−重量分析装置（ＴＧ−ＤＴＡ２０００）で昇温速度１０℃／分、空気流量５０ｍｌ／分で８００℃まで測定し、２００℃を基準に重量減少率が０．５質量％になる温度を測定した。
Thermal decomposition start temperature:
The thermal decomposition start temperature of the aluminum hydroxide particles was measured up to 800 ° C. at a heating rate of 10 ° C./min and an air flow rate of 50 ml / min with a differential thermal-gravimetric analyzer (TG-DTA2000) manufactured by Mac Science Co., Ltd. The temperature at which the weight loss rate became 0.5% by mass was measured.
表面フッ素含有量：
水酸化アルミニウム粒子の表面に存在するフッ素の存在量は、アルバック・ファイ株式会社製のＸ線光電子分光分析装置５４００型でフッ素の１ｓ軌動、アルミニウムの２ｐ軌動、酸素の１ｓ軌動、炭素の１ｓ軌動のピーク面積を測定し、面積比から算出した。
Surface fluorine content:
The amount of fluorine present on the surface of the aluminum hydroxide particles is as follows: 1s trajectory of fluorine, 2p trajectory of aluminum, 1s trajectory of oxygen, carbon using X-ray photoelectron spectrometer 5400 manufactured by ULVAC-PHI The 1s trajectory peak area was measured and calculated from the area ratio.
（実施例１）
原料となる水酸化アルミニウム粒子として昭和電工株式会社製のＨＰ−３６０（平均粒径３．２μｍ、比表面積１．３ｍ２／ｇ、熱分解開始温度２４８℃、脱水量３４．４質量％）を使用した。
水酸化アルミニウム粒子２５ｇとフッ化アンモニウム（和光純薬試薬特級）０．７１ｇとを良く混合した。その後、容量５０ｍｌの磁性坩堝に充填し、熱風循環タイプのボックス炉（ヤマト科学製ファインオーブンＤＨ４２）中、２４０℃で３時間加熱処理し耐熱性水酸化アルミニウム粒子を作製した。
Example 1
HP-360 (average particle size: 3.2 μm, specific surface area: 1.3 m 2 / g, thermal decomposition start temperature: 248 ° C., dehydration amount: 34.4% by mass) manufactured by Showa Denko KK as aluminum hydroxide particles as a raw material used.
25 g of aluminum hydroxide particles and 0.71 g of ammonium fluoride (special grade of Wako Pure Chemical Industries, Ltd.) were mixed well. Then, the magnetic crucible with a capacity of 50 ml was filled and heat-treated at 240 ° C. for 3 hours in a hot air circulation type box furnace (Fine Oven DH42 manufactured by Yamato Kagaku) to produce heat-resistant aluminum hydroxide particles.
示差熱−重量分析装置による評価では熱分解開始温度は２８１℃、脱水量３３．５ｗｔ％であった。Ｘ線光電子分光分析装置による評価では水酸化アルミニウム粒子表面の原子パーセントは炭素１６．２ａｔ％、酸素５２．１ａｔ％、アルミニウム２２．１ａｔ％、フッ素９．６ａｔ％であり、フッ素が粒子表面に存在していることが確認できた。 In the evaluation by the differential thermal-gravimetric analyzer, the thermal decomposition starting temperature was 281 ° C. and the dehydration amount was 33.5 wt%. According to the evaluation by the X-ray photoelectron spectrometer, the atomic percentage of the aluminum hydroxide particle surface is 16.2 at% carbon, 52.1 at% oxygen, 22.1 at% aluminum, and 9.6 at% fluorine, and fluorine exists on the particle surface. I was able to confirm.
（実施例２）
フッ化アンモニウムの添加量を０．０３５ｇとしたこと以外は実施例２と同様に耐熱性水酸化アルミニウム粒子を作製した。
示差熱−重量分析装置による評価では熱分解開始温度は２７１℃、脱水量３３．６ｗｔ％であった。Ｘ線光電子分光分析装置による評価では水酸化アルミニウム粒子表面のフッ素含有量が２．２ａｔ％であり、フッ素が粒子表面に存在していることが確認できた。
(Example 2)
Heat-resistant aluminum hydroxide particles were produced in the same manner as in Example 2 except that the amount of ammonium fluoride added was 0.035 g.
In the evaluation by the differential thermal-gravimetric analyzer, the thermal decomposition starting temperature was 271 ° C. and the dehydration amount was 33.6 wt%. In the evaluation by the X-ray photoelectron spectrometer, the fluorine content on the aluminum hydroxide particle surface was 2.2 at%, and it was confirmed that fluorine was present on the particle surface.
（実施例３）
原料となる水酸化アルミニウム粒子として住友化学株式会社製ＣＬ−３０３（平均粒径４．１μｍ、熱分解開始温度は２４２℃、脱水量３４．４ｗｔ％））を使用した以外は実施例１と同様に耐熱性水酸化アルミニウム粒子を作製した。
示差熱−重量分析装置による評価では熱分解開始温度は２７８℃、脱水量３２．７ｗｔ％であった。Ｘ線光電子分光分析装置による評価では水酸化アルミニウム粒子表面のフッ素含有量が１０．１ａｔ％であり、フッ素が粒子表面に存在していることが確認できた。
(Example 3)
The same as Example 1 except that Sumitomo Chemical Co., Ltd. CL-303 (average particle size 4.1 μm, thermal decomposition start temperature is 242 ° C., dehydration amount 34.4 wt%) was used as aluminum hydroxide particles as a raw material. Heat-resistant aluminum hydroxide particles were prepared.
In the evaluation by the differential thermal-gravimetric analyzer, the thermal decomposition starting temperature was 278 ° C., and the dehydration amount was 32.7 wt%. In the evaluation by the X-ray photoelectron spectrometer, the fluorine content on the aluminum hydroxide particle surface was 10.1 at%, and it was confirmed that fluorine was present on the particle surface.
（実施例４）
原料となる水酸化アルミニウム粒子として昭和電工株式会社製ＨＰ−３６０（平均粒径３．２μｍ、熱分解開始温度は２４８℃、脱水量３４．４ｗｔ％）を使用した。５００ｍｌのプラスチックス容器に水酸化アルミニウム粒子５０ｇと純水１５０ｇとを添加し攪拌した。その後、５５質量％フッ酸（和光純薬化学用）を２．８ｇを添加し室温で１時間攪拌した。続いてろ過、１５０℃での乾燥を行い、フッ素置換水酸化アルミニウム粒子を得た。続いて容量５０ｍｌの磁性坩堝に充填し、熱風循環タイプのボックス炉（ヤマト科学製ファインオーブンＤＨ４２）中、２２０℃で３時間加熱処理し耐熱性水酸化アルミニウム粒子を作製した。
示差熱−重量分析装置による評価では熱分解開始温度は２６９℃、脱水量３３．１ｗｔ％であった。Ｘ線光電子分光分析装置による評価では水酸化アルミニウム粒子表面のフッ素含有量が１１．８ａｔ％であり、フッ素が粒子表面に存在していることが確認できた。
Example 4
As an aluminum hydroxide particle used as a raw material, HP-360 (average particle diameter: 3.2 μm, thermal decomposition start temperature: 248 ° C., dehydration amount: 34.4 wt%) manufactured by Showa Denko KK was used. In a 500 ml plastic container, 50 g of aluminum hydroxide particles and 150 g of pure water were added and stirred. Thereafter, 2.8 g of 55% by mass hydrofluoric acid (for Wako Pure Chemical) was added and stirred at room temperature for 1 hour. Subsequently, filtration and drying at 150 ° C. were performed to obtain fluorine-substituted aluminum hydroxide particles. Subsequently, a magnetic crucible with a capacity of 50 ml was filled and heat-treated at 220 ° C. for 3 hours in a hot air circulation type box furnace (Fine Oven DH42 manufactured by Yamato Kagaku) to produce heat-resistant aluminum hydroxide particles.
In the evaluation by the differential thermal-gravimetric analyzer, the thermal decomposition starting temperature was 269 ° C. and the dehydration amount was 33.1 wt%. In the evaluation by the X-ray photoelectron spectrometer, the fluorine content on the surface of the aluminum hydroxide particles was 11.8 at%, and it was confirmed that fluorine was present on the particle surface.
（比較例１）
フッ化アンモニウムを添加しないこと以外は実施例１と同様に水酸化アルミニウム粒子を作製した。示差熱−重量分析装置による評価では熱分解開始温度は２５２℃、脱水量３０．２ｗｔ％であった。
(Comparative Example 1)
Aluminum hydroxide particles were prepared in the same manner as in Example 1 except that ammonium fluoride was not added. In the evaluation by the differential thermal-gravimetric analyzer, the thermal decomposition starting temperature was 252 ° C. and the dehydration amount was 30.2 wt%.
上記実施例１〜４及び比較例１の水酸化アルミニウム粒子６５部をそれぞれエポキシ樹脂として、ビスフェノールＡノボラック型エポキシ樹脂（大日本インキ化学工業株式会社製ＥＰＩＣＬＯＮ Ｎ８６５、エポキシ当量：２０５）を６５．４部、硬化剤として、フェノールノボラック樹脂（明和化成株式会社製ＨＦ−４、水酸基当量：１０８）を３４．６部、硬化促進剤として、２−エチル−４−メチルイミダゾール（四国化成株式会社製２Ｅ４ＭＺ）を０．２部、平均粒径０．５μｍの球状溶融シリカ３０部、難燃助剤として、モリブデン酸亜鉛担持タルク（シャーウインウイリアムズ社製Ｋｅｍｇａｒｄ ９１１Ｃ）を５部、メチルエチルケトン８５．８部と配合し、固形分７０重量％のワニスを調製した。 Using 65 parts of the aluminum hydroxide particles of Examples 1 to 4 and Comparative Example 1 as an epoxy resin, 65.4 bisphenol A novolac type epoxy resin (EPICLON N865 manufactured by Dainippon Ink & Chemicals, Inc., epoxy equivalent: 205). Part, 34.6 parts phenol novolac resin (HF-4, hydroxyl equivalent: 108 manufactured by Meiwa Kasei Co., Ltd.) as a curing agent, 2-ethyl-4-methylimidazole (2E4MZ manufactured by Shikoku Kasei Co., Ltd.) as a curing accelerator ) 0.2 parts, 30 parts of spherical fused silica having an average particle diameter of 0.5 μm, 5 parts of zinc molybdate-supported talc (Keggard 911C manufactured by Sherwin Williams) as a flame retardant aid, and 85.8 parts of methyl ethyl ketone A varnish having a solid content of 70% by weight was prepared.
実施例１〜４及び比較例１の水酸化アルミニウム粒子を含む上記ワニスを厚さ約０．１ｍｍのガラス布（＃２１１６，Ｅ−ガラス）に含浸後、１６０℃で３〜１０分加熱乾燥して樹脂分４８重量％のプリプレグを得た。これらプリプレグ４枚を重ね、その両側に厚みが１８μｍの銅箔を重ね、１８０℃、９０分、３．０ＭＰａのプレス条件で両面銅張積層板を作製した。この基材を使用して吸湿耐熱性評価と燃燃性の評価を行った。 After impregnating the glass cloth (# 2116, E-glass) with a thickness of about 0.1 mm with the varnish containing the aluminum hydroxide particles of Examples 1 to 4 and Comparative Example 1, it was dried by heating at 160 ° C. for 3 to 10 minutes. Thus, a prepreg having a resin content of 48% by weight was obtained. Four of these prepregs were stacked, and a copper foil having a thickness of 18 μm was stacked on both sides thereof, and a double-sided copper-clad laminate was produced under press conditions of 180 ° C., 90 minutes, 3.0 MPa. Using this substrate, moisture absorption heat resistance evaluation and flame retardant evaluation were performed.
吸湿対熱性評価は作製した基材を２ｃｍ四角に裁断したサンプルをそれぞれ３個作製し、１２５℃のプレッシャークッカー装置で５時間吸湿処理を行い、重量変化から吸湿量を測定し、２８８℃のはんだバスに２０秒浸漬し、膨れの発生状況を観察した。
難燃性評価は作製した基材の銅箔をエッチングで除去し、１．３ｃｍ×１０ｃｍに裁断したサンプルをそれぞれ５個作製し、縦型の燃焼試験を行い、５サンプルの平均燃焼時間と最大燃焼時間を測定した。また、ＵＬ−９４垂直法に準拠した難燃性（平均燃焼時間（ｎ＝５））の評価結果も求めた。下記表１に結果を示す。
The hygroscopicity vs. thermal evaluation was made by making three samples each of the produced substrate cut into 2 cm squares, performing a moisture absorption treatment with a 125 ° C pressure cooker for 5 hours, measuring the amount of moisture absorption from the weight change, and soldering at 288 ° C. It was immersed in a bath for 20 seconds, and the occurrence of swelling was observed.
For the evaluation of flame retardancy, the copper foil of the prepared substrate was removed by etching, 5 samples each cut to 1.3 cm × 10 cm were prepared, a vertical combustion test was performed, and the average burning time and maximum of 5 samples were measured. The burning time was measured. Moreover, the evaluation result of the flame retardance (average burning time (n = 5)) based on the UL-94 vertical method was also obtained. The results are shown in Table 1 below.
実施例１〜４で得られた高耐熱水酸化アルミニウム粒子を用いた積層板は吸湿低熱性および難燃性にいずれも良好な特性を示した。これに対して、フッ化アンモニウムを添加せずに加熱処理した加熱処理した比較例１の水酸化アルミニウム粒子を用いた積層板は多孔質のχ−アルミナの含有量が多いため吸湿量が大きく、吸湿耐熱性に劣り、含水量が減るため難燃性に劣った。
以上から、本発明によれば、合成樹脂に難燃材として添加するのに適した熱分解開始温度が高く、脱水量の多い耐熱性水酸化アルミニウム粒子を提供することができるといえる。
The laminates using the high heat-resistant aluminum hydroxide particles obtained in Examples 1 to 4 showed good characteristics in both moisture absorption and low heat resistance and flame retardancy. On the other hand, the laminate using the aluminum hydroxide particles of Comparative Example 1 that was heat-treated without adding ammonium fluoride has a large amount of moisture absorption because of the high content of porous χ-alumina, It was inferior in moisture absorption heat resistance and inferior in flame retardancy due to a decrease in water content.
From the above, it can be said that according to the present invention, it is possible to provide heat-resistant aluminum hydroxide particles having a high thermal decomposition starting temperature suitable for addition as a flame retardant to a synthetic resin and a large amount of dehydration.
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|---|---|---|---|---|
| JPH0328121A (en) * | 1989-06-23 | 1991-02-06 | Showa Denko Kk | Heat-resistant and fine-granular aluminum hydroxide and its production |
| JPH11292520A (en) * | 1998-04-14 | 1999-10-26 | Showa Denko Kk | Metal oxide sol with fluorinated surface and its production |
| WO2004080897A1 (en) * | 2003-03-10 | 2004-09-23 | Kawai-Lime Ind. Co., Ltd. | Heat-resistant aluminum hydroxide and method for preparation thereof |
| JP2011084431A (en) * | 2009-10-15 | 2011-04-28 | Hitachi Chem Co Ltd | High heat-resistant aluminum hydroxide particle, method for producing the same, resin composition containing the particle, and printed wiring board using the resin composition |
-
2015
- 2015-11-05 JP JP2015217731A patent/JP6052369B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0328121A (en) * | 1989-06-23 | 1991-02-06 | Showa Denko Kk | Heat-resistant and fine-granular aluminum hydroxide and its production |
| JPH11292520A (en) * | 1998-04-14 | 1999-10-26 | Showa Denko Kk | Metal oxide sol with fluorinated surface and its production |
| WO2004080897A1 (en) * | 2003-03-10 | 2004-09-23 | Kawai-Lime Ind. Co., Ltd. | Heat-resistant aluminum hydroxide and method for preparation thereof |
| JP2011084431A (en) * | 2009-10-15 | 2011-04-28 | Hitachi Chem Co Ltd | High heat-resistant aluminum hydroxide particle, method for producing the same, resin composition containing the particle, and printed wiring board using the resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102212341B1 (en) * | 2020-11-19 | 2021-02-04 | 주식회사 백승 | Heating Appliance Assembly for Experiments |
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| JP6052369B2 (en) | 2016-12-27 |
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