JP5463586B2 - Prepreg, laminate, and metal foil-clad laminate - Google Patents
Prepreg, laminate, and metal foil-clad laminate Download PDFInfo
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- JP5463586B2 JP5463586B2 JP2009289732A JP2009289732A JP5463586B2 JP 5463586 B2 JP5463586 B2 JP 5463586B2 JP 2009289732 A JP2009289732 A JP 2009289732A JP 2009289732 A JP2009289732 A JP 2009289732A JP 5463586 B2 JP5463586 B2 JP 5463586B2
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- 229910052751 metal Inorganic materials 0.000 title claims description 20
- 239000002184 metal Substances 0.000 title claims description 20
- 239000011342 resin composition Substances 0.000 claims description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000011521 glass Substances 0.000 claims description 22
- 239000004744 fabric Substances 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 20
- 239000012463 white pigment Substances 0.000 claims description 16
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 13
- 239000011888 foil Substances 0.000 claims description 11
- 229920002050 silicone resin Polymers 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 150000004696 coordination complex Chemical class 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000002966 varnish Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002845 discoloration Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000002310 reflectometry Methods 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、発光ダイオード素子を実装するためのプリント配線基板の製造に使用されるプリプレグ、およびそれを積層した積層板、金属箔張り積層板に関する。 The present invention relates to a prepreg used for manufacturing a printed wiring board for mounting a light-emitting diode element, a laminated board on which the prepreg is laminated, and a metal foil-clad laminated board.
近年、携帯電話、液晶テレビ、携帯ゲーム等の電子機器は、軽量化、薄型化が進んでおり、外観、操作性や視認性等の付加価値が求められるようになった。そのために視覚的効果の高い発光体が多数使われるようになってきており、この発光体には小型で消費電力の少ない発光ダイオード（以後ＬＥＤと表記）が用いられている。 In recent years, electronic devices such as mobile phones, liquid crystal televisions, and mobile games have been reduced in weight and thickness, and added values such as appearance, operability, and visibility have been demanded. For this reason, a large number of light emitters having high visual effects have been used, and light-emitting diodes (hereinafter referred to as LEDs) that are small in size and consume less power are used.
ところでこれらのＬＥＤは、青色や白色のＬＥＤの実用化が急速に拡大しており、高輝度化も著しい速度で進んでいる。 By the way, in these LEDs, the practical application of blue and white LEDs is rapidly expanding, and the increase in luminance is progressing at a remarkable speed.
従来は、発光体部を樹脂で封止した砲弾型タイプのＬＥＤが主に用いられていたが、近年、電子機器の小型、薄型化から、基板表面に素子を直接実装したチップＬＥＤの使用が増加してきた。このチップＬＥＤは、当初、砲弾型タイプのＬＥＤに比べて輝度が低いという問題もあったが、その後の改良により、十分な輝度が得られるようになった。チップＬＥＤの輝度が向上したことにより、チップＬＥＤを種々のプリント基板上に複数個実装することで面光源、すなわち照明器具部品としての利用も可能になった。また、薄型・低発熱・長寿命であることが要求される液晶ディスプレイ用バックライトにも実用化が始まっている。 Conventionally, bullet-type LEDs with a light-emitting part sealed with resin were mainly used. However, in recent years, chip LEDs in which elements are directly mounted on the substrate surface have been used due to the miniaturization and thinning of electronic devices. It has increased. This chip LED originally had a problem that its luminance was lower than that of a bullet-type LED, but sufficient luminance has been obtained by subsequent improvements. Since the brightness of the chip LED is improved, it is possible to use a plurality of chip LEDs on a variety of printed circuit boards as a surface light source, that is, a luminaire component. Moreover, practical use has begun for backlights for liquid crystal displays that are required to be thin, low heat generation and long life.
ところで、白色ＬＥＤの発光方法には、青色発光素子と黄色蛍光体を併用したタイプ、赤色、青色、緑色の３原色併用タイプ、若しくは紫外発光素子と蛍光体を併用したタイプがある。 By the way, the light emitting method of the white LED includes a type in which a blue light emitting element and a yellow phosphor are used in combination, a red, blue, and green primary color combination type, or a type in which an ultraviolet light emitting element and a phosphor are used in combination.
表面実装型ＬＥＤ用のＬＥＤチップ実装用プリント配線基板としては、従来から、熱硬化性樹脂を含浸したシート状ガラス繊維基材（プリプレグ）の層を加熱加圧成形した積層板が使用されている（下記特許文献１参照）。特に、チップＬＥＤの輝度を向上させるためには、基板表面の反射が重要であり、熱硬化性樹脂に着色顔料として反射率の高い二酸化チタン等を含有させた白色のものが従来から使用されている。 Conventionally, as a printed wiring board for mounting LED chips for surface-mounted LEDs, a laminated sheet obtained by heat-pressing a layer of a sheet-like glass fiber substrate (prepreg) impregnated with a thermosetting resin has been used. (See Patent Document 1 below). In particular, in order to improve the brightness of the chip LED, the reflection of the substrate surface is important, and a white one in which titanium dioxide having a high reflectance as a coloring pigment is contained in a thermosetting resin has been conventionally used. Yes.
ところが、これまでのプリント配線基板用白色積層板は、熱硬化性樹脂部分が長期使用や加工時の熱によって変色し、反射率が低下する問題があった。特に紫外発光素子や高輝度青色ＬＥＤを用いたチップＬＥＤでは、ＬＥＤチップを実装した基板が紫外線や青色のような高エネルギーの光により容易に劣化、変色するため、最近の高輝度ＬＥＤの実装には不適となった。また、これまでのプリント配線基板用白色積層板は、ＬＥＤチップから放出される光のほか、ＬＥＤチップの発熱によっても熱劣化が進行し、着色するという問題も併せて起こる。そのため、紫外線や熱による変色の極めて少ない基板材料の要求が強くなっている。 However, the conventional white laminates for printed wiring boards have a problem that the thermosetting resin portion is discolored by long-term use or heat during processing, and the reflectance is lowered. Especially in chip LEDs using ultraviolet light emitting elements and high-intensity blue LEDs, the substrate on which the LED chip is mounted is easily deteriorated and discolored by high-energy light such as ultraviolet rays or blue. Became unfit. In addition, the conventional white laminates for printed wiring boards have a problem in that they are colored due to heat deterioration caused by the heat generated by the LED chip, in addition to the light emitted from the LED chip. For this reason, there is an increasing demand for substrate materials that are extremely less discolored by ultraviolet rays and heat.
さらに、チップＬＥＤを実装する際、チップＬＥＤの封止工程において液漏れ等の不具合を起こさないよう高い板厚精度も要求されており、両者を兼ね備えた基板が求められている。
Furthermore, when mounting the chip LED, high plate thickness accuracy is also required so as not to cause problems such as liquid leakage in the sealing process of the chip LED, and a substrate having both is required.
本発明は、可視光領域の反射率が高く、しかも加熱や紫外線による劣化・変色、反射率低下が極めて少なく、さらには高い耐熱性および板厚精度を有する基板材料であるプリプレグ、およびそれを積層した積層板、金属箔張り積層板の提供を目的とする。 The present invention relates to a prepreg that is a substrate material having a high visible light region reflectivity, deterioration and discoloration due to heating and ultraviolet rays, and extremely low reflectivity reduction, and also having high heat resistance and plate thickness accuracy, and a laminate thereof An object of the present invention is to provide a laminated plate and a metal foil-clad laminate.
本発明は、上記課題を解決するために下記の構成を有する。
（１）過酸化物ないし金属錯体触媒を用いて硬化させる付加硬化型シリコーンレジンを主成分とする樹脂組成物をガラス布基材に含浸、乾燥させてなることを特長とするプリプレグ。
（２）前記樹脂組成物が、有機官能基を有するモノアルコキシシラン、ジアルコキシシラン、トリアルコキシシランから選ばれる1種または２種以上の化合物を、樹脂組成物全体に対し０．０５〜１５重量％含有することを特長とする前記（１）記載のプリプレグ。
（３）前記樹脂組成物が、グリシジル（メタ）アクリレート重合体、もしくはグリシジル（メタ）アクリレートを共重合成分として含有する共重合体から選ばれる１種または２種以上のポリマーを、樹脂組成物全体に対し０．０５〜１５重量％含有することを特長とする前記（１）または（２）記載のプリプレグ。
（４）前記樹脂組成物が、白色顔料を含有することを特長とする前記（１）乃至（３）のいずれか一項に記載のプリプレグ。
（５）前記白色顔料が、二酸化チタン、酸化亜鉛、硫酸バリウムからなる群から選ばれる少なくとも一種以上の白色顔料であることを特長とする前記（４）記載のプリプレグ。
（６）前記白色顔料の他に、シリカ、アルミナ、窒化ホウ素からなる群から選ばれる少なくとも一種以上の無機充填材を含有することを特長とする前記（４）記載のプリプレグ。
（７）前記（１）記載のプリプレグを１枚、または複数枚重ねて、加熱加圧成形してなることを特長とする積層板。
（８）前記（１）記載のプリプレグを１枚、または複数枚重ね、さらに金属箔を重ねて、加熱加圧成形してなることを特長とする金属箔張り積層板。
The present invention has the following configuration in order to solve the above problems.
(1) A prepreg obtained by impregnating and drying a glass cloth base material with a resin composition mainly composed of an addition-curable silicone resin that is cured using a peroxide or a metal complex catalyst.
(2) The resin composition contains 0.05 to 15 weight percent of one or more compounds selected from monoalkoxysilanes, dialkoxysilanes, and trialkoxysilanes having an organic functional group with respect to the entire resin composition. % Of the prepreg as described in (1) above.
(3) The resin composition comprises one or more polymers selected from a glycidyl (meth) acrylate polymer or a copolymer containing glycidyl (meth) acrylate as a copolymerization component. The prepreg as described in (1) or (2) above, which is contained in an amount of 0.05 to 15% by weight.
(4) The prepreg according to any one of (1) to (3), wherein the resin composition contains a white pigment.
(5) The prepreg according to (4), wherein the white pigment is at least one or more white pigments selected from the group consisting of titanium dioxide, zinc oxide, and barium sulfate.
(6) The prepreg as described in (4) above, which contains at least one inorganic filler selected from the group consisting of silica, alumina and boron nitride in addition to the white pigment.
(7) A laminate comprising one or a plurality of the prepregs described in (1) above, and heat-pressed.
(8) A metal foil-clad laminate comprising one or a plurality of the prepregs described in (1) above, further laminated with metal foil, and heat-pressed.
本発明のプリプレグ、積層板、金属箔張り積層板は、ガラス布基材に含浸させる樹脂組成物の主成分として、過酸化物ないし金属錯体触媒を用いて硬化させる付加硬化型シリコーンレジンを用いることにより、可視光領域の反射率が高く、しかも加熱や紫外線によって劣化・変色、反射率低下が極めて少なく、さらには高い耐熱性および板厚精度を有する。 The prepreg, laminate, and metal foil-clad laminate of the present invention use an addition-curable silicone resin that is cured using a peroxide or metal complex catalyst as the main component of the resin composition impregnated into the glass cloth substrate. Thus, the reflectance in the visible light region is high, and deterioration, discoloration, and reflectance reduction due to heating and ultraviolet rays are extremely small, and the heat resistance and the plate thickness accuracy are high.
本発明のプリプレグは、過酸化物ないし金属錯体触媒を用いて硬化させる付加硬化型シリコーンレジンを主成分とする樹脂組成物をガラス布基材に含浸、乾燥させてなる。 The prepreg of the present invention is obtained by impregnating a glass cloth substrate with a resin composition mainly composed of an addition-curable silicone resin that is cured using a peroxide or a metal complex catalyst, and drying the resin composition.
上記付加硬化型シリコーンレジンは、ジフェニル型、ジメチル型、より好ましくはメチルフェニル型の骨格を有し、分子末端ないし分子中にビニル基を有していることが条件である。また、架橋剤として、ジフェニル型、ジメチル型、より好ましくはメチルフェニル型の骨格を有し、分子末端ないし分子中にシリル基を有しているものを用い、白金錯体などの金属錯体触媒を用いて反応・硬化させる。または、付加硬化型シリコーンレジンとして、ジフェニル型、ジメチル型、より好ましくはメチルフェニル型の骨格を有し、分子末端ないし分子中にビニル基を有しているものを、過酸化物などで架橋させることも可能である。上記付加硬化型シリコーンレジンは、熱硬化性樹脂の一つであり、これをガラス布基材に含浸させる主成分として使用することにより、紫外線および加熱による劣化、変色が極めて少なく、反射率低下も極めて少ないプリプレグを得ることが可能となる。 The addition-curable silicone resin has a diphenyl type, a dimethyl type, more preferably a methylphenyl type skeleton, and a vinyl group in the molecular terminal or molecule. In addition, as a cross-linking agent, one having a skeleton of diphenyl type, dimethyl type, more preferably methylphenyl type, having a silyl group in the molecular terminal or molecule, and using a metal complex catalyst such as a platinum complex React and cure. Alternatively, an addition-curable silicone resin having a diphenyl-type, dimethyl-type, more preferably methylphenyl-type skeleton, and having a vinyl group in the molecular terminal or molecule is crosslinked with a peroxide or the like. It is also possible. The above addition curable silicone resin is one of thermosetting resins, and when used as a main component for impregnating a glass cloth base material, the deterioration and discoloration due to ultraviolet rays and heating are extremely small, and the reflectance is also reduced. An extremely small number of prepregs can be obtained.
本発明のプリプレグは、前記樹脂組成物に、有機官能基を有するモノアルコキシシラン、ジアルコキシシラン、トリアルコキシシランから選ばれる1種または２種以上の化合物を配合するのが好ましい。有機官能基を有するモノアルコキシシラン、ジアルコキシシラン、トリアルコキシシランから選ばれる1種または２種以上の化合物を含有することにより、プリプレグに金属箔を積層した際の接着性が向上する。 The prepreg of the present invention preferably contains one or more compounds selected from monoalkoxysilanes, dialkoxysilanes, and trialkoxysilanes having an organic functional group in the resin composition. By containing one or more compounds selected from monoalkoxysilanes, dialkoxysilanes, and trialkoxysilanes having an organic functional group, adhesion when a metal foil is laminated on a prepreg is improved.
上記有機官能基を有するモノアルコキシシラン、ジアルコキシシラン、トリアルコキシシランとしては、分子中に含まれる有機官能基の極性が高い方が望ましく、例えば、ビニルトリクロルシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、２−（３，４−エポキシシクロヘキシル）トリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、ｐ−スチリルトリメトキシシラン、３−メタクリロイロキシプロピルメチルジメトキシシラン、３−メタクリロイロキシプロピルトリメトキシシラン、３−メタクリロイロキシプロピルメチルジエトキシシラン、３−メタクリロイロキシプロピルトリメトキシシラン、３−アクリロイロキシプロピルトリメトキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィドなどがあげられる。 As the monoalkoxysilane, dialkoxysilane, and trialkoxysilane having an organic functional group, it is desirable that the organic functional group contained in the molecule has a higher polarity. For example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxy Silane, 2- (3,4-epoxycyclohexyl) trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid Xylpropylmethyldiethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3- Taku Leroy trimethoxy silane, 3-acryloyloxy propyl trimethoxy silane, bis (triethoxysilylpropyl) tetrasulfide and the like.
前記有機官能基を有するモノアルコキシシラン、ジアルコキシシラン、トリアルコキシシランから選ばれる1種または２種以上の化合物の配合量は、樹脂組成物全体に対し０．０５〜１５重量％であるのが好ましく、さらに０．１〜１５重量％、ことさらに０．５〜１５重量％、特に２〜５重量％含有するのがさらに好ましい。有機官能基を有するモノアルコキシシラン、ジアルコキシシラン、トリアルコキシシランから選ばれる1種または２種以上の化合物の配合量が０．０５重量％未満であると配合の効果が現れにくく、１５重量％を超えるとプリプレグ中の樹脂組成物に粘着性が生じて保管しにくくなる。また、プリプレグの加熱・加圧成形後、耐変色性が低下する。 The compounding quantity of the 1 type, or 2 or more types of compound chosen from the monoalkoxysilane which has the said organic functional group, dialkoxysilane, trialkoxysilane is 0.05 to 15 weight% with respect to the whole resin composition. More preferably, it is 0.1 to 15% by weight, more preferably 0.5 to 15% by weight, particularly 2 to 5% by weight. When the blending amount of one or more compounds selected from monoalkoxysilanes, dialkoxysilanes, and trialkoxysilanes having an organic functional group is less than 0.05% by weight, the blending effect hardly appears, and 15% by weight If it exceeds 1, the resin composition in the prepreg will become sticky, making it difficult to store. Further, after the prepreg is heated and pressure-molded, the discoloration resistance is lowered.
また、本発明のプリプレグは、前記樹脂組成物に、グリシジル（メタ）アクリレート重合体、もしくはグリシジル（メタ）アクリレートを共重合成分として含有する共重合体から選ばれる１種または２種以上のポリマーを配合してもよい。上記ポリマーを配合することにより、プリプレグの金属箔との接着性が向上する。また、プリプレグ中の樹脂組成物からの粉の発生が抑えられる。 Moreover, the prepreg of the present invention contains one or more polymers selected from a glycidyl (meth) acrylate polymer or a copolymer containing glycidyl (meth) acrylate as a copolymerization component in the resin composition. You may mix | blend. By blending the polymer, the adhesion of the prepreg to the metal foil is improved. Moreover, generation | occurrence | production of the powder from the resin composition in a prepreg is suppressed.
本発明においては、グリシジル（メタ）アクリレート重合体もしくはグリシジル（メタ）アクリレートとラジカル重合性モノマーとの共重合体を使用するのが、接着性や反応性の点から、好ましい。 In the present invention, it is preferable from the viewpoint of adhesiveness and reactivity to use a glycidyl (meth) acrylate polymer or a copolymer of glycidyl (meth) acrylate and a radical polymerizable monomer.
上記グリシジル（メタ）アクリレートとラジカル重合性モノマーとの共重合体において、共重合の割合は、共重合体全体に対し、ラジカル重合性モノマーが５〜７５重量％の範囲であるのが好ましい。又、好適に使用できるラジカル重合性モノマーとしては、スチレン、メチル（メタ）アクリレート等の（メタ）アクリレート誘導体、シクロヘキシル（メタ）アクリレート等を挙げることができる。 In the copolymer of glycidyl (meth) acrylate and a radical polymerizable monomer, the copolymerization ratio is preferably in the range of 5 to 75% by weight of the radical polymerizable monomer with respect to the entire copolymer. Moreover, as a radically polymerizable monomer which can be used conveniently, (meth) acrylate derivatives, such as styrene and methyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. can be mentioned.
上記のグリシジル（メタ）アクリレート重合体、もしくはグリシジル（メタ）アクリレートを共重合成分として含有する共重合体としては、エポキシ当量が好ましくは１００〜１０００ｇ／ｅｑ、重量平均分子量が好ましくは２００〜２５０，０００であるのが良い。重量平均分子量が２００未満であるとポリマーとしての物性が発現しにくく、２５０，０００を超えると重合が難しくなる。 As a glycidyl (meth) acrylate polymer or a copolymer containing glycidyl (meth) acrylate as a copolymerization component, the epoxy equivalent is preferably 100 to 1000 g / eq, and the weight average molecular weight is preferably 200 to 250, 000 is good. When the weight average molecular weight is less than 200, physical properties as a polymer are hardly exhibited, and when it exceeds 250,000, polymerization becomes difficult.
前記グリシジル（メタ）アクリレート重合体、もしくはグリシジル（メタ）アクリレートを共重合成分として含有する共重合体から選ばれる１種または２種以上のポリマーの配合量は、樹脂組成物全体に対し０．０５〜１５重量％含有であるのが好ましい。樹脂組成物全体に対し０．０５重量％未満であれば接着性向上の効果が得られにくく、１５重量％を超えるとプリプレグの耐熱変色性が低下しやすくなる。 The compounding quantity of the 1 type (s) or 2 or more types of polymer chosen from the copolymer containing the said glycidyl (meth) acrylate polymer or a glycidyl (meth) acrylate as a copolymerization component is 0.05 with respect to the whole resin composition. It is preferable to contain -15 wt%. If the amount is less than 0.05% by weight relative to the entire resin composition, the effect of improving adhesiveness is difficult to obtain, and if it exceeds 15% by weight, the heat discoloration of the prepreg tends to be lowered.
本発明のプリプレグは、前記樹脂組成物に白色顔料を含有させることで、白色プリプレグとすることができる。前記白色顔料としては、酸化亜鉛、炭酸カルシウム、二酸化チタン、アルミナ、合成スメクタイト、硫酸バリウムなどが例示でき、白色の無機粉末であれば特に限定されるものではないが、二酸化チタン、酸化亜鉛、硫酸バリウムから選ばれる白色顔料を使用するのが好ましく、可視光反射率や白色度、或いは電気特性といった観点から二酸化チタンを用いるのが最も好ましい。上記白色顔料は1種を単独で使用しても、２種以上を併用しても良い。 The prepreg of the present invention can be made into a white prepreg by containing a white pigment in the resin composition. Examples of the white pigment include zinc oxide, calcium carbonate, titanium dioxide, alumina, synthetic smectite, and barium sulfate. The white pigment is not particularly limited as long as it is a white inorganic powder, but is titanium dioxide, zinc oxide, sulfuric acid. A white pigment selected from barium is preferably used, and titanium dioxide is most preferably used from the viewpoint of visible light reflectance, whiteness, or electrical characteristics. The white pigments may be used alone or in combination of two or more.
二酸化チタンの結晶構造はアナターゼ型とルチル型がある。両者の特徴を挙げると、アナターゼ型は可視光短波長領域の反射率が良好であり、本発明の樹脂組成物に添加する白色顔料としてはどちらでも良く、特に限定されるものではない。両者を混合して使用することも勿論可能である。 The crystal structure of titanium dioxide includes anatase type and rutile type. When both characteristics are mentioned, the anatase type has good reflectivity in the visible light short wavelength region, and any of the white pigments to be added to the resin composition of the present invention is not particularly limited. It is of course possible to use a mixture of both.
本発明において、前記樹脂組成物に含まれる白色顔料の含有量は、樹脂組成物全体に対し１０〜７５重量％となるようにするのが好ましい。１０重量％以上であれば十分な白色度、反射率を得ることができ、７５重量％以下であればガラス布基材への含浸性が低下したり金属箔との接着強度が低下したりと いった不具合が発生することはない。 In this invention, it is preferable to make content of the white pigment contained in the said resin composition into 10 to 75 weight% with respect to the whole resin composition. If it is 10% by weight or more, sufficient whiteness and reflectance can be obtained, and if it is 75% by weight or less, the impregnation property to the glass cloth substrate is lowered or the adhesive strength to the metal foil is lowered. Such a problem does not occur.
また、白色顔料として二酸化チタンを使用する場合、二酸化チタンには表面処理としてアルミナ、シリカ、ジルコニア処理等を行っても良い。又、シラン系カップリング剤やチタネート系カップリング剤処理も可能である。 When titanium dioxide is used as the white pigment, the titanium dioxide may be subjected to alumina, silica, zirconia treatment or the like as a surface treatment. Moreover, a silane coupling agent or titanate coupling agent treatment is also possible.
本発明においては、前記樹脂組成物に、前記白色顔料の他に、無機充填材を含有させてもよい。 In the present invention, the resin composition may contain an inorganic filler in addition to the white pigment.
上記無機充填材としては、シリカ、アルミナ、窒化ホウ素、水酸化アルミニウム、水酸化マグネシウム、Ｅガラス粉末、酸化マグネシウム、チタン酸カリウム、ケイ酸カルシウム、クレイ、タルク等が挙げられ、シリカ、アルミナ、窒化ホウ素からなる群から選ばれる少なくとも一種以上の無機充填材を使用するのが好ましい。上記無機充填材は、単体で使用しても良く、２種以上を併用しても良い。これらの無機充填材を含有することにより、基板の剛性率が向上する。無機充填材配合量は特に限定しないが、前記樹脂組成物に対して５０重量％以下であることが好ましい。配合量が５０重量％以下であればガラス布基材への含浸性が低下したり、金属箔との接着強度が低下したりといった不具合が発生する可能性はほとんど生じない。 Examples of the inorganic filler include silica, alumina, boron nitride, aluminum hydroxide, magnesium hydroxide, E glass powder, magnesium oxide, potassium titanate, calcium silicate, clay, and talc. It is preferable to use at least one inorganic filler selected from the group consisting of boron. The said inorganic filler may be used individually and may use 2 or more types together. By containing these inorganic fillers, the rigidity of the substrate is improved. The blending amount of the inorganic filler is not particularly limited, but is preferably 50% by weight or less with respect to the resin composition. If the blending amount is 50% by weight or less, there is almost no possibility that the impregnation property to the glass cloth substrate is lowered or the adhesive strength with the metal foil is lowered.
本発明のプリプレグに使用するガラス布基材としては、ガラスクロス、不織布のいずれでもよく、ガラスクロスと不織布とを併用してもよい。ガラスクロスの場合、平織り構造を基本とするが、ななこ織り、繻子織り、綾織り等の織物構造でもよく、特に限定するものではない。外観や加工性を損なわないために経糸と緯糸の交差部の隙間が小さい織り構造を使用することが好ましい。ガラスクロスの厚みについては、特に制限はないが０．０２〜０．３ｍｍの範囲のものが取り扱いやすく好ましい。 As a glass cloth base material used for the prepreg of the present invention, either a glass cloth or a nonwoven fabric may be used, and a glass cloth and a nonwoven fabric may be used in combination. In the case of a glass cloth, a plain weave structure is basically used, but a woven structure such as Nanako weave, satin weave or twill weave may be used, and is not particularly limited. In order not to impair the appearance and workability, it is preferable to use a woven structure in which the gap between the intersections of the warp and the weft is small. Although there is no restriction | limiting in particular about the thickness of a glass cloth, The thing of the range of 0.02-0.3 mm is easy to handle and preferable.
また、上記ガラス布基材に、シランカップリング剤等による表面処理を行ってもよい。さらに、ガラス布基材自身が白色に着色されたものでもよい。 Moreover, you may perform the surface treatment by a silane coupling agent etc. to the said glass cloth base material. Furthermore, the glass cloth base material itself may be colored white.
本発明のプリプレグは、上記樹脂組成物に、トルエン等の溶剤を加え、樹脂ワニスを調製し、ガラスクロス等からなるガラス布基材に含浸、乾燥して製造される。上記樹脂組成物をガラス布基材に含浸・乾燥させる方法は特に限定されるものではなく、例えば樹脂組成物中に、ガラス布基材を浸漬するなどして含浸させた後、８０℃〜１５０℃程度の温度で加熱して溶剤の除去および付加硬化型シリコーン樹脂を半硬化させる方法等が採用できる。ガラス布基材に含浸・乾燥して製造するプリプレグの樹脂組成物含浸量は、特に限定されないが、ガラス布基材に対して３０〜６０重量％とするのが好ましい。 The prepreg of the present invention is produced by adding a solvent such as toluene to the resin composition to prepare a resin varnish, impregnating and drying the glass cloth substrate made of glass cloth or the like. The method of impregnating and drying the resin composition on the glass cloth substrate is not particularly limited. For example, after impregnating the glass cloth substrate into the resin composition by impregnation, the temperature is 80 ° C. to 150 ° C. A method of removing the solvent and semi-curing the addition-curable silicone resin by heating at a temperature of about 0 ° C. can be employed. The impregnation amount of the resin composition of the prepreg produced by impregnating and drying the glass cloth substrate is not particularly limited, but is preferably 30 to 60% by weight with respect to the glass cloth substrate.
本発明の積層板は、上記プリプレグを１枚、または複数枚重ねて、加熱加圧成形して形成される。また、本発明の金属箔張り積層板は、前記プリプレグを１枚、または複数枚重ね、さらに金属箔を重ねて、加熱加圧成形して形成される。プリプレグを重ね合わせる枚数は特に制限はないが、単層基板としての積層板はプリプレグ１枚、又は２〜１０枚を重ね、金属箔張り積層板の場合はその上に、又は上下に金属箔を積層配置するのが一般的である。金属箔としては、銅箔、アルミニウム箔等が用いられる。又、金属箔の厚みは３μｍ〜１０５μｍが一般的であり、特に９μｍ〜３５μｍとするのが好ましい。また、多層構成とする場合、本発明のプリプレグを積層する表面層のみに使用し、中間層には従来技術によるプリプレグを使用することも可能である。このようにして得られた本発明の積層板及び金属箔張り積層板は、可視光領域の反射率が９０％以上と高く、しかも加熱や紫外線による変色もなく、高い耐熱性を持った板厚精度に優れる。 The laminated board of the present invention is formed by stacking one or a plurality of the above prepregs and heating and pressing. In addition, the metal foil-clad laminate of the present invention is formed by one or a plurality of the above prepregs, and further by overlapping the metal foils, followed by heating and pressing. The number of prepregs to be stacked is not particularly limited, but a laminate as a single-layer substrate is a single prepreg, or 2 to 10 laminates. In general, they are stacked. As the metal foil, copper foil, aluminum foil or the like is used. The thickness of the metal foil is generally 3 μm to 105 μm, and particularly preferably 9 μm to 35 μm. Moreover, when setting it as a multilayer structure, it is also possible to use only for the surface layer which laminates the prepreg of this invention, and to use the prepreg by a prior art for an intermediate | middle layer. The laminate and the metal foil-clad laminate of the present invention thus obtained have a high reflectivity in the visible light region of 90% or more, and are not discolored by heating or ultraviolet rays, and have a high heat resistance. Excellent accuracy.
本発明の積層板に、アディティブ法にて導体パターンを形成し、プリント配線基板を製造する。又、本発明の金属箔張り積層板の金属箔上に回路パターンを印刷し、エッチングを施してプリント配線基板を製造する。チップＬＥＤを該プリント配線基板に実装するには、先ずプリント配線基板上に半田を塗布し、その上にチップＬＥＤを載置したのち、これをリフロー等に通して半田を溶融することでチップＬＥＤをプリント基板に固定する。チップＬＥＤを高密度集積させることで面光源としての利用も可能になり、このような面光源は特に薄型であることが要求される液晶ディスプレイ用バックライトに好適に利用される。その他、面発光型の照明装置として誘導表示照明灯、避難口照明灯、広告灯等へ応用される。 A conductive pattern is formed on the laminate of the present invention by an additive method, and a printed wiring board is manufactured. In addition, a circuit pattern is printed on the metal foil of the metal foil-clad laminate of the present invention and etched to produce a printed wiring board. In order to mount the chip LED on the printed wiring board, first, solder is applied on the printed wiring board, and the chip LED is placed on the printed wiring board, and then the chip LED is melted by passing it through reflow or the like. Is fixed to the printed circuit board. By integrating chip LEDs with high density, it can be used as a surface light source, and such a surface light source is suitably used for a backlight for a liquid crystal display that is particularly required to be thin. In addition, it is applied to induction display illumination lamps, evacuation exit illumination lamps, advertisement lights, etc. as surface emitting illumination devices.
次に本発明を実施例によってさらに詳細に説明するが、本発明は、その要旨を逸脱しないかぎり、以下に限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to the following, unless it deviates from the summary.
実施例１
樹脂組成物として、付加硬化型シリコーンレジン：ＫＲ−２６２１−１＋Ｄ−２６２１（信越化学工業（株）製）１００重量部 、３−メタクリロイロキシプロピルトリメトキシシラン：ＫＢＭ−５０３（信越化学工業（株）製）５重量部をトルエン１００重量部に溶解させた。そこに、白色顔料としてルチル型二酸化チタンＣＲ−６７（石原産業（株）製）７５重量部を添加し、室温で１時間攪拌して白色シリコーンワニスを得た。この白色シリコーンワニスを０．１ｍｍ厚ガラスクロスＷＥＡ−１１６Ｅ（日東紡（株）製）に含浸させ、１３０℃で５分間予備乾燥し、樹脂組成物含有量５０重量％のプリプレグを得た。該プリプレグ４枚、及び１０枚積層したものに対し、それぞれの上下に３５μｍ厚さの銅箔を重ね、圧力２０ｋｇｆ／ｃｍ２、温度２００℃で加熱加圧成形して、０．４ｍｍ厚、及び１ｍｍ厚の銅箔張り白色積層板をそれぞれ得た。
Example 1
As the resin composition, 100 parts by weight of addition-curable silicone resin: KR-2621-1 + D-2621 (manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloyloxypropyltrimethoxysilane: KBM-503 (Shin-Etsu Chemical Co., Ltd.) ) 5 parts by weight was dissolved in 100 parts by weight of toluene. Thereto, 75 parts by weight of rutile titanium dioxide CR-67 (Ishihara Sangyo Co., Ltd.) was added as a white pigment and stirred at room temperature for 1 hour to obtain a white silicone varnish. This white silicone varnish was impregnated into 0.1 mm thick glass cloth WEA-116E (manufactured by Nittobo Co., Ltd.) and pre-dried at 130 ° C. for 5 minutes to obtain a prepreg having a resin composition content of 50% by weight. For the laminates of 4 and 10 prepregs, 35 μm-thick copper foils are stacked on top and bottom of each, and heat-pressed at a pressure of 20 kgf / cm 2 and a temperature of 200 ° C., 0.4 mm thickness, and Each 1 mm thick copper foil-clad white laminate was obtained.
参考例１
白色シリコーンワニスの組成を下記のように変え、他は実施例１と同様にして白色積層板を得た。付加硬化型シリコーンレジン：ＫＲ−２６２１−１＋Ｄ−２６２１（信越化学工業（株）製）１００重量部 をトルエン１００重量部に溶解させた。そこに、白色顔料としてルチル型二酸化チタンＣＲ−６７（石原産業（株）製）７５重量部を添加し、室温で１時間攪拌して白色シリコーンワニスを得た。
Reference example 1
A white laminate was obtained in the same manner as in Example 1 except that the composition of the white silicone varnish was changed as follows. Addition-curing silicone resin: 100 parts by weight of KR-2621-1 + D-2621 (manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 100 parts by weight of toluene. Thereto, 75 parts by weight of rutile titanium dioxide CR-67 (Ishihara Sangyo Co., Ltd.) was added as a white pigment and stirred at room temperature for 1 hour to obtain a white silicone varnish.
比較例１
白色シリコーンワニスの変わりに、エポキシ樹脂を下記の組成で配合した白色エポキシワニスを得、他は実施例１と同様にして白色積層板を得た。エポキシ樹脂：ＡＥＲ６０５１（旭化成エポキシ（株）製）１００重量部 をＭＥＫ１００重量部に溶解させた。そこに、ジシアンジアミドを樹脂１００重量部に対して２．５重量部、２フェニルイミダゾールを樹脂１００重量部に対して０．１重量部、白色顔料としてルチル型二酸化チタンＣＲ−６７（石原産業（株）製）７５重量部を添加し、室温で１時間攪拌して白色エポキシワニスを得た。
Comparative Example 1
Instead of the white silicone varnish, a white epoxy varnish was obtained by blending an epoxy resin with the following composition, and a white laminate was obtained in the same manner as in Example 1. Epoxy resin: 100 parts by weight of AER6051 (Asahi Kasei Epoxy Co., Ltd.) was dissolved in 100 parts by weight of MEK. There, 2.5 parts by weight of dicyandiamide with respect to 100 parts by weight of resin, 0.1 part by weight of 2 phenylimidazole with respect to 100 parts by weight of resin, and rutile titanium dioxide CR-67 (Ishihara Sangyo Co., Ltd.) as a white pigment. ) Made by adding 75 parts by weight and stirring at room temperature for 1 hour to obtain a white epoxy varnish.
［効果確認試験］
１）耐熱変色性
実施例１、参考例１、比較例１で得られた０．４ｍｍの銅箔張り白色積層板の銅箔をエッチング処理によって除去した後、該積層板表面の白色度・明度をコニカミノルタ製のＣＭ−３６００ｄにて測定し、さらに２００℃で７０時間加熱処理した後の白色度・明度も同様に測定した。その結果を表１に示す。表1から明らかなように、実施例１、参考例1の積層板は、エポキシ樹脂を用いた比較例１の積層板と比べて初期の白色度・明度が高く、加熱後の白色度・明度の低下が著しく小さく、耐熱性が高いのがわかる。
２）耐紫外線性
実施例１、参考例１、比較例１で得られた０．４ｍｍ厚の銅箔張り白色積層板の銅箔をエッチング処理によって除去した後、該積層板表面の白色度・明度を測定し、さらに５６００Ｗの高圧水銀灯光（紫外部発光スペクトル：２５３．７ｎｍ，３６５ｎｍ）３本を基板に対して照射距離１５ｃｍ（照射強度＝約３ＫＷ／ｍ２、１回当たり３０秒）で１００回照射処理した後の白色度・明度を同様に測定した。その結果を表１に示す。表1から明らかなように、実施例１、参考例1の積層板は、比較例１の積層板と比べて、明らかに紫外線照射後の白色度・明度の低下が小さく、耐紫外線性も著しく向上しているのが分かる。
３）銅箔剥離強度
銅箔の接着強度はＪＩＳ−Ｃ６４８１に準拠して、剥離強度を求めた。すなわち実施例１、参考例１、比較例１で得られた０．４ｍｍ厚の銅箔張り白色積層板の銅箔を１０ｍｍ幅で剥離させ、９０度剥離試験により求めた。その結果を表１に示す。実施例１、比較例１の銅箔剥離強度は、それぞれ０．７ｋＮ、１．２ｋＮであった。この結果から実施例１の銅箔張り白色積層板は、十分な銅箔剥離強度も得られている。
[Effectiveness confirmation test]
1) Heat discoloration resistance After removing the copper foil of the 0.4 mm copper foil-clad white laminate obtained in Example 1, Reference Example 1 and Comparative Example 1 by etching treatment, the whiteness / lightness of the laminate plate surface Was measured with CM-3600d manufactured by Konica Minolta, and the whiteness and brightness after heat treatment at 200 ° C. for 70 hours were also measured in the same manner. The results are shown in Table 1. As is clear from Table 1, the laminates of Example 1 and Reference Example 1 had higher initial whiteness and brightness than the laminate of Comparative Example 1 using epoxy resin, and the brightness and brightness after heating. It can be seen that the decrease in resistance is extremely small and the heat resistance is high.
2) UV resistance After removing the copper foil of the 0.4 mm-thick copper foil-clad white laminate obtained in Example 1, Reference Example 1 and Comparative Example 1 by etching treatment, The lightness was measured, and further, 3 pieces of 5600 W high-pressure mercury lamp light (ultraviolet part emission spectrum: 253.7 nm, 365 nm) were applied to the substrate at an irradiation distance of 15 cm (irradiation intensity = about 3 kW / m 2 , 30 seconds per time). The whiteness and lightness after 100 irradiation treatments were measured in the same manner. The results are shown in Table 1. As can be seen from Table 1, the laminates of Example 1 and Reference Example 1 clearly have a smaller decrease in whiteness and lightness after UV irradiation than the laminate of Comparative Example 1, and the UV resistance is remarkably high. You can see that it has improved.
3) Copper foil peel strength The bond strength of the copper foil was determined in accordance with JIS-C6481. That is, the copper foil of the 0.4 mm-thick copper foil-clad white laminate obtained in Example 1, Reference Example 1 and Comparative Example 1 was peeled off at a width of 10 mm, and the 90-degree peeling test was performed. The results are shown in Table 1. The copper foil peel strengths of Example 1 and Comparative Example 1 were 0.7 kN and 1.2 kN, respectively. From this result, the copper foil-clad white laminate of Example 1 has sufficient copper foil peel strength.
※紫外線照射は、３０秒／回で１００回
本発明のプリプレグ、積層板、金属箔張り積層板は、紫外発光素子や高輝度青色ＬＥＤによる紫外線や青色のような高エネルギーの光による劣化・変色が極めて少なく、高い耐熱性および板厚精度を有するため、チップ型発光ダイオードを実装するためのプリント配線基板や、チップＬＥＤの反射枠として好適に使用できる。 The prepregs, laminates, and metal foil-clad laminates of the present invention are extremely resistant to deterioration and discoloration due to ultraviolet light or high energy light such as blue light emitted from ultraviolet light emitting elements or high-intensity blue LEDs, and have high heat resistance and thickness accuracy. Therefore, it can be suitably used as a printed wiring board for mounting a chip-type light-emitting diode or a reflection frame of a chip LED.
Claims (6)
前記樹脂組成物が、グリシジル（メタ）アクリレート重合体、もしくはグリシジル（メタ）アクリレートを共重合成分として含有する共重合体から選ばれる１種または２種以上のポリマーを、樹脂組成物全体に対し０．０５〜１５重量％含有し、
前記白色顔料が、二酸化チタン、酸化亜鉛、硫酸バリウムからなる群から選ばれる少なくとも一種以上の白色顔料であることを特長とするプリプレグ。 Peroxide or impregnated with a resin composition mainly composed of an addition-curable silicone resin is cured using a metal complex catalyst to the glass fabric substrate, Ri Na dried,
The resin composition contains one or more polymers selected from a glycidyl (meth) acrylate polymer or a copolymer containing glycidyl (meth) acrylate as a copolymerization component with respect to the entire resin composition. 0.05 to 15% by weight,
A prepreg characterized in that the white pigment is at least one or more white pigments selected from the group consisting of titanium dioxide, zinc oxide, and barium sulfate .
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| JP6072662B2 (en) * | 2013-10-10 | 2017-02-01 | 信越化学工業株式会社 | Silicone resin composition, laminate using the composition, and LED device having the laminate |
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| CN105778505B (en) * | 2014-12-25 | 2019-04-30 | 广东生益科技股份有限公司 | A kind of organosilicon resin composition and white prepreg and white laminated plate using it |
| JP6570104B2 (en) * | 2014-12-26 | 2019-09-04 | 株式会社シマノ | Colored prepreg and tubular body |
| JP6089144B1 (en) * | 2016-03-30 | 2017-03-01 | 日本タングステン株式会社 | Copper-clad laminate and manufacturing method thereof |
| CN107303743B (en) * | 2016-04-21 | 2023-04-07 | 广东生益科技股份有限公司 | Polysiloxane composition laminated board and metal foil-clad laminated board thereof |
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