JPH10182985A - Resin composition for laminated plate and laminated plate - Google Patents
Resin composition for laminated plate and laminated plateInfo
- Publication number
- JPH10182985A JPH10182985A JP34420396A JP34420396A JPH10182985A JP H10182985 A JPH10182985 A JP H10182985A JP 34420396 A JP34420396 A JP 34420396A JP 34420396 A JP34420396 A JP 34420396A JP H10182985 A JPH10182985 A JP H10182985A
- Authority
- JP
- Japan
- Prior art keywords
- phosphorus
- resin
- resin composition
- compound
- laminate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 31
- 239000011574 phosphorus Substances 0.000 claims abstract description 31
- 239000003365 glass fiber Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 16
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 150000002367 halogens Chemical class 0.000 claims abstract description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 6
- 239000002759 woven fabric Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 7
- 238000010030 laminating Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 4
- XPXVJLZTBUUIGC-UHFFFAOYSA-N azanium dihydrogen phosphate phosphane Chemical compound OP(O)(O)=O.N.P XPXVJLZTBUUIGC-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 239000011888 foil Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 4
- -1 phosphorus compound Chemical class 0.000 abstract description 3
- 239000002341 toxic gas Substances 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 2
- 230000036571 hydration Effects 0.000 abstract 2
- 238000006703 hydration reaction Methods 0.000 abstract 2
- 238000003475 lamination Methods 0.000 abstract 1
- 238000010526 radical polymerization reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000004114 Ammonium polyphosphate Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 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 3
- 239000011190 CEM-3 Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 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
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、プリント配線板な
どに加工して使用される積層板用樹脂組成物及び積層板
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a laminated board used for processing a printed wiring board and the like, and a laminated board.
【０００２】[0002]
【従来の技術】プリント配線板などに用いられる積層板
は、ガラス布等の基材に樹脂を含浸し、そしてこれを複
数枚重ねると共に必要に応じてさらに銅箔等の金属箔を
重ね、これを加熱成形することによって、製造されてい
る。このような積層板を難燃化するために、臭素や塩素
等のハロゲン元素を分子の骨格に導入した難燃性樹脂を
用いて積層板を製造することが従来から行なわれてい
る。2. Description of the Related Art A laminated board used for a printed wiring board or the like is formed by impregnating a base material such as a glass cloth with a resin, laminating a plurality of the layers and, if necessary, further laminating a metal foil such as a copper foil. Is manufactured by heat molding. In order to make such a laminated board flame-retardant, it has been conventionally performed to manufacture a laminated board using a flame-retardant resin in which a halogen element such as bromine or chlorine is introduced into a molecular skeleton.
【０００３】[0003]
【発明が解決しようとする課題】しかし、このような臭
素や塩素等を含有する難燃性樹脂を用いて製造した積層
板を燃やすと、樹脂骨格中の臭素や塩素が解離し、臭化
水素ガス、塩化水素ガス、あるいはダイオキシン等の有
毒ガスが発生するおそれがあるという問題があった。However, when a laminate manufactured using such a flame-retardant resin containing bromine and chlorine is burned, bromine and chlorine in the resin skeleton are dissociated, and hydrogen bromide is dissociated. There is a problem that a toxic gas such as gas, hydrogen chloride gas, or dioxin may be generated.
【０００４】本発明は上記の点に鑑みてなされたもので
あり、ハロゲン元素による有毒ガスの発生のおそれなく
高い難燃性を得ることができる積層板用樹脂組成物及び
積層板を提供することを目的とするものである。[0004] The present invention has been made in view of the above points, and provides a resin composition for laminates and a laminate capable of obtaining high flame retardancy without fear of generation of toxic gas due to halogen elements. It is intended for.
【０００５】[0005]
【課題を解決するための手段】本発明に係る積層板用樹
脂組成物は、ハロゲンを含有しないラジカル重合型樹脂
１００重量に対して、リン含有化合物がリン分換算で１
〜３０重量部、無機水和化合物が１０〜２００重量部配
合されて成ることを特徴とするものである。また請求項
２の発明は、上記のリン含有化合物として赤燐を用いる
ことを特徴とするものである。The resin composition for a laminate according to the present invention is characterized in that a phosphorus-containing compound is contained in an amount of 1 in terms of phosphorus based on 100 parts by weight of a radical-polymerizable resin containing no halogen.
-30 parts by weight, and 10-200 parts by weight of an inorganic hydrate compound. The invention according to claim 2 is characterized in that red phosphorus is used as the phosphorus-containing compound.
【０００６】また請求項３の発明は、上記の赤燐として
平均粒径が１０μ以下の赤燐を用いることを特徴とする
ものである。また請求項４の発明は、リン含有化合物と
してポリリン酸アンモニウムを用いることを特徴とする
ものである。また請求項５の発明は、上記の無機水和化
合物として水酸化アルミニウムを用いることを特徴とす
るものである。A third aspect of the present invention is characterized in that red phosphorus having an average particle diameter of 10 μm or less is used as the red phosphorus. The invention according to claim 4 is characterized in that ammonium polyphosphate is used as the phosphorus-containing compound. The invention of claim 5 is characterized in that aluminum hydroxide is used as the inorganic hydrated compound.
【０００７】本発明に係る積層板は、上記の積層板用樹
脂組成物を基材に含浸すると共にこれを重ねて成形して
形成されたことを特徴とするものである。また請求項７
の発明は、上記の基材としてガラス繊維不織布と、ガラ
ス繊維織布とを組み合わせて用いることを特徴とするも
のである。A laminate according to the present invention is characterized by being formed by impregnating a base material with the above resin composition for a laminate and laminating and molding the same. Claim 7
The present invention is characterized in that a glass fiber nonwoven fabric and a glass fiber woven fabric are used in combination as the base material.
【０００８】[0008]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。本発明においてラジカル重合型樹脂としてはビニ
ルエステル樹脂を用いることができるものであり、ビニ
ルエステル樹脂の他にエポキシ樹脂、フェノール樹脂、
不飽和ポリエステル樹脂、ポリイミド樹脂などもラジカ
ル重合型樹脂として用いることができる。そして本発明
ではこれらのラジカル重合型樹脂として、分子骨格中に
臭素や塩素等のハロゲン元素が導入されていないノンハ
ロゲンのものを用いるものである。また、ラジカル重合
型樹脂としてウレタン基やアニリン基、メラミン基など
Ｎを含む基を導入したものを用いると、ラジカル重合型
樹脂自身が難燃性を有するので後述の赤燐などのリン含
有化合物の使用量を低減することができるものである。Embodiments of the present invention will be described below. In the present invention, a vinyl ester resin can be used as the radical polymerization type resin, and in addition to the vinyl ester resin, an epoxy resin, a phenol resin,
Unsaturated polyester resins, polyimide resins and the like can also be used as radical polymerization type resins. In the present invention, non-halogen resins in which a halogen element such as bromine or chlorine is not introduced into the molecular skeleton are used as these radical polymerization resins. Further, when a radical-polymerizable resin having a group containing N such as a urethane group, an aniline group, or a melamine group is used, the radical-polymerizable resin itself has flame retardancy, so that a phosphorus-containing compound such as red phosphorus described below is used. The use amount can be reduced.
【０００９】また本発明においてリン含有化合物として
は、リンを含有するものであれば無機化合物、有機化合
物を問わず使用することができるが、無機リン化合物と
しては赤燐を用いるのが好ましく、有機リン化合物とし
てはポリリン酸アンモニウムを用いるのが好ましい。赤
燐を用いる場合には、平均粒径が１０μｍ以下のものを
用いるのが好ましい。平均粒径が１０μｍを超える赤燐
を用いると、赤燐をラジカル重合型樹脂に混合する際に
沈降が発生するおそれがあって難燃性を高める効果を十
分に発揮させることができず、また得られた積層板にス
ルーホールをドリル加工する際にドリル磨耗が大きく発
生するおそれがある。赤燐の平均粒径の下限は特に設定
されるものではないが、０．１μｍを下回らない範囲が
好ましい。In the present invention, as the phosphorus-containing compound, any inorganic compound or organic compound can be used as long as it contains phosphorus. As the inorganic phosphorus compound, red phosphorus is preferably used. It is preferable to use ammonium polyphosphate as the phosphorus compound. When using red phosphorus, it is preferable to use one having an average particle size of 10 μm or less. When red phosphorus having an average particle size of more than 10 μm is used, sedimentation may occur when red phosphorus is mixed with the radical polymerization type resin, and the effect of increasing the flame retardancy cannot be sufficiently exerted. When drilling through holes in the obtained laminate, drill abrasion may be significantly generated. The lower limit of the average particle diameter of red phosphorus is not particularly set, but is preferably in a range not less than 0.1 μm.
【００１０】さらに本発明において無機水和化合物とし
ては、水酸化アルミニウムや水酸化マグネシウムなどを
使用することができるが、水酸化アルミニウムを用いる
のが好ましい。そして、ラジカル重合型樹脂にリン含有
化合物と無機水和化合物を配合し、さらにラジカル重合
開始剤などを配合することによって、本発明に係る積層
板用樹脂組成物を得ることができるものである。ラジカ
ル重合開始剤としては特に限定されるものではないが、
例えば「化１」に示すようなパーブチルＯを用いること
ができる。In the present invention, as the inorganic hydrated compound, aluminum hydroxide and magnesium hydroxide can be used, but aluminum hydroxide is preferably used. Then, a resin composition for a laminated board according to the present invention can be obtained by mixing a phosphorus-containing compound and an inorganic hydrate compound with a radical polymerization type resin, and further mixing a radical polymerization initiator and the like. The radical polymerization initiator is not particularly limited,
For example, perbutyl O as shown in “Formula 1” can be used.
【００１１】[0011]
【化１】 Embedded image
【００１２】ここで、リン含有化合物は、ラジカル重合
型樹脂１００重量部に対して、リン分換算で１〜３０重
量部の範囲で配合するのが好ましい。本発明は、ラジカ
ル重合型樹脂にリン含有化合物と無機水和化合物を併用
して配合することによって、難燃性を高く得ることがで
きるようにしたものであり、リン含有化合物の配合量が
リン分換算で１重量部未満であると、リン含有化合物を
配合することによって難燃性を高める効果を十分に得る
ことができず、逆にリン含有化合物の配合量がリン分換
算で３０重量部を超えると、耐熱性が低下すると共に吸
湿率が高くなるおそれがあり、好ましくない。また無機
水和化合物は、ラジカル重合型樹脂１００重量部に対し
て１０〜２００重量部の範囲で配合するのが好ましい。
無機水和化合物の配合量が１０重量部未満であると、無
機水和化合物をリン含有化合物と併用して配合すること
によって難燃性を高める効果を十分に得ることができ
ず、逆に無機水和化合物の配合量が２００重量部を超え
ると、耐熱性が低下すると共に吸湿率が高くなるおそれ
があり、好ましくない。Here, the phosphorus-containing compound is preferably blended in an amount of 1 to 30 parts by weight in terms of phosphorus based on 100 parts by weight of the radical polymerization type resin. The present invention is intended to obtain a high flame retardancy by combining a radical polymerization type resin with a phosphorus-containing compound and an inorganic hydrated compound. When the amount is less than 1 part by weight, the effect of enhancing the flame retardancy cannot be sufficiently obtained by compounding the phosphorus-containing compound. Conversely, the compounding amount of the phosphorus-containing compound is 30 parts by weight in terms of phosphorus. If it exceeds, the heat resistance may decrease and the moisture absorption may increase, which is not preferred. Further, the inorganic hydrated compound is preferably blended in a range of 10 to 200 parts by weight based on 100 parts by weight of the radical polymerization type resin.
If the amount of the inorganic hydrated compound is less than 10 parts by weight, the effect of enhancing the flame retardancy cannot be sufficiently obtained by combining the inorganic hydrated compound with the phosphorus-containing compound, and conversely, the inorganic hydrated compound cannot be obtained. If the amount of the hydrated compound exceeds 200 parts by weight, the heat resistance may decrease and the moisture absorption may increase, which is not preferable.
【００１３】上記のようにして得られる積層板用樹脂組
成物を用いて、積層板を製造することができる。すなわ
ち、ラジカル重合型樹脂が液状樹脂であればそのまま
（あるいは溶剤で粘度を調整して）用い、ラジカル重合
型樹脂が固形樹脂であれば溶剤に溶解してワニス状に積
層板用樹脂組成物を調製し、ガラス布などの基材にこの
積層板用樹脂組成物を含浸した後、この基材を複数枚重
ねると共に必要に応じてその外側に銅箔等の金属箔を重
ね、これを加熱成形してラジカル重合型樹脂を硬化させ
ることによって、積層板を製造することができるもので
ある。Using the resin composition for a laminate obtained as described above, a laminate can be manufactured. That is, if the radical polymerizable resin is a liquid resin, it is used as it is (or the viscosity is adjusted with a solvent), and if the radical polymerizable resin is a solid resin, it is dissolved in a solvent and the varnish-shaped resin composition for a laminate is used. After preparing and impregnating a base material such as a glass cloth with the resin composition for a laminate, a plurality of the base materials are stacked, and a metal foil such as a copper foil is stacked on the outside of the base material as necessary, and then heated and formed. Then, by curing the radical polymerization type resin, a laminate can be manufactured.
【００１４】図１は連続工法による積層板の製造の一例
を示すものであり、ロール状に巻いた長尺帯状のガラス
繊維織布１とガラス繊維不織布２をそれぞれ繰り出して
連続して送るようにしてある。基材としてこのようにガ
ラス繊維織布１とガラス繊維不織布２を用いるものであ
り、ガラス繊維織布１で積層板の表層部を形成するよう
に、ガラス繊維不織布２で積層板の芯部を形成するよう
にガラス繊維織布１とガラス繊維不織布２をそれぞれ配
置してある。そして上記の積層板用樹脂組成物を供給し
た含浸槽１０にガラス繊維織布１とガラス繊維不織布２
を連続して送りつつ通すことによって、ガラス繊維織布
１とガラス繊維不織布２にそれぞれ積層板用樹脂組成物
を含浸させ、樹脂含浸基材１１，１２を得る。ここで、
ガラス繊維不織布２を基材とする樹脂含浸基材１２には
必要量丁度あるいは必要量を少し超える程度の積層板用
樹脂組成物を含浸させるようにしてあり、またガラス繊
維織布１を基材とする樹脂含浸基材１１には必要量を超
える量の積層板用樹脂組成物を含浸させ、この樹脂含浸
基材１１を長尺帯状の銅箔など金属箔３と重ねて絞りロ
ール６，６間に通し、過剰な積層板用樹脂組成物を除去
すると共に樹脂含浸基材１１の外面側に金属箔３を圧着
させるようにしてある。次に、金属箔３を圧着した樹脂
含浸基材１１と樹脂含浸基材１２を連続して送りつつ積
層ロール４，４間に通し、積層一体化した後、さらにこ
の積層物を連続して送りつつ、硬化炉５を通過させて加
熱することによって、両面金属箔貼りの積層板を連続的
に製造することができるものであり、これを所定寸法に
切断した後、さらに加熱して硬化反応を完了させること
によって、仕上げることができるものである。FIG. 1 shows an example of the production of a laminated board by a continuous method, in which a long belt-shaped glass fiber woven fabric 1 and a glass fiber non-woven fabric 2 wound in a roll are respectively fed out and fed continuously. It is. The glass fiber woven fabric 1 and the glass fiber non-woven fabric 2 are used as the base material in this manner, and the glass fiber non-woven fabric 2 forms the core of the laminate such that the glass fiber woven fabric 1 forms the surface layer of the laminate. The glass fiber woven fabric 1 and the glass fiber nonwoven fabric 2 are arranged so as to be formed. Then, the glass fiber woven fabric 1 and the glass fiber non-woven fabric 2 are placed in the impregnation tank 10 supplied with the resin composition for a laminate.
Are continuously fed and passed, thereby impregnating the glass fiber woven fabric 1 and the glass fiber nonwoven fabric 2 with the resin composition for a laminate, respectively, to obtain resin-impregnated substrates 11 and 12. here,
The resin impregnated base material 12 based on the glass fiber nonwoven fabric 2 is impregnated with the required amount of the resin composition for a laminate just or slightly over the required amount. The resin-impregnated base material 11 is impregnated with a resin composition for a laminate in an amount exceeding a required amount, and the resin-impregnated base material 11 is superimposed on a metal foil 3 such as a long strip-shaped copper foil, and the drawing rolls An excess amount of the resin composition for a laminate is removed therefrom, and the metal foil 3 is pressed against the outer surface of the resin-impregnated base material 11. Next, the resin-impregnated base material 11 and the resin-impregnated base material 12 to which the metal foil 3 has been pressed are passed between the laminating rolls 4 and 4 while being continuously fed, and are laminated and integrated. While passing through the curing furnace 5 and heating, it is possible to continuously produce a double-sided metal foil-laminated laminate, which is cut into a predetermined size, and further heated to carry out a curing reaction. It can be finished by completing it.
【００１５】このようにして、ガラス繊維不織布２を芯
部とし、ガラス繊維織布１を表層部とするＣＥＭ−３の
コンポジット構成の積層板を得ることができるものであ
り、そしてラジカル重合型樹脂にリン含有化合物と無機
水和化合物を併用して配合した樹脂組成物を用いること
によって、高い難燃性を実現した積層板を得ることがで
きるものである。尚、片面金属箔貼り積層板を製造する
場合には、一方の金属箔３の変わりに有機樹脂フィルム
を用い、成形後に有機樹脂フィルムを剥がすようにすれ
ばよい。In this way, it is possible to obtain a CEM-3 composite laminate having the glass fiber nonwoven fabric 2 as the core and the glass fiber woven fabric 1 as the surface layer. By using a resin composition in which a phosphorus-containing compound and an inorganic hydrated compound are used together, a laminate having high flame retardancy can be obtained. When a single-sided metal foil-laminated laminate is manufactured, an organic resin film may be used instead of one metal foil 3, and the organic resin film may be peeled off after molding.
【００１６】[0016]
【実施例】次に、本発明を実施例によって具体的に説明
する。 （実施例１〜実施例５、比較例１，２）表１に示す配合
で表層部用の樹脂組成物Ａ〜Ｇを、表２に示す配合で芯
部用の樹脂組成物Ａ〜Ｇをそれぞれ調製した。ここで、
ビニルエステル樹脂はノンハロゲンタイプのエポキシア
クリレート樹脂であり、昭和高分子社製Ｒ−８００（色
数（ガードナー）１６以下、粘度（２５℃）４〜８ポア
ズ、比重（１２５℃）１．０４２）を使用し、ラジカル
重合開始剤としては日本油脂社製パーブチルＯを使用し
た。Next, the present invention will be described specifically with reference to examples. (Examples 1 to 5 and Comparative Examples 1 and 2) Resin compositions A to G for the surface layer portion in the composition shown in Table 1 and resin compositions A to G for the core portion in the composition shown in Table 2 Each was prepared. here,
The vinyl ester resin is a non-halogen type epoxy acrylate resin and has a R-800 (Gardner) of 16 or less, a viscosity (25 ° C.) of 4 to 8 poise, and a specific gravity (125 ° C. of 1.042) manufactured by Showa Polymer Co., Ltd. Perbutyl O manufactured by NOF Corporation was used as a radical polymerization initiator.
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【表２】 [Table 2]
【００１９】そして図１に示す装置で両面銅貼り積層板
を製造した。すなわち、ガラス繊維織布１として日東紡
績社製７６２８タイプを２枚、ガラス繊維不織布２とし
て日本バイリーン社製の秤量６０ｇ／ｃｍ2 、厚み０．
４ｍｍのものを３枚、それぞれ用い、ガラス繊維織布１
に表層部用の樹脂組成物ａを含浸させると共にガラス繊
維不織布２に芯部用の樹脂組成物ｂを含浸させて樹脂含
浸基材１１，１２を調製し、絞りロール６，６間の間隔
０．１９ｍｍ、積層ロール４，４間の間隔１．６０ｍｍ
に設定した条件下で樹脂含浸基材１１，１２及び銅箔３
を重ねると共に、硬化炉５での加熱を１００℃、２５
分、切断後の加熱を１６０℃、３０分に設定して樹脂を
硬化させることによって、板厚１．６ｍｍのＣＥＭ−３
の構成の積層板を得た。Then, a double-sided copper-clad laminate was manufactured using the apparatus shown in FIG. That is, two pieces of 7628 type manufactured by Nitto Boseki Co., Ltd. were used as the glass fiber woven fabric 1, and the glass fiber nonwoven fabric 2 was weighed 60 g / cm 2 manufactured by Nippon Vileen Co., Ltd.
3 pieces each of 4 mm, each using a glass fiber woven fabric 1
Are impregnated with the resin composition a for the surface layer and the resin composition b for the core in the glass fiber nonwoven fabric 2 to prepare the resin-impregnated substrates 11 and 12. .19 mm, spacing 1.60 mm between stacking rolls 4 and 4
The resin-impregnated substrates 11 and 12 and the copper foil 3
And heating in the curing furnace 5 at 100 ° C., 25
CEM-3 having a thickness of 1.6 mm by curing the resin by setting the heating after the cutting to 160 ° C. for 30 minutes.
Was obtained.
【００２０】上記のようにして得た積層板について、Ｕ
Ｌ法に従って難燃性を評価した。結果を表３に示す。With respect to the laminate obtained as described above, U
Flame retardancy was evaluated according to the L method. Table 3 shows the results.
【００２１】[0021]
【表３】 [Table 3]
【００２２】表３にみられるように、ラジカル重合型樹
脂にリン含有化合物（赤燐）のみを配合した樹脂組成物
Ｆを用いた比較例１や、ラジカル重合型樹脂に無機水和
化合物（水酸化アルミニウム）のみを配合した樹脂組成
物Ｇを用いた比較例２のものでは、燃焼が発生するのに
対して、ラジカル重合型樹脂にリン含有化合物と無機水
和化合物を併用して配合した樹脂組成物Ａ〜Ｅを用いた
実施例１〜５のものでは、高い難燃性能を実現できるも
のであった。また実施例２と実施例３の比較にみられる
ように、赤燐は平均粒径が１０μｍ以下のものを用いる
のが好ましいことが確認され、実施例４と実施例５の比
較にみられるように、有機リン含有化合物としてはポリ
リン酸アンモニウムを用いるのが好ましいことが確認さ
れる。As shown in Table 3, Comparative Example 1 using a resin composition F containing only a phosphorus-containing compound (red phosphorus) in a radical polymerizable resin, an inorganic hydrate compound (water In the case of Comparative Example 2 using the resin composition G containing only the aluminum oxide), combustion occurs. On the other hand, a resin prepared by using a phosphorus-containing compound and an inorganic hydrated compound in combination with a radical polymerization resin. In Examples 1 to 5 using compositions A to E, high flame retardancy was realized. Also, as can be seen from the comparison between Example 2 and Example 3, it was confirmed that it is preferable to use red phosphorus having an average particle diameter of 10 μm or less, and it can be seen from the comparison between Example 4 and Example 5. In addition, it is confirmed that it is preferable to use ammonium polyphosphate as the organic phosphorus-containing compound.
【００２３】[0023]
【発明の効果】上記のように本発明に係る積層板用樹脂
組成物は、ハロゲンを含有しないラジカル重合型樹脂１
００重量に対して、リン含有化合物をリン分換算で１〜
３０重量部、無機水和化合物を１０〜２００重量部配合
したので、リン含有化合物と無機水和化合物を併用して
配合することによって、ラジカル重合型樹脂に臭素や塩
素などのハロゲンを含有しないにもかかわらず、高い難
燃性を付与することができるものであり、人体や環境に
悪影響を及ぼすことなく難燃性の高い積層板を得ること
ができるものである。As described above, the resin composition for a laminate according to the present invention comprises a radical-polymerizable resin 1 containing no halogen.
The weight of the phosphorus-containing compound is 1 to 100 weight
Since 30 parts by weight and 10 to 200 parts by weight of the inorganic hydrated compound were blended, by combining the phosphorus-containing compound and the inorganic hydrated compound, the radical polymerizable resin contained no halogen such as bromine or chlorine. Nevertheless, high flame retardancy can be imparted, and a laminate having high flame retardancy can be obtained without adversely affecting the human body and the environment.
【００２４】また上記のリン含有化合物として赤燐を用
いることによって、難燃性を向上させる効果を高く得る
ことができる。また上記の赤燐として平均粒径が１０μ
以下のものを用いることによって、赤燐をラジカル重合
型樹脂に均一に混合することができ、赤燐による難燃性
向上の効果を高く得ることができる。By using red phosphorus as the phosphorus-containing compound, it is possible to obtain a high effect of improving flame retardancy. The red phosphorus has an average particle diameter of 10 μm.
By using the following, red phosphorus can be uniformly mixed with the radical polymerization type resin, and the effect of improving the flame retardancy by red phosphorus can be highly obtained.
【００２５】またリン含有化合物としてポリリン酸アン
モニウムを用いることによって、難燃性を向上させる効
果を高く得ることができる。また無機水和化合物として
水酸化アルミニウムを用いることによって、難燃性を向
上させる効果を高く得ることができる。本発明に係る積
層板は、基材としてガラス繊維不織布と、ガラス繊維織
布とを組み合わせて用いるようにしたので、ガラス繊維
不織布とガラス繊維織布の組み合わせで、ＣＥＭ−３の
コンポジット基板を得ることができるものである。By using ammonium polyphosphate as the phosphorus-containing compound, the effect of improving the flame retardancy can be enhanced. In addition, by using aluminum hydroxide as the inorganic hydrated compound, the effect of improving the flame retardancy can be enhanced. Since the laminated board according to the present invention uses a glass fiber nonwoven fabric and a glass fiber woven fabric in combination as a base material, a CEM-3 composite substrate is obtained by a combination of the glass fiber nonwoven fabric and the glass fiber woven fabric. Is what you can do.
【図１】積層板の製造の一例を示す概略図である。FIG. 1 is a schematic view showing an example of manufacturing a laminate.
１ ガラス繊維織布 ２ ガラス繊維不織布 1 Glass fiber woven fabric 2 Glass fiber non-woven fabric
フロントページの続き (72)発明者 野末 明義 大阪府門真市大字門真1048番地松下電工株 式会社内Continued on the front page (72) Inventor Akiyoshi Nozue 1048 Odomo Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Works, Ltd.
Claims (7)
脂１００重量に対して、リン含有化合物がリン分換算で
１〜３０重量部、無機水和化合物が１０〜２００重量部
配合されて成ることを特徴とする積層板用樹脂組成物。The present invention is characterized in that 1 to 30 parts by weight of a phosphorus-containing compound and 10 to 200 parts by weight of an inorganic hydrate compound are blended with respect to 100 parts by weight of a radical-polymerizable resin containing no halogen. And a resin composition for a laminate.
を特徴とする請求項１に記載の積層板用樹脂組成物。2. The resin composition for a laminate according to claim 1, wherein red phosphorus is used as the phosphorus-containing compound.
とを特徴とする請求項２に記載の積層板用樹脂組成物。3. The resin composition for a laminated board according to claim 2, wherein red phosphorus having an average particle size of 10 μm or less is used.
ニウムを用いることを特徴とする請求項１に記載の積層
板用樹脂組成物。4. The resin composition for a laminate according to claim 1, wherein ammonium phosphorus phosphate is used as the phosphorus-containing compound.
ムを用いることを特徴とする請求項１乃至４のいずれか
に記載の積層板用樹脂組成物。5. The resin composition for a laminated board according to claim 1, wherein aluminum hydroxide is used as the inorganic hydrated compound.
板用樹脂組成物を基材に含浸すると共にこれを重ねて成
形して形成されたことを特徴とする積層板。6. A laminate formed by impregnating a base material with the resin composition for a laminate according to any one of claims 1 to 5, and laminating and molding the same.
繊維織布とを組み合わせて用いることを特徴とする請求
項６に記載の積層板。7. The laminate according to claim 6, wherein a glass fiber nonwoven fabric and a glass fiber woven fabric are used in combination as a base material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34420396A JPH10182985A (en) | 1996-12-24 | 1996-12-24 | Resin composition for laminated plate and laminated plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34420396A JPH10182985A (en) | 1996-12-24 | 1996-12-24 | Resin composition for laminated plate and laminated plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10182985A true JPH10182985A (en) | 1998-07-07 |
Family
ID=18367433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34420396A Pending JPH10182985A (en) | 1996-12-24 | 1996-12-24 | Resin composition for laminated plate and laminated plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10182985A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011065372A1 (en) * | 2009-11-25 | 2011-06-03 | パナソニック電工株式会社 | Laminate plate, use therefor, and production method thereof |
| WO2012164997A1 (en) * | 2011-05-30 | 2012-12-06 | パナソニック株式会社 | Laminate sheet, application therefor, and method for producing same |
-
1996
- 1996-12-24 JP JP34420396A patent/JPH10182985A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011065372A1 (en) * | 2009-11-25 | 2011-06-03 | パナソニック電工株式会社 | Laminate plate, use therefor, and production method thereof |
| JP2011132540A (en) * | 2009-11-25 | 2011-07-07 | Panasonic Electric Works Co Ltd | Laminate plate, metal foil-clad laminate plate, printed-wiring board, circuit board, led backlight unit, led illumination device, and method for producing laminate plate |
| JP4893873B1 (en) * | 2009-11-25 | 2012-03-07 | パナソニック電工株式会社 | Laminate, metal foil-clad laminate, printed wiring board, circuit board, LED backlight unit, LED lighting device, and method for producing laminate |
| KR101178785B1 (en) | 2009-11-25 | 2012-09-07 | 파나소닉 주식회사 | Laminate plate, use therefor, and production method thereof |
| WO2012164997A1 (en) * | 2011-05-30 | 2012-12-06 | パナソニック株式会社 | Laminate sheet, application therefor, and method for producing same |
| CN103582564A (en) * | 2011-05-30 | 2014-02-12 | 松下电器产业株式会社 | Laminate sheet, application therefor, and method for producing same |
| TWI452949B (en) * | 2011-05-30 | 2014-09-11 | Panasonic Corp | Multilayer board, metal foil laminated board, printed wiring board and circuit board, LED backlight unit, LED lighting device, and manufacturing method of laminated board |
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