JPH04239542A - Polypropylene resin composition - Google Patents
Polypropylene resin compositionInfo
- Publication number
- JPH04239542A JPH04239542A JP4142991A JP4142991A JPH04239542A JP H04239542 A JPH04239542 A JP H04239542A JP 4142991 A JP4142991 A JP 4142991A JP 4142991 A JP4142991 A JP 4142991A JP H04239542 A JPH04239542 A JP H04239542A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- polypropylene resin
- type resin
- polypropylene
- resin composition
- 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
- -1 Polypropylene Polymers 0.000 title claims abstract description 64
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 58
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 58
- 239000011342 resin composition Substances 0.000 title claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 87
- 239000011347 resin Substances 0.000 claims abstract description 87
- 239000005011 phenolic resin Substances 0.000 claims abstract description 28
- 229920003986 novolac Polymers 0.000 claims abstract description 19
- 229920003987 resole Polymers 0.000 claims abstract description 17
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 abstract description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000005452 bending Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000004898 kneading Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920001342 Bakelite® Polymers 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229920006127 amorphous resin Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は，優れた機械的強度，衝
撃強度等を有するポリプロピレン樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene resin composition having excellent mechanical strength, impact strength, etc.
【０００２】0002
【従来技術】近年，自動車に関しては燃費向上，軽量化
という社会的要請に応えて，その構成部品の一部が金属
からプラスチックに変換されつつあり，その実用化も進
んでいる。プラスチック材料のうちポリプロピレン樹脂
は，機械的強度等の各種の物性バランスがとれた材料で
あり，かつ比較的安価であるため自動車の内装用，外装
用の部品に大量に使用されている。そして，特にタルク
，ガラス繊維，炭酸カルシウム等の無機充填剤及びこれ
らの混合物を，ポリプロピレン樹脂に充填した強化ポリ
プロピレン樹脂は，強度，耐熱性に優れているため，ホ
イールカバー，コンソールボックス，インストルメント
パネル等の自動車部品に使用されている。また，機械部
品，家庭用ケース，コンテナー容器，インテリア部材に
も広く使用されている。一方，最近では，特に自動車に
対して，成形品の外観向上，軽量化等を目的として無機
充填材の代わりに熱変形温度，強度，剛性の高い非晶性
樹脂，例えばフェノール樹脂をポリプロピレン樹脂にブ
レンドしてポリプロピレン樹脂の機械的性質を改良する
試みがなされている。[Prior Art] In recent years, in response to social demands for improved fuel economy and weight reduction, some of the component parts of automobiles are being converted from metal to plastic, and their practical use is also progressing. Among plastic materials, polypropylene resin is a material with well-balanced physical properties such as mechanical strength, and is relatively inexpensive, so it is used in large quantities for interior and exterior parts of automobiles. In particular, reinforced polypropylene resin, which is made by filling polypropylene resin with inorganic fillers such as talc, glass fiber, calcium carbonate, and mixtures thereof, has excellent strength and heat resistance, so it is used for wheel covers, console boxes, and instrument panels. Used in automotive parts such as It is also widely used in mechanical parts, household cases, containers, and interior parts. On the other hand, recently, amorphous resins with high heat deformation temperature, strength, and rigidity, such as phenolic resins, have been replaced with polypropylene resins in place of inorganic fillers to improve the appearance and reduce weight of molded products, especially for automobiles. Attempts have been made to improve the mechanical properties of polypropylene resins by blending them.
【０００３】0003
【解決しようとする課題】しかしながら，上記従来のポ
リプロピレン樹脂とフェノール樹脂とのブレンド樹脂組
成物は，相溶性が悪いため，熱変形温度，強度，剛性が
未だ低いという問題がある。本発明は，上記問題点に鑑
み鋭意研究を重ねた結果なされたもので，優れた機械的
強度，耐衝撃性を有するポリプロピレン樹脂組成物を提
供しようとするものである。[Problems to be Solved] However, the conventional blend resin compositions of polypropylene resin and phenol resin have poor compatibility, and therefore have problems in that their heat distortion temperature, strength, and rigidity are still low. The present invention was made as a result of intensive research in view of the above problems, and is intended to provide a polypropylene resin composition having excellent mechanical strength and impact resistance.
【０００４】0004
【課題の解決手段】本発明は，変性ポリプロピレン樹脂
を含有するポリプロピレン樹脂５０〜９０重量％と，フ
ェノール樹脂１０〜５０重量％とからなり，該フェノー
ル樹脂はレゾール型樹脂に対するノボラック型樹脂の割
合が０．２５〜４であることを特徴とするポリプロピレ
ン樹脂組成物にある。本発明において最も注目すべきこ
とは，変性ポリプロピレン樹脂を含有するポリプロピレ
ン樹脂と，上記フェノール樹脂との樹脂混合物を上記割
合に混合して，更に該フェノール樹脂はレゾール型樹脂
に対するノボラック型樹脂の割合を０．２５〜４にした
ことである。上記変性ポリプロピレン樹脂を含有するポ
リプロピレン樹脂とは，変性ポリプロピレン樹脂と，変
性していない通常のポリプロピレン樹脂とからなるもの
をいう。[Means for Solving the Problem] The present invention consists of 50 to 90% by weight of a polypropylene resin containing a modified polypropylene resin and 10 to 50% by weight of a phenol resin, and the phenol resin has a ratio of novolak type resin to resol type resin. 0.25 to 4. What is most noteworthy about the present invention is that a resin mixture of a polypropylene resin containing a modified polypropylene resin and the above phenol resin is mixed in the above ratio, and the phenol resin is further mixed in a ratio of novolac type resin to resol type resin. The value was set to 0.25 to 4. The polypropylene resin containing the above-mentioned modified polypropylene resin refers to one consisting of a modified polypropylene resin and an unmodified normal polypropylene resin.
【０００５】また，上記変性ポリプロピレン樹脂は，ポ
リプロピレン樹脂と無水マレイン酸等の不飽和カルボン
酸またはその誘導体とを，有機過酸化物の存在下で反応
させて変性したものである。そのため，該変性ポリプロ
ピレン樹脂は，その分子構造の一部にカルボン酸基を有
する。上記通常のポリプロピレン樹脂としては，ホモポ
リプロピレンの他にプロピレン−エチレンランダム共重
合体（エチレン含量２０重量％以下），プロピレン−エ
チレンブロック共重合体（エチレン含量２０重量％以下
）及びこれらの混合物がある。The above-mentioned modified polypropylene resin is modified by reacting a polypropylene resin with an unsaturated carboxylic acid such as maleic anhydride or a derivative thereof in the presence of an organic peroxide. Therefore, the modified polypropylene resin has a carboxylic acid group in a part of its molecular structure. In addition to homopolypropylene, the above-mentioned normal polypropylene resins include propylene-ethylene random copolymers (ethylene content of 20% by weight or less), propylene-ethylene block copolymers (ethylene content of 20% by weight or less), and mixtures thereof. .
【０００６】また，変性ポリプロピレン樹脂は，上記通
常のポリプロピレン樹脂とフェノール樹脂とからなる樹
脂混合物中に５〜９０％（重量比，以下同じ）含まれて
いることが好ましい。即ち，変性ポリプロピレン樹脂は
，全ポリプロピレン樹脂中の一部として含有されている
場合，ポリプロピレン樹脂中の殆どを占めている場合（
上記９０％）もある。また，全ポリプロピレン樹脂のメ
ルトフローインデックスは１〜５０が好ましく，これら
が１未満の場合には成形加工性及び成形品の外観が悪く
なり，５０を越える場合には耐衝撃性の低下が著しくな
る。上記変性ポリプロピレン樹脂を含有するポリプロピ
レン樹脂は，樹脂混合物中の含量が５０％未満では機械
的強度，耐熱性が低下し，一方９０％を越えると熱変形
温度が低下する。[0006] Furthermore, it is preferable that the modified polypropylene resin is contained in an amount of 5 to 90% (weight ratio, hereinafter the same) in the resin mixture consisting of the above-mentioned ordinary polypropylene resin and phenol resin. In other words, if the modified polypropylene resin is contained as a part of the total polypropylene resin, or if it occupies most of the polypropylene resin (
90% above). In addition, the melt flow index of all polypropylene resins is preferably 1 to 50; if it is less than 1, the moldability and appearance of the molded product will be poor, and if it exceeds 50, the impact resistance will be significantly reduced. . If the content of the polypropylene resin containing the above-mentioned modified polypropylene resin in the resin mixture is less than 50%, the mechanical strength and heat resistance will decrease, while if it exceeds 90%, the heat distortion temperature will decrease.
【０００７】次に，上記フェノール樹脂は，一般に強靱
で，特に耐熱性に優れた熱硬化性樹脂である。該フェノ
ール樹脂は，樹脂混合物中に１０〜５０％含有させる。
１０％未満ではその配合効果が少なく，一方５０％を越
えると機械的強度，耐熱性，耐衝撃性が配合量に見合う
ほど向上しない。また，上記フェノール樹脂は上記レゾ
ール型樹脂とノボラック樹脂との混合物からなり，その
混合割合は重量比で１：４〜４：１である。上記レゾー
ル型樹脂はアルカリ触媒によりフェノールとホルムアル
デヒドとを反応して得られる，液状又は固形粉末状で多
数の反応性メチロール基を有する熱硬化性樹脂である。Next, the above-mentioned phenolic resin is a thermosetting resin that is generally tough and particularly has excellent heat resistance. The phenolic resin is contained in the resin mixture in an amount of 10 to 50%. If it is less than 10%, the blending effect will be small, while if it exceeds 50%, the mechanical strength, heat resistance, and impact resistance will not improve to the extent commensurate with the blended amount. The phenol resin is a mixture of the resol type resin and the novolak resin, and the mixing ratio thereof is 1:4 to 4:1 by weight. The above-mentioned resol type resin is a thermosetting resin having a large number of reactive methylol groups in liquid or solid powder form and is obtained by reacting phenol and formaldehyde using an alkali catalyst.
【０００８】一方，上記ノボラック型樹脂は，酸触媒に
よりフェノールとホルムアルデヒドとを反応して得られ
る，固形粉末状の縮合物である。該ノボラック型樹脂は
反応性メチロール基を殆ど有しないため，ヘキサメチレ
ンテトラミン等のメチレン基供給源を添加しない限り，
熱可塑性を維持する。ところで，上記フェノール樹脂中
でレゾール型樹脂の配合割合を増加すると，硬化が早く
進み，樹脂組成物は混練性，流動性，分散性が悪くなる
。その結果，該樹脂組成物を用いて，例えば混練押出機
により成形用ペレットを作成する際に，ペレットの成形
性の尺度となる，ストランド引き取り性，成形品外観が
悪くなる。一方，上記フェノール樹脂中のノボラック型
樹脂の配合割合が増すと，フェノール樹脂の硬化が遅れ
，その結果，耐熱性，機械的強度等が悪くなる。On the other hand, the novolac type resin is a solid powder condensate obtained by reacting phenol and formaldehyde using an acid catalyst. Since the novolac type resin has almost no reactive methylol groups, it cannot be used unless a methylene group source such as hexamethylenetetramine is added.
Remains thermoplastic. By the way, when the blending ratio of the resol type resin in the above-mentioned phenol resin is increased, curing proceeds quickly and the kneading properties, fluidity, and dispersibility of the resin composition deteriorate. As a result, when molding pellets are produced using the resin composition using, for example, a kneading extruder, the strand drawability and appearance of the molded product, which are indicators of the moldability of the pellets, deteriorate. On the other hand, when the proportion of novolac type resin in the phenol resin increases, the curing of the phenol resin is delayed, resulting in poor heat resistance, mechanical strength, etc.
【０００９】次に，上記ポリプロピレン樹脂組成物は，
一軸押出機，二軸押出機，ニーダー，ブラベンダー，バ
ンバリーミキサー等の通常の混練機を用いて製造するこ
とができる。通常は，各配合成分を所定の割合にてタン
ブラー式ブレンダー，ヘンシェルミキサー，リボンミキ
サー等により混合し，その後押出機等で混練してペレッ
ト状のコンパウンドとなし，その後ホイールカバー，タ
イミングベルトカバー，ヒータハウジング等の所望する
成形品の形状に成形する。また，本発明においては，前
記成分以外に，無機充填剤，酸化防止剤，紫外線吸収剤
，滑剤，帯電防止剤，核剤，顔料，難燃剤，増量剤，加
工助剤等の添加物を混合しても良い。上記無機充填剤と
しては，タルク，炭酸カルシウム，ガラス繊維などがあ
る。本発明のポリプロピレン樹脂組成物は，自動車の各
種部品，例えばスポイラー，ホイールカバー，ヒータハ
ウジング，エアブロワケース，インスツルメントパネル
等の自動車用品，或いはその他の電気部品，機械部品に
使用することができる。Next, the above polypropylene resin composition is
It can be produced using a conventional kneading machine such as a single screw extruder, a twin screw extruder, a kneader, a Brabender, or a Banbury mixer. Usually, each component is mixed in a predetermined ratio using a tumbler blender, Henschel mixer, ribbon mixer, etc., and then kneaded using an extruder etc. to form a pellet-like compound. Molded into the shape of a desired molded product such as a housing. In addition, in the present invention, in addition to the above-mentioned components, additives such as inorganic fillers, antioxidants, ultraviolet absorbers, lubricants, antistatic agents, nucleating agents, pigments, flame retardants, fillers, and processing aids are mixed. You may do so. Examples of the above-mentioned inorganic fillers include talc, calcium carbonate, and glass fiber. The polypropylene resin composition of the present invention can be used for various automotive parts, such as spoilers, wheel covers, heater housings, air blower cases, instrument panels, etc., as well as other electrical and mechanical parts. .
【００１０】0010
【作用及び効果】本発明は，前記組成によりポリプロピ
レン樹脂組成物を構成している。そのため，本発明のポ
リプロピレン樹脂組成物は，ポリプロピレン樹脂とフェ
ノール樹脂とを単にブレンドして機械的強度，耐熱性を
向上させようとするものとは異なり，更に優れた機械的
強度，耐熱性を有する。このように，機械的強度，耐熱
性が更に向上した理由は，次のように考えられる。[Operations and Effects] The present invention constitutes a polypropylene resin composition with the above composition. Therefore, the polypropylene resin composition of the present invention has even better mechanical strength and heat resistance, unlike those that simply blend polypropylene resin and phenol resin to improve mechanical strength and heat resistance. . The reason why the mechanical strength and heat resistance were further improved is considered to be as follows.
【００１１】即ち，上記樹脂組成物にはフェノール樹脂
の硬化剤を添加混合していないにも拘らず，変性ポリプ
ロピレン樹脂中に含まれるカルボン酸基と，ノボラック
型樹脂の末端における反応基とが，レゾール型樹脂中の
多数のメチロール基を仲介として付加反応を生じる。ま
た，上記変性ポリプロピレン樹脂とレゾール型樹脂とノ
ボラック型樹脂との三つの樹脂を混合することにより，
レゾール型樹脂が，粉末状の変性ポリプロピレン樹脂と
ノボラック型樹脂との両樹脂の相容化剤として働き，上
記変性ポリプロピレン樹脂とノボラック型樹脂とを，イ
オン的に引き合わせる。[0011] That is, although the above resin composition does not contain a curing agent for phenolic resin, the carboxylic acid groups contained in the modified polypropylene resin and the reactive groups at the terminals of the novolac type resin, An addition reaction occurs mediated by the large number of methylol groups in the resol type resin. In addition, by mixing the above-mentioned modified polypropylene resin, resol type resin, and novolak type resin,
The resol type resin acts as a compatibilizer for both the powdered modified polypropylene resin and the novolak type resin, and ionically attracts the modified polypropylene resin and the novolak type resin.
【００１２】そのため，変性ポリプロピレン樹脂と，ノ
ボラック型樹脂とレゾール型樹脂からなるフェノール樹
脂とは，親和性を増大する。その結果，変性ポリプロピ
レン樹脂とフェノール樹脂との両樹脂の相溶性は著しく
向上する。そこで，これらの樹脂の界面結合も著しく良
好となり，変性ポリプロピレン樹脂とフェノール樹脂と
の両樹脂が本来有する機械的強度，耐衝撃性，耐熱性等
の優れた諸物性に加えて，更に機械的強度，耐熱性が上
積みされて向上するものと推察される。以上のごとく，
本発明によれば，特に機械的強度，耐衝撃性に優れ，か
つ優れた諸性能を有するポリプロピレン樹脂組成物を提
供することができる。[0012] Therefore, the affinity between the modified polypropylene resin and the phenol resin consisting of a novolac type resin and a resol type resin increases. As a result, the compatibility between the modified polypropylene resin and the phenol resin is significantly improved. Therefore, the interfacial bonding of these resins has become extremely good, and in addition to the excellent physical properties such as mechanical strength, impact resistance, and heat resistance that both modified polypropylene resin and phenol resin inherently have, they have even greater mechanical strength. , it is presumed that the heat resistance is further improved. As mentioned above,
According to the present invention, it is possible to provide a polypropylene resin composition that is particularly excellent in mechanical strength and impact resistance, and has excellent various performances.
【００１３】[0013]
【実施例】以下，本発明のポリプロピレン樹脂組成物に
かかる実施例及び比較例につき説明する。諸物性の測定
は，以下の方法により行った。また，表１，表２におけ
る成分の配合割合，試験片の測定結果は同表に示した。
即ち，実施例，比較例に掲げる試験片の作製は，所定割
合に混合した組成物を異方向回転２軸押出機で溶融混練
し，ペレットとした。次いで，このペレットを８０℃，
３時間乾燥した後，５Ｏ Ｚ 射出成形機にて成形し，
作製した。また，曲げ強度及び曲げ弾性率はＡＳＴＭＤ
−７９０により測定し，熱変形温度は，ＡＳＴＭＤ−６
４８により測定した。EXAMPLES Examples and comparative examples of the polypropylene resin composition of the present invention will be explained below. Measurements of various physical properties were performed using the following methods. In addition, the mixing ratios of the components in Tables 1 and 2 and the measurement results of the test pieces are shown in the same table. That is, the test pieces listed in Examples and Comparative Examples were prepared by melt-kneading the compositions mixed at a predetermined ratio in a twin-screw extruder rotating in opposite directions to form pellets. Next, this pellet was heated to 80°C.
After drying for 3 hours, it was molded using a 5OZ injection molding machine.
Created. In addition, the bending strength and bending modulus are as per ASTM
-790, and the heat distortion temperature is ASTM D-6
48.
【００１４】次に，実施例１〜９，比較例１〜４につき
，表１及び表２を用いて説明する。なお，同表において
，ポリプロピレン，変性ポリプロピレン，フェノール樹
脂としてのレゾール型樹脂とノボラック型樹脂は，全組
成物中の重量％で示した。また，レゾール型樹脂に対す
るノボラック型樹脂の割合は同表より知られる。また，
上記ポリプロピレン樹脂としては，三菱油化（株）製の
三菱ノーブレン（登録商標）ＢＣ−２Ｅを用いた。
また，変性ポリプロピレン樹脂としては，三井石油化学
（株）製のアドマー（登録商標）ＡＴ−６４６を用いた
。Next, Examples 1 to 9 and Comparative Examples 1 to 4 will be explained using Tables 1 and 2. In addition, in the same table, polypropylene, modified polypropylene, resol type resin and novolac type resin as phenol resins are shown in weight percent of the total composition. Further, the ratio of novolak type resin to resol type resin is known from the same table. Also,
As the polypropylene resin, Mitsubishi Noblen (registered trademark) BC-2E manufactured by Mitsubishi Yuka Co., Ltd. was used. Furthermore, Admer (registered trademark) AT-646 manufactured by Mitsui Petrochemicals, Ltd. was used as the modified polypropylene resin.
【００１５】また，上記レゾール型樹脂は，住友ベーク
ライト（株）製のＰＲ５１１４１（融点が６０℃）を用
いた。また，表中のノボラック型樹脂Ａとしては，住友
ベークライト（株）製のＰＲ５０７１６（融点が８０℃
）を用いた。また，ノボラック型樹脂Ｂとしては，ＮＢ
Ｒ共重合タイプのフェノール樹脂（同住友ベークライト
（株）製）を用いた。両表より知られるごとく，曲げ強
度に関し，本発明の実施例１〜９は，３８０〜４５０ｋ
ｇ／ｃｍ２ である。これに対し，比較例１〜４は，２
８０〜４１０ｋｇ／ｃｍ２ である。また，曲げ弾性率
に関しては，実施例１〜９は１５８００〜１８５００ｋ
ｇ／ｃｍ２ である。これに対し，比較例１〜４は，１
２４００〜１８８００ｋｇ／ｃｍ２ である。また，実
施例２では１５８００ｋｇ／ｃｍ２ であるのに対して
比較例２，３では１７１００〜１８８００ｋｇ／ｃｍ２
である。しかし，比較例２，３では，下記に述べるス
トランド引き取り性，成形品外観等が悪く，実用上問題
がある。[0015] As the resol type resin, PR51141 (melting point: 60°C) manufactured by Sumitomo Bakelite Co., Ltd. was used. In addition, as novolac type resin A in the table, PR50716 manufactured by Sumitomo Bakelite Co., Ltd. (melting point is 80 ° C.
) was used. In addition, as novolac type resin B, NB
An R copolymerization type phenol resin (manufactured by Sumitomo Bakelite Co., Ltd.) was used. As can be seen from both tables, in terms of bending strength, Examples 1 to 9 of the present invention have a bending strength of 380 to 450 k.
g/cm2. On the other hand, in Comparative Examples 1 to 4, 2
It is 80 to 410 kg/cm2. In addition, regarding the bending elastic modulus, Examples 1 to 9 were 15,800 to 18,500k.
g/cm2. On the other hand, in Comparative Examples 1 to 4, 1
It is 2400 to 18800 kg/cm2. Moreover, in Example 2, it was 15,800 kg/cm2, whereas in Comparative Examples 2 and 3, it was 17,100 to 18,800 kg/cm2.
It is. However, Comparative Examples 2 and 3 have poor strand take-up properties, poor appearance of the molded product, etc., which will be described below, and have practical problems.
【００１６】このように，本発明の実施例１〜９が，比
較例１〜４に比して，曲げ強度，曲げ弾性率等の機械的
強度が高くなった理由としては，次のように考えられる
。即ち，変性ポリプロピレン樹脂中に含まれるカルボン
酸基，ノボラック型樹脂中の末端の反応基，メチレン基
がレゾール型樹脂の多数のメチロール基を仲介として，
付加反応し又はイオン的に引き合う。そのため，変性ポ
リプロピレン樹脂とフェノール樹脂との両樹脂は，その
界面結合が良好となり，その結果，相容性が向上する。
それ故，機械的強度，耐熱性が向上するものと推察され
る。The reason why Examples 1 to 9 of the present invention have higher mechanical strengths such as bending strength and flexural modulus than Comparative Examples 1 to 4 is as follows. Conceivable. That is, the carboxylic acid group contained in the modified polypropylene resin, the terminal reactive group in the novolac type resin, and the methylene group are mediated by the many methylol groups in the resol type resin.
Addition reaction or ionic attraction. Therefore, both the modified polypropylene resin and the phenol resin have good interfacial bonding, resulting in improved compatibility. Therefore, it is presumed that mechanical strength and heat resistance are improved.
【００１７】また，４．６ｋｇ／ｃｍ２ 荷重における
熱変形温度に関し，実施例１〜９は１１８〜１３８℃で
ある。これに対し，比較例１〜４では９０〜１３８℃で
ある。また，１８．６ｋｇ／ｃｍ２ 荷重における熱変
形温度は，実施例１〜９では９５〜１１２℃である。こ
れに対し，比較例１〜４では，５６〜１１１℃である。
このうち，特に比較例２が５６℃と低いのは，フェノー
ル樹脂がノボラック型樹脂のみからなるため，レゾール
型樹脂の仲介的作用がなく，フェノール樹脂の硬化が不
充分のためと考えられる。[0017] Furthermore, regarding the heat deformation temperature under a load of 4.6 kg/cm2, Examples 1 to 9 are 118 to 138°C. On the other hand, in Comparative Examples 1 to 4, the temperature was 90 to 138°C. Further, the thermal deformation temperature under a load of 18.6 kg/cm2 is 95 to 112°C in Examples 1 to 9. On the other hand, in Comparative Examples 1 to 4, the temperature was 56 to 111°C. Among these, the reason why Comparative Example 2 was particularly low at 56°C is thought to be because the phenol resin consists only of novolak type resin, so there is no intermediary effect of the resol type resin, and the phenol resin is insufficiently cured.
【００１８】次に，ストランド引き取り性に関しては，
実施例１〜９では実施例３を除き，すべて良好である。
これに対し，比較例１〜４では，特に３，４が悪い。ま
た，成形品外観に関しては，実施例１〜９では，上記３
を除き，すべて良好である。これに対し，比較例１〜４
では，特に３，４が悪い。このように３，４のストラン
ド引き取り性及び成形外観が悪いのは，フェノール樹脂
がレゾール樹脂のみからなるためと考えられる。なお，
表中上記ストランド引き取り性及び成形品外観に関し，
○印は良好，△印はやや良，×は不良を示す。なお，上
記ストランド引き取り性とは，例えば混練押出機により
樹脂材料を引き出す時の難易を示す尺度をいう。以上の
ごとく，本発明のポリプロピレン樹脂組成物は，従来の
ポリプロピレン樹脂よりも曲げ強度，曲げ弾性率等の機
械的強度が向上し，また熱変形温度等の耐熱性が若干向
上していることが知られる。Next, regarding the strand take-up property,
All of Examples 1 to 9 were good except for Example 3. On the other hand, in Comparative Examples 1 to 4, 3 and 4 were particularly bad. In addition, regarding the appearance of the molded product, in Examples 1 to 9, the above 3
All are in good condition except for. On the other hand, Comparative Examples 1 to 4
So, 3 and 4 are particularly bad. The reason why the strand take-up properties and molded appearance of samples 3 and 4 are poor is thought to be because the phenolic resin consists only of resol resin. In addition,
Regarding the above-mentioned strand retractability and molded product appearance in the table,
○ indicates good, △ indicates slightly good, and × indicates poor. Note that the above-mentioned strand drawability is a measure indicating the difficulty in drawing out the resin material using, for example, a kneading extruder. As described above, the polypropylene resin composition of the present invention has improved mechanical strength such as bending strength and flexural modulus, as well as slightly improved heat resistance such as heat distortion temperature, compared to conventional polypropylene resins. known.
【００１９】[0019]
【表１】[Table 1]
【００２０】[0020]
【表２】[Table 2]
Claims (1)
ロピレン樹脂５０〜９０重量％と，フェノール樹脂１０
〜５０重量％とからなり，該フェノール樹脂はレゾール
型樹脂に対するノボラック型樹脂の割合が０．２５〜４
であることを特徴とするポリプロピレン樹脂組成物。Claim 1: 50 to 90% by weight of polypropylene resin containing modified polypropylene resin and 10% by weight of phenolic resin.
~50% by weight, and the phenolic resin has a ratio of novolak type resin to resol type resin of 0.25 to 4.
A polypropylene resin composition characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4142991A JPH04239542A (en) | 1991-01-23 | 1991-01-23 | Polypropylene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4142991A JPH04239542A (en) | 1991-01-23 | 1991-01-23 | Polypropylene resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04239542A true JPH04239542A (en) | 1992-08-27 |
Family
ID=12608127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4142991A Pending JPH04239542A (en) | 1991-01-23 | 1991-01-23 | Polypropylene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04239542A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320053C (en) * | 2005-12-29 | 2007-06-06 | 上海交通大学 | Process for preparing thermoplastic phenolic aldehyde resin/polypropylene coblend |
| JP2010043235A (en) * | 2008-08-13 | 2010-02-25 | Takashi Inoue | Modified polypropylene and method for producing the same |
-
1991
- 1991-01-23 JP JP4142991A patent/JPH04239542A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320053C (en) * | 2005-12-29 | 2007-06-06 | 上海交通大学 | Process for preparing thermoplastic phenolic aldehyde resin/polypropylene coblend |
| JP2010043235A (en) * | 2008-08-13 | 2010-02-25 | Takashi Inoue | Modified polypropylene and method for producing the same |
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