JPS629616B2 - - Google Patents
Info
- Publication number
- JPS629616B2 JPS629616B2 JP16040783A JP16040783A JPS629616B2 JP S629616 B2 JPS629616 B2 JP S629616B2 JP 16040783 A JP16040783 A JP 16040783A JP 16040783 A JP16040783 A JP 16040783A JP S629616 B2 JPS629616 B2 JP S629616B2
- Authority
- JP
- Japan
- Prior art keywords
- phenolic resin
- parts
- impact strength
- fibers
- molding
- 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.)
- Expired
Links
- 239000005011 phenolic resin Substances 0.000 claims description 51
- 239000000835 fiber Substances 0.000 claims description 50
- 229920001568 phenolic resin Polymers 0.000 claims description 47
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 45
- 239000012778 molding material Substances 0.000 claims description 35
- 238000001746 injection moulding Methods 0.000 claims description 23
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 8
- -1 bisphenol A modified phenolic resin Chemical class 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000011134 resol-type phenolic resin Substances 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 1
- 229920002978 Vinylon Polymers 0.000 description 33
- 239000000463 material Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 8
- 239000003365 glass fiber Substances 0.000 description 7
- 235000013312 flour Nutrition 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- 229920002302 Nylon 6,6 Polymers 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
Description
発明の技術分野
本発明は衝撃強度の優れた射出成形用フエノー
ル樹脂成形材料に関し、更に詳しくは射出成形に
よりシヤルピー衝撃強度が向上した成形品が得ら
れる射出成形用フエノール樹脂成形材料に関す
る。
発明の利用分野
本発明の射出成形用フエノール樹脂成形材料
は、フエノール樹脂の特性である耐熱性、耐熱ク
リープ性、電気特性に加えて、優れた衝撃強度を
有するので、多くのエンジニアリング・プラスチ
ツクよりも広い分野において射出成形品として利
用することができる。例えば、ブレーカー、マイ
クロスイツチ、ボビンなどの電気電子部品、ギ
ヤ、カム、軸受、ワツシヤー、シールリングなど
の機械部品、或いはコネクター、プーリーなどの
自動車部品などに利用することができる。
従来技術及びその問題点
従来、フエノール樹脂をはじめとする熱硬化性
樹脂を使用した成形材料は、通常の熱可塑性樹脂
成形材料と比較して、衝撃強度が低いという問題
を有しており、この問題を解決する方策として、
一般には、パルプ、綿布チツプ、ポリアミド繊
維、ポリビニルアルコール繊維、アスベスト繊維
又はガラス繊維などの有機質繊維や無機質繊維を
補強材として使用して、衝撃強度の向上が計られ
ている。
しかしながら、熱硬化性樹脂成形材料の中で
も、フエノール樹脂成形材料においては、圧縮成
形やトランスフアー成形では高い衝撃強度を示す
ものが得られているが、射出成形では高い衝撃強
度を示すものは得られておらず、シヤルピー衝撃
強度３〜５Kg・cm／cm2程度が現行材料では最高と
されているのが実情である。
この原因は、パルプ、綿布チツプ、アスベスト
繊維などでは、各繊維自体の引張強度が低いため
であり、ガラス繊維では、繊維自体の引張強度は
高いものの、フエノール樹脂成形材料の製造時或
いは射出成形時にシエアーを受けることにより、
簡単に切断されてしまうためである。
また、ポリアミド繊維やポリビニルアルコール
繊維の中には高強力のものもあるが、これらの繊
維はフエノール樹脂中で加熱されると繊維がフエ
ノール樹脂に溶けるという問題があつた。
特に、射出成形のように、成形時に数分間以上
加熱されると繊維自体が溶けてそれ自体の引張強
度が低下するために、得られた成形品のシヤルピ
ー衝撃強度はほとんど向上しないか、向上しても
わずかに向上するに過ぎないことを見出した。
発明の目的
本発明の目的は前記した従来のフエノール樹脂
成形材料の問題点を解決し、射出成形においてシ
ヤルピー衝撃強度が向上した成形品を得ることが
できるフエノール樹脂成形材料を提供することに
ある。
発明の構成
本発明に係る射出成形用フエノール樹脂は、溶
解度パラメーター（以下SP値と称す）が9.0〜
11.0のフエノール樹脂又は変性フエノール樹脂
100重量部に対し、引張強度が６ｇ／デニール
（以下、ｇ／ｄと略称する）以上のポリビニルア
ルコール繊維（以下ビニロン繊維と称す）５〜
100重量部含有させてなる。
発明の構成及び作用効果の具体的説明
本発明者らの研究によれば、ビニロン繊維自体
の強度とこれを使用して得られるフエノール樹脂
成形材料のシヤルピー衝撃強度とは一義的であ
り、高強度のビニロン繊維を使用すると極めて高
い衝撃強度の成形品を与えるフエノール樹脂成形
材料が得られることを見出した。また、ビニロン
繊維を少量使用した場合でも強度の改良効果が大
きい。更に、SP値9.0〜11.0のフエノール樹脂、
例えばベンジリツクエーテル型フエノール樹脂に
ビニロン繊維を組み合わせて製造したフエノール
樹脂成形材料においては、ベンジリツクエーテル
型フエノール樹脂は、材料製造時又は射出成形時
に、ビニロン繊維を溶解しないか或いは僅かに溶
解させる程度の作用しかせず、従つてビニロン繊
維はそれ自体の強度を維持でき、かつ、ビニロン
繊維とベンジリツクエーテル型フエノール樹脂間
の密着性を増す。更にビニロン繊維はそれ自体の
引張強度が６ｇ／ｄ以上であり、適度の柔軟性を
有するため、材料製造時又は射出成形時にシエア
ーを受けても切断されることが少なく、繊維形状
のビニロンができるだけ多く成形品中に残ること
になる。
前記技術的手段及びその作用により、本発明の
フエノール樹脂成形材料を使用すれば、射出成形
により、シヤルピー衝撃強度の非常に高い、例え
ば10Kg・cm／cm2前後の成形品が得られる。また、
ビニロン繊維の添加量が少量の場合でも、衝撃強
度の向上した成形品を与えるフエノール樹脂成形
材料が得られる。本発明に従えば、更には、ガラ
ス繊維使用のフエノール樹脂成形材料よりも摺動
特性や耐摩耗性が良好でかつ、材料自体の比重が
小さいため、軽量化された成形品を得ることがで
きる。
本発明者等は、前記従来技術の問題点に鑑み、
従来の射出成形用フエノール樹脂成形材料よりシ
ヤルピー衝撃強度が高く、かつ摺動性、耐摩耗性
の優れた射出成形用フエノール樹脂成形材料の研
究開発に着手した。
当初、ガラス繊維以外の合成繊維について、種
種検討した結果、ナイロン66、およびビニロン繊
維が好適なものとして選択され、さらに該繊維の
引張強度を変えたものについて種々検討したが、
射出成形で、高いシヤルピー衝撃強度を示す成形
材料は得られなかつた。その原因を究明したとこ
ろ、ナイロン66繊維及びビニロン繊維が熱履歴を
受けることにより、フエノール樹脂に溶解するこ
とが原因であることを解明した。このことは、シ
ヤルピー衝撃強度の低かつた試験片の破断面をみ
るとナイロン66繊維又はビニロン繊維がフエノー
ル樹脂に溶解しているということから明らかであ
る。
そこで、種々のフエノール樹脂と、ナイロン66
繊維又はビニロン繊維との組み合わせについて、
熱時の溶解性を研究した結果、ビニロン繊維につ
いて衝撃強度の高い成形材料を与えるいくつかの
フエノール樹脂を見出した。また、ナイロン66繊
維はインジエクシヨン成形においては、大半のフ
エノール樹脂に溶解され、高いシヤルピー衝撃強
度を発現しないことがわかつた。
次に、このビニロン繊維を熱時溶解する樹脂と
溶解しない樹脂との、その本質的な差について鋭
意研究を重ねた結果、フエノール樹脂のSP値と
ビニロン繊維の溶解度が一義的に関係しているこ
とを見出し、具体的にもビニロン繊維を熱時溶解
しない多くのフエノール樹脂を見出し、本発明を
なすに至つたものである。
即ち、本発明に従えば、前記したように、SP
値9.0〜11.0のフエノール樹脂又は、変性フエノ
ール樹脂100重量部に対し、引張強度が６ｇ／ｄ
以上であるビニロン繊維５〜100重量部を含有さ
せることによつて、目的とする射出成形用フエノ
ール樹脂成形材料を得ることができる。
本発明でいうSP値は、接着百科（上）（芝崎一
郎著、高分子刊行会発行 51年版、33頁）に基づ
くものであり、その測定法は以下の通りである。
即ち、１〜２ｇのポリマーを試験管にとり、実
際に用いられる最終溶液における割合の溶剤量を
加え、ガラス棒でかきまぜながら、加温して溶解
する。溶解度は溶液を冷却して室温で観察する。
溶液が透明で曇りがなく、ゲル粒子がなければ、
ポリマーはその溶剤に溶解すると判定する。ポリ
マーを溶解する２つの溶剤のSP値がそれぞれ端
の値を示し、ポリマーのSP値範囲が求められ
る。
本発明で使用されるSP値9.0〜11.0のフエノー
ル樹脂とは、例えばベンジリツクエーテル型フエ
ノール樹脂（SP値9.6〜10.0）、アンモニアレゾー
ル型フエノール樹脂（SP値9.9〜10.0）などであ
り、変性フエノール樹脂とは例えばビスフエノー
ルＡ変性フエノール樹脂（SP値9.9〜10.7）、アニ
リン変性フエノール樹脂（SP値9.9〜10.7）、アミ
ン変性フエノール樹脂（SP値9.6〜10.7）などで
ある。
本発明で使用されるビニロン繊維はその引張強
度が６ｇ／ｄ以上のものが良く、更に好ましく
は、7.5ｇ／ｄ以上のものが良い。６ｇ／ｄに満
たないものは大量に使用しても高い衝撃強度のも
のが得られず、また、少量使用した場合は、強度
の改良効果は極めて小さい。又、ビニロン繊維は
前記フエノール樹脂100重量部に対し５〜100重量
部の量で使用するのが良く、更に好ましくは15〜
70重量部の量で使用するのが良い。ビニロン繊維
の使用量が５重量部より少ないとシヤルピー衝撃
強度の向上が実質的に著しく小さく、逆に100重
量部より多くなると、シヤルピー衝撃強度はより
高くなるが、射出成形が不可能な材料になつてし
まう。本発明では、ビニロン繊維の長さは別に規
定してないが、一般に使用されている１〜５mmの
ものが好適である。尚、本発明においては、ビニ
ロン繊維だけでなく、耐熱性、曲げ強度、引張強
度などを考慮して、通常フエノール樹脂成形材料
に使用されるセルロース類や、ガラス繊維、その
他の無機質フイラーの併用は有効である。
本発明の成形材料は一般に行われている製造方
法で製造されるが、その中の好適な一方法を例示
すれば以下に説明する通りである。
SP値9.0〜11.0のフエノール樹脂又は変性フエ
ノール樹脂100重量部、引張強度が６ｇ／ｄ以上
であるビニロン繊維５〜100重量部、必要に応
じ、セルロース類や、ガラス繊維、無機質フイラ
ーなどを併用し、更に硬化剤、硬化助剤、離型
剤、着色剤などの適当量をヘンシエルミキサーに
て均一分散混合し、次にこの混合配合物を二軸連
続式ニーダーにて60〜80℃で加熱混練後、２〜４
mmφのスクリーンを装着したダブルペレツターに
て押し出し造粒する。この造粒物を冷却後、粉砕
することにより、射出成形可能なペレツト状の成
形材料を得ることができる。
実施例
以下、本発明の好適な実施例を説明するが、本
発明の技術的範囲をこれらの実施例に限定するも
のでないことはいうまでもない。尚、以下の例に
おいても「部」は『重量部』を示す。
実施例 １
SP値9.6〜10.0のベンジリツクエーテル型フエ
ノール樹脂100部、引張強度7.8ｇ／ｄを有するビ
ニロン繊維（１mmカツト品）50部、木粉（120メ
ツシユ品）20部、酸化マグネシウム10部、ステア
リン酸10部及びスピリツトブラツク５部をヘンシ
エルミキサーにて均一分散混合した。次にこの配
合物を二軸連続式ニーダーにて60〜80℃で加熱混
練後、３mmφのスクリーンを装着したダブルペレ
ツターにて押し出して造粒した。この造粒物を冷
却後、粉砕してペレツト状成形材料を得た。この
成形材料を使用して、一般に行われている成形条
件（射出成形圧力1200〜1500Kg／cm2、金型温度
160〜170℃、成形時間60〜90秒）で射出成形を行
ない（MEIKI製 RJ−140C射出成形機）、シヤ
ルピー衝撃強度測定用JIS試験片を得た。テスト
の結果、この試験片のシヤルピー強度は9.7Kg・
cm／cm2であつた。その他の射出成形による材料の
物性は第１表に示す通りであつた。尚、物性は
JIS−Ｋ−6911に基づいて測定した。
実施例 ２
引張強度7.8ｇ／ｄのビニロン繊維30部及び木
粉40部を使用した以外は実施例１と同様にして成
形材料を得た。
この材料から実施例１と同様にして成形した試
験片のシヤルピー衝撃強度は5.5Kg・cm／cm2であ
り、その他の物性は第１表に示す通りであつた。
実施例 ３
ビニロン繊維50部及び木粉20部の代りに引張強
度7.8ｇ／ｄのビニロン繊維70部を使用した以外
は、実施例１と同様にして成形材料を得た。
この成形材料から実施例１と同様にして成形し
た試験片のシヤルピー衝撃強度は10.5Kg・cm／cm2
であり、その他の物性は第１表に示す通りであつ
た。
実施例 ４
ベンジリツクエーテル型フエノール樹脂のかわ
りにSP値9.9〜10.0のメタキシレンジアミン変性
フエノール樹脂を使用し、更にヘキサメチレンテ
トラミン15部を追加した以外は実施例１と同様に
して成形材料を得た。
この材料から実施例１と同様にして成形した試
験片のシヤルピー衝撃強度は9.0Kg・cm／cm2であ
り、その他の物性は第１表に示す通りであつた。
比較例 １
SP値12.7〜14.5のノボラツク型フエノール樹脂
100部、引張強度7.8ｇ／ｄのビニロン繊維（１mm
カツト品）50部、木粉（120メツシユ品）20部、
ヘキサメチレンテトラミン15部、酸化マグネシウ
ム10部、ステアリン酸10部及びスピリツトブラツ
ク５部をヘンシエルミキサーにて均一分散混合し
た。この混合配合物を二軸連続式ニーダーにて60
〜80℃で加熱混練後、３mmφのスクリーンを有す
るダブルペレツターにて押し出し、造粒した。こ
の造粒物を冷却後、粉砕してペレツト状の成形材
料を得た。
この材料を実施例１と同様に射出成形した試験
片のシヤルピー衝撃強度は5.3Kg・cm／cm2であ
り、その他の物性は第１表に示す通りであつた。
比較例 ２
SP値9.6〜10.0のベンジリツクエーテル型フエ
ノール樹脂100部、引張強度3.0ｇ／ｄを有するビ
ニロン繊維（３mmカツト品）50部、木粉（120メ
ツシユ品）20部、酸化マグネシウム10部、ステア
リン酸10部及びスピリツトブラツク５部をヘンシ
エルミキサーにて均一分散混合した。この配合物
を二軸連続式ニーダーにて60〜80℃にて押し出
し、造粒した。これを冷却後粉砕してペレツト状
の成形材料を得た。
この材料を実施例１と同様にして成形した試験
片のシヤルピー衝撃強度は4.0Kg・cm／cm2であ
り、その他の物性は第１表に示す通りであつた。
比較例 ３
ビニロン繊維及び木粉の代りに引張強度15.3
ｇ／ｄのガラス繊維（３mmカツト品）を50部を使
用した以外は、比較例１と同様にして成形材料を
得た。
この材料を実施例１と同様にして成形した試験
片のシヤルピー衝撃強度は5.0Kg・cm／cm2であ
り、その他の物性は第１表に示す通りであつた。
TECHNICAL FIELD OF THE INVENTION The present invention relates to a phenolic resin molding material for injection molding that has excellent impact strength, and more particularly to a phenolic resin molding material for injection molding that allows molded products with improved Charpy impact strength to be obtained by injection molding. Field of Application of the Invention The phenolic resin molding material for injection molding of the present invention has excellent impact strength in addition to the heat resistance, heat creep resistance, and electrical properties that are the characteristics of phenolic resin, so it is better than many engineering plastics. It can be used as injection molded products in a wide range of fields. For example, it can be used in electrical and electronic parts such as breakers, microswitches, and bobbins, mechanical parts such as gears, cams, bearings, washers, and seal rings, and automobile parts such as connectors and pulleys. Conventional technology and its problems Conventionally, molding materials using thermosetting resins such as phenolic resins have had the problem of lower impact strength than ordinary thermoplastic resin molding materials. As a way to solve the problem,
Generally, organic or inorganic fibers such as pulp, cotton fabric chips, polyamide fibers, polyvinyl alcohol fibers, asbestos fibers, or glass fibers are used as reinforcing materials to improve impact strength. However, among thermosetting resin molding materials, phenolic resin molding materials that exhibit high impact strength can be obtained by compression molding or transfer molding, but cannot be obtained by injection molding. The reality is that a Shalpy impact strength of about 3 to 5 Kg·cm/cm 2 is considered the highest among current materials. The reason for this is that pulp, cotton cloth chips, asbestos fibers, etc. have low tensile strength of each fiber itself, while glass fibers have high tensile strength, but during the production of phenolic resin molding materials or injection molding. By receiving the sear,
This is because it is easily cut off. Furthermore, some polyamide fibers and polyvinyl alcohol fibers have high strength, but these fibers have a problem in that when heated in a phenolic resin, the fibers dissolve in the phenolic resin. In particular, as in injection molding, when heated for more than a few minutes during molding, the fiber itself melts and its own tensile strength decreases, so the shear py impact strength of the resulting molded product hardly improves or does not improve at all. It was found that there was only a slight improvement. OBJECTS OF THE INVENTION The purpose of the present invention is to provide a phenolic resin molding material that solves the problems of the conventional phenolic resin molding materials described above and allows molded products with improved Shapey impact strength to be obtained by injection molding. Structure of the Invention The phenolic resin for injection molding according to the present invention has a solubility parameter (hereinafter referred to as SP value) of 9.0 to
11.0 phenolic resin or modified phenolic resin
Polyvinyl alcohol fiber (hereinafter referred to as vinylon fiber) having a tensile strength of 6 g/denier (hereinafter referred to as g/d) or more per 100 parts by weight
Contains 100 parts by weight. Detailed explanation of the structure and effects of the invention According to the research conducted by the present inventors, the strength of vinylon fiber itself and the Charpy impact strength of the phenolic resin molding material obtained using the same are unique, and high strength It has been found that a phenolic resin molding material that gives molded articles with extremely high impact strength can be obtained by using vinylon fibers. Further, even when a small amount of vinylon fiber is used, the strength is greatly improved. In addition, phenolic resin with an SP value of 9.0 to 11.0,
For example, in a phenolic resin molding material manufactured by combining vinylon fiber with benzyl ether type phenolic resin, the benzyl ether type phenolic resin does not dissolve the vinylon fiber or only slightly dissolves it during material production or injection molding. Therefore, the vinylon fiber can maintain its own strength, and the adhesion between the vinylon fiber and the benzyl ether type phenolic resin is increased. Furthermore, vinylon fiber itself has a tensile strength of 6 g/d or more and has appropriate flexibility, so it is less likely to break even when subjected to shearing during material production or injection molding, making vinylon in fiber form as easy as possible. Much of it will remain in the molded product. By using the phenolic resin molding material of the present invention by means of the above-mentioned technical means and its effects, a molded product having a very high shear pea impact strength, for example around 10 kg·cm/cm 2 , can be obtained by injection molding. Also,
Even when the amount of vinylon fiber added is small, a phenolic resin molding material that gives molded products with improved impact strength can be obtained. According to the present invention, it is possible to obtain a molded product that is lighter in weight because it has better sliding properties and wear resistance than a phenolic resin molding material using glass fiber, and the specific gravity of the material itself is lower. . In view of the problems of the prior art, the present inventors
We have begun research and development of a phenolic resin molding material for injection molding that has higher Shalpy impact strength and superior sliding properties and wear resistance than conventional phenolic resin molding materials for injection molding. Initially, as a result of examining various synthetic fibers other than glass fibers, nylon 66 and vinylon fibers were selected as suitable ones, and various types of fibers with different tensile strengths were also investigated.
No molding material exhibiting high Shapey impact strength could be obtained by injection molding. After investigating the cause, it was discovered that the nylon 66 fiber and vinylon fiber were dissolved in the phenol resin when subjected to heat history. This is clear from the fact that nylon 66 fibers or vinylon fibers are dissolved in the phenolic resin when looking at the fractured surface of a test piece with low Charpy impact strength. Therefore, various phenolic resins and nylon 66
Regarding the combination with fiber or vinylon fiber,
As a result of research on hot solubility, we discovered several phenolic resins that provide molding materials with high impact strength for vinylon fibers. In addition, it was found that nylon 66 fibers are dissolved in most of the phenolic resin during injection molding, and do not exhibit high shear py impact strength. Next, as a result of extensive research into the essential differences between resins that dissolve vinylon fibers when heated and resins that do not, it was found that there is a unique relationship between the SP value of phenolic resin and the solubility of vinylon fibers. They discovered this, and specifically discovered many phenolic resins that do not dissolve vinylon fibers when heated, leading to the present invention. That is, according to the present invention, as described above, SP
Tensile strength is 6 g/d for 100 parts by weight of phenolic resin or modified phenolic resin with a value of 9.0 to 11.0.
By containing 5 to 100 parts by weight of vinylon fibers, the desired phenolic resin molding material for injection molding can be obtained. The SP value referred to in the present invention is based on Adhesion Encyclopedia (Part 1) (written by Ichiro Shibasaki, published by Kobunshi Kankai, 1951 edition, p. 33), and its measurement method is as follows. That is, 1 to 2 g of polymer is placed in a test tube, a solvent amount corresponding to the final solution actually used is added, and the mixture is heated and dissolved while stirring with a glass rod. Solubility is observed at room temperature by cooling the solution.
If the solution is clear, cloudless, and free of gel particles,
It is determined that the polymer is soluble in the solvent. The SP values of the two solvents that dissolve the polymer each indicate an end value, and the SP value range of the polymer is determined. The phenolic resins with an SP value of 9.0 to 11.0 used in the present invention include, for example, benzyl ether type phenolic resins (SP values 9.6 to 10.0), ammonia resol type phenolic resins (SP values 9.9 to 10.0), and modified phenolic resins. Examples of the resin include bisphenol A-modified phenol resin (SP value 9.9-10.7), aniline-modified phenol resin (SP value 9.9-10.7), and amine-modified phenol resin (SP value 9.6-10.7). The vinylon fiber used in the present invention preferably has a tensile strength of 6 g/d or more, more preferably 7.5 g/d or more. If the content is less than 6 g/d, high impact strength cannot be obtained even if a large amount is used, and if a small amount is used, the strength improvement effect is extremely small. The vinylon fiber is preferably used in an amount of 5 to 100 parts by weight, more preferably 15 to 100 parts by weight, per 100 parts by weight of the phenolic resin.
It is best used in an amount of 70 parts by weight. If the amount of vinylon fiber used is less than 5 parts by weight, the improvement in shear py impact strength will be substantially smaller; if it is more than 100 parts by weight, the shar py impact strength will be higher, but the material will not be injection moldable. I get used to it. In the present invention, the length of the vinylon fiber is not particularly specified, but the generally used length of 1 to 5 mm is suitable. In addition, in the present invention, in addition to vinylon fiber, in consideration of heat resistance, bending strength, tensile strength, etc., cellulose, glass fiber, and other inorganic fillers that are usually used in phenolic resin molding materials can be used in combination. It is valid. The molding material of the present invention is manufactured by a commonly used manufacturing method, and one preferred method is as described below. 100 parts by weight of a phenolic resin or modified phenolic resin with an SP value of 9.0 to 11.0, 5 to 100 parts by weight of vinylon fiber with a tensile strength of 6 g/d or more, and if necessary, a combination of cellulose, glass fiber, inorganic filler, etc. Further, appropriate amounts of curing agent, curing aid, mold release agent, coloring agent, etc. are uniformly dispersed and mixed in a Henschel mixer, and then this mixed mixture is heated at 60 to 80°C in a twin-screw continuous kneader. After kneading, 2-4
Extrude and granulate using a double pelleter equipped with a mmφ screen. By cooling and pulverizing this granulated material, a pellet-shaped molding material that can be injection molded can be obtained. Examples Preferred examples of the present invention will be described below, but it goes without saying that the technical scope of the present invention is not limited to these examples. In the following examples, "parts" also indicate "parts by weight." Example 1 100 parts of benzyl ether type phenolic resin with an SP value of 9.6 to 10.0, 50 parts of vinylon fiber (1 mm cut product) with a tensile strength of 7.8 g/d, 20 parts of wood flour (120 mesh product), 10 parts of magnesium oxide , 10 parts of stearic acid, and 5 parts of spirit black were uniformly dispersed and mixed using a Henschel mixer. Next, this mixture was heated and kneaded at 60 to 80°C in a twin-screw continuous kneader, and then extruded and granulated using a double pelleter equipped with a 3 mmφ screen. After cooling the granules, they were pulverized to obtain a pellet-shaped molding material. Using this molding material, the commonly used molding conditions (injection molding pressure 1200-1500Kg/cm 2 , mold temperature
Injection molding was performed at 160-170° C. and molding time 60-90 seconds (MEIKI RJ-140C injection molding machine) to obtain a JIS test piece for measuring Charpy impact strength. As a result of the test, the shear strength of this specimen was 9.7Kg.
cm/ cm2 . Other physical properties of the injection molded material were as shown in Table 1. Furthermore, the physical properties are
Measured based on JIS-K-6911. Example 2 A molding material was obtained in the same manner as in Example 1, except that 30 parts of vinylon fiber with a tensile strength of 7.8 g/d and 40 parts of wood flour were used. A test piece molded from this material in the same manner as in Example 1 had a Charpy impact strength of 5.5 kg·cm/cm 2 and other physical properties as shown in Table 1. Example 3 A molding material was obtained in the same manner as in Example 1, except that 70 parts of vinylon fiber with a tensile strength of 7.8 g/d was used instead of 50 parts of vinylon fiber and 20 parts of wood flour. The Charpy impact strength of a test piece molded from this molding material in the same manner as in Example 1 was 10.5 Kg・cm/cm 2
The other physical properties were as shown in Table 1. Example 4 A molding material was obtained in the same manner as in Example 1, except that a metaxylene diamine-modified phenolic resin with an SP value of 9.9 to 10.0 was used instead of the benzyl ether type phenolic resin, and 15 parts of hexamethylenetetramine was added. Ta. A test piece molded from this material in the same manner as in Example 1 had a Charpy impact strength of 9.0 Kg·cm/cm 2 and other physical properties as shown in Table 1. Comparative example 1 Novolac type phenolic resin with SP value of 12.7 to 14.5
100 parts, vinylon fiber (1 mm
Cut products) 50 parts, wood flour (120 mesh products) 20 parts,
15 parts of hexamethylenetetramine, 10 parts of magnesium oxide, 10 parts of stearic acid, and 5 parts of spirit black were uniformly dispersed and mixed using a Henschel mixer. This mixed compound was mixed in a twin-screw continuous kneader for 60 minutes.
After heating and kneading at ~80°C, the mixture was extruded and granulated using a double pelleter with a 3 mmφ screen. After cooling, this granulated material was crushed to obtain a pellet-shaped molding material. A test piece made of this material by injection molding in the same manner as in Example 1 had a Charpy impact strength of 5.3 kg·cm/cm 2 and other physical properties as shown in Table 1. Comparative Example 2 100 parts of benzyl ether type phenolic resin with an SP value of 9.6 to 10.0, 50 parts of vinylon fiber (3 mm cut product) with a tensile strength of 3.0 g/d, 20 parts of wood flour (120 mesh product), 10 parts of magnesium oxide , 10 parts of stearic acid, and 5 parts of spirit black were uniformly dispersed and mixed using a Henschel mixer. This blend was extruded and granulated at 60 to 80°C using a twin-screw continuous kneader. After cooling, this was crushed to obtain a pellet-shaped molding material. The Charpy impact strength of a test piece molded from this material in the same manner as in Example 1 was 4.0 Kg·cm/cm 2 , and other physical properties were as shown in Table 1. Comparative Example 3 Tensile strength 15.3 instead of vinylon fiber and wood flour
A molding material was obtained in the same manner as in Comparative Example 1, except that 50 parts of g/d glass fiber (3 mm cut product) was used. A test piece made of this material in the same manner as in Example 1 had a Charpy impact strength of 5.0 Kg·cm/cm 2 and other physical properties as shown in Table 1.
【表】【table】
Claims (1)
ル樹脂または変性フエノール樹脂100重量部に、
引張強度が６ｇ／デニール以上のポリビニルアル
コール繊維５〜100重量部を含有させてなること
を特徴とする射出成形用フエノール樹脂成形材
料。 ２ 溶解度パラメーターが9.0〜11.0のフエノー
ル樹脂または変性フエノール樹脂がベンジリツク
エーテル型フエノール樹脂、アンモニアレゾール
型フエノール樹脂、ビスフエノールＡ変性フエノ
ール樹脂、アニリン変性フエノール樹脂又はアミ
ン変性フエノール樹脂であることを特徴とする特
許請求の範囲第１項記載の射出成形用フエノール
樹脂成形材料。[Claims] 1. 100 parts by weight of a phenolic resin or modified phenolic resin having a solubility parameter of 9.0 to 11.0,
A phenolic resin molding material for injection molding, characterized in that it contains 5 to 100 parts by weight of polyvinyl alcohol fibers having a tensile strength of 6 g/denier or more. 2. The phenolic resin or modified phenolic resin having a solubility parameter of 9.0 to 11.0 is a benzyl ether type phenolic resin, an ammonia resol type phenolic resin, a bisphenol A modified phenolic resin, an aniline modified phenolic resin, or an amine modified phenolic resin. A phenolic resin molding material for injection molding according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58160407A JPS6053555A (en) | 1983-09-02 | 1983-09-02 | Phenolic resin molding compound for injection molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58160407A JPS6053555A (en) | 1983-09-02 | 1983-09-02 | Phenolic resin molding compound for injection molding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6053555A JPS6053555A (en) | 1985-03-27 |
| JPS629616B2 true JPS629616B2 (en) | 1987-03-02 |
Family
ID=15714265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58160407A Granted JPS6053555A (en) | 1983-09-02 | 1983-09-02 | Phenolic resin molding compound for injection molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6053555A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60248766A (en) * | 1984-05-24 | 1985-12-09 | Asahi Organic Chem Ind Co Ltd | Phenolic resin molding material |
| JPS60248767A (en) * | 1984-05-24 | 1985-12-09 | Asahi Organic Chem Ind Co Ltd | Phenolic resin molding material for compression molding |
| JPH0615655B2 (en) * | 1985-06-03 | 1994-03-02 | 旭有機材工業株式会社 | Resin molding material for injection molding |
| JPH0615654B2 (en) * | 1985-06-03 | 1994-03-02 | 旭有機材工業株式会社 | Resin molding material for injection molding |
| JPH0622136B2 (en) * | 1986-10-22 | 1994-03-23 | 昭和電工株式会社 | Manufacturing method of carbon plate for fuel cell separator |
| CN110343224A (en) * | 2019-07-16 | 2019-10-18 | 沙县宏盛塑料有限公司 | The preparation method of bisphenol A modified phenolic resin and modified alkyd resin moulding material |
-
1983
- 1983-09-02 JP JP58160407A patent/JPS6053555A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6053555A (en) | 1985-03-27 |
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