JPS6069149A - Crosslinkable vinyl chloride resin composition - Google Patents
Crosslinkable vinyl chloride resin compositionInfo
- Publication number
- JPS6069149A JPS6069149A JP17783083A JP17783083A JPS6069149A JP S6069149 A JPS6069149 A JP S6069149A JP 17783083 A JP17783083 A JP 17783083A JP 17783083 A JP17783083 A JP 17783083A JP S6069149 A JPS6069149 A JP S6069149A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- dithiol
- group
- 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.)
- Granted
Links
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は架橋性塩化ビニル系樹脂組成物に関するもので
あり、特には建築材料として充分に実用化に耐え得る機
械的特性を備えた成形品を与える架橋性塩化ビニル系樹
脂組成物の提供を目的とするものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a crosslinkable vinyl chloride resin composition, and particularly to a crosslinkable vinyl chloride resin composition that provides a molded article with mechanical properties sufficient for practical use as a building material. The purpose is to provide a resin composition.
従来、塩化ビニル系樹脂成形品はバランスのとれた機械
的特性と価格の点から建築材料等広い分野で使用されて
おり、硬質成形品としてはパイプ、波板、デツキ材、窓
枠材などが、また軟質成形品としては床材、電線被覆材
、フィルムあるいはシートなど各種のものが製造されて
いる。Conventionally, polyvinyl chloride resin molded products have been used in a wide range of fields such as construction materials due to their well-balanced mechanical properties and price, and hard molded products include pipes, corrugated sheets, decking materials, window frame materials, etc. In addition, various soft molded products such as flooring materials, wire covering materials, films, and sheets are manufactured.
しかして、塩化ビニル系樹脂成形品(二ついては。However, there are two types of vinyl chloride resin molded products.
耐熱性あるいは機械的強度を一段と向上させる試みがい
ろいろ行われており、その改質手段の一つとして塩化ビ
ニル系樹脂の架橋を行う方法がある。Various attempts have been made to further improve heat resistance or mechanical strength, and one of the modification methods is to crosslink vinyl chloride resin.
具体的には、塩化ビニル系樹脂に■過酸化物のようなラ
ジカル発生剤、■過酸化物と多官能基を有する架橋助剤
、または■ジアミン、テトラミンなどの核型架橋剤など
を添加した組成物、あるいは■架橋しやすい基を導入し
た塩化ビニル系樹脂組成物を放射線架橋あるいは熱架橋
(加熱5二より架橋させる)させるものである。しかし
ながら、放射線架橋は大がかりな照射設備を要し、高額
な経費がかかるほか、用途的I:限定されるため一般的
な方法ではない。また上記組成物を熱架橋させる方法は
、架橋と同時に塩化ビニル系樹脂の看色、分解が促進さ
れ、著しく外観が阻害されたり、成形機の中でスコーチ
を生じ、成形不能となる等の問題がある。Specifically, to vinyl chloride resin, ■ a radical generator such as peroxide, ■ a crosslinking aid having peroxide and a polyfunctional group, or ■ a nuclear crosslinking agent such as diamine or tetramine are added. The composition or (2) a vinyl chloride resin composition into which a group that is easily crosslinked is crosslinked by radiation or thermally (crosslinked by heating 52). However, radiation crosslinking requires large-scale irradiation equipment, is expensive, and is not a common method because it is limited in terms of use. In addition, the method of thermally crosslinking the above composition has problems such as promoting the discoloration and decomposition of the vinyl chloride resin at the same time as crosslinking, significantly impairing the appearance, and causing scorch in the molding machine, making it impossible to mold. There is.
一方、塩化ビニル系樹脂(:多量の補強性無機質充填剤
を添加することにより成形品の耐熱性、寸法安定性が向
上することも知られており、この充填剤としてガラス繊
維、アスベスト等の針状・繊維状充填剤が用いられてい
る。しかしながら、耐熱性1寸法安定性を向上せしめる
ため5二はそれらの配合量をきわめて多量とする必要が
あり、この多量添加が逆に成形品の機械的強度を低下せ
しめると共t:著しく成形側工性が阻害されるという問
題がある。On the other hand, it is also known that the heat resistance and dimensional stability of molded products can be improved by adding a large amount of reinforcing inorganic fillers to vinyl chloride resins. However, in order to improve heat resistance and dimensional stability, it is necessary to add a very large amount of these fillers, and this addition of a large amount may adversely affect the machine of the molded product. There is a problem in that when the mechanical strength is lowered, the side workability of molding is significantly inhibited.
本発明は従来のかかる問題点を解決し、建築材料等とし
て充分に実用化に耐え得る機械的特性をもった成形品を
製造することができる塩化ビニル系樹脂組成物を提供す
るもので、これは塩化ビニル系樹脂に結晶性けい酸カル
シウムとジチオール−8−)リアジン化合物とを添加し
たものである。The present invention solves these conventional problems and provides a vinyl chloride resin composition that can produce molded products with sufficient mechanical properties that can be put to practical use as building materials, etc. is a vinyl chloride resin to which crystalline calcium silicate and a dithiol-8-) riazine compound are added.
この本発明によれば、熱架橋の際に塩化ビニル系樹脂の
看色をともなうとか、あるいは補強性無機質充填剤の高
充填による前記問題点が解消され、本来塩化ビニル系樹
脂が有する物性を損うことなく、均一に熱架橋させるこ
とができ、耐衝撃性、剛性1寸法安定性、耐燃焼性等を
著しく向上させることができる。According to the present invention, the above-mentioned problems caused by the discoloration of the vinyl chloride resin during thermal crosslinking or the high filling of the reinforcing inorganic filler are solved, and the physical properties originally possessed by the vinyl chloride resin are impaired. Thermal crosslinking can be uniformly carried out without any oxidation, and impact resistance, rigidity, one-dimensional stability, flame resistance, etc. can be significantly improved.
本発明について以下順を追って説明する。The present invention will be explained step by step below.
本発明に用いられる塩化ビニル系樹脂は、塩化ビニルホ
モポリマーに限定されず、これには塩化ビニルを主体と
する共重合体、グラフト共重合体。The vinyl chloride resin used in the present invention is not limited to vinyl chloride homopolymers, but includes copolymers and graft copolymers mainly composed of vinyl chloride.
さらg二は塩化ビニル樹脂を主体とするポリ・脅−ブレ
ンドが包含される。塩化ビニルと共重合されるコモノマ
ーとしては、酢酸ビニル、塩化ビニリデン、アクリル酸
およびそのエステル、アクリロニトリル類、エチレン、
プロピレン等のオレフィン類、マレイン酸およびその無
水物などが例示され、これらは1種または2種以上の混
合物として使用される。また、塩化ビニル樹脂にポリマ
ーブレンドされる樹脂としては、親和性のよいエチレン
−酢酸ビニル共重合体、メチルメタクリレート−ブタジ
ーエン−スチレン共重合体、メチルメタクリレート−ブ
タジェン−スチレン共重合体、アクリロニトリル−ブタ
ジェン−スチレン共重合体、塩素化ポリエチレン、ニト
リル−ブタジェン共重合体などが例示される。Furthermore, G2 includes a poly blend mainly composed of vinyl chloride resin. Comonomers copolymerized with vinyl chloride include vinyl acetate, vinylidene chloride, acrylic acid and its esters, acrylonitriles, ethylene,
Examples include olefins such as propylene, maleic acid and its anhydride, and these may be used alone or as a mixture of two or more. In addition, resins to be blended with vinyl chloride resin include ethylene-vinyl acetate copolymer, methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and acrylonitrile-butadiene-styrene copolymer. Examples include styrene copolymers, chlorinated polyethylene, and nitrile-butadiene copolymers.
本発明は上記した塩化ビニル系樹脂に対して。The present invention relates to the above-mentioned vinyl chloride resin.
結晶性けい酸カルシウムおよびジチオール−S −トリ
アジン化合物を配合するのであるが、この結晶性けい酸
カルシウムは一般に石灰とけい酸とを水和反応させるこ
とにより得られる合成けい酸カルシウムであり、配合比
を調整し温度と圧力をかけて結晶を生成させたシーツト
ライ) (60aO・上記結晶性けい酸カルシウムの配
合量は、塩化ビニル系樹脂100重量部当り5〜200
重量部好ましくは10〜100重量部の範囲とすること
がよい。Crystalline calcium silicate and dithiol-S-triazine compound are blended, and this crystalline calcium silicate is generally a synthetic calcium silicate obtained by hydration reaction of lime and silicic acid. (Sheet trial in which crystals were generated by applying controlled temperature and pressure) (60aO・The amount of the above crystalline calcium silicate is 5 to 200 parts by weight per 100 parts by weight of vinyl chloride resin)
Parts by weight preferably range from 10 to 100 parts by weight.
つぎに本発明に使用されるジチオール−8−トリアジン
化合物は、一般式
(式中のRはOR”、 SR” 、 NR” R’で示
される基、またはフェニル基、ナフチル基1モルホリル
基であり、ここにR”、R”、R”およびR4は各個1
;水素原子または一価炭化水素基である)で示される化
合物ならびにその金属塩である。これらのうちでも塩化
ビニル系樹脂の橋かけ剤的効果としては、Rが塩基性の
大なるもの、たとえばNR” R4,SFF 。Next, the dithiol-8-triazine compound used in the present invention has the general formula (wherein R is a group represented by OR", SR", NR"R', a phenyl group, a naphthyl group, a morpholyl group, , where R'', R'', R'' and R4 are each 1
; a hydrogen atom or a monovalent hydrocarbon group) and metal salts thereof. Among these, the crosslinking effect of vinyl chloride resins is that R is large in basicity, such as NR'' R4, SFF.
OR”であるものがすぐれている。このようなジチオー
ル−8−)リアジン化合物としてはRが2−ジメチルア
ミノ基、2−ジブチルアミノ基、2−オクチルアミノ基
、2−シクロへキシルアミノ基、2−ベンジルアミノ基
、2−ジベンジルアミノ基。OR". As such dithiol-8-) riazine compounds, R is a 2-dimethylamino group, 2-dibutylamino group, 2-octylamino group, 2-cyclohexylamino group, 2 -benzylamino group, 2-dibenzylamino group.
2−フェニルアミノ基、2−フェニルベンジルアミノ基
、2−メチルフェニルアミノ基、2−アニリノ基、2−
ジフェニルアミノ基、2−α−ナフチルアミノ基、2−
β−ナフチルアミノ基、2−ペンチルチオ基、2−エト
キシ基、2−フェノキシ基であるような各化合物が例示
される。またジチオール−8−)リアジン化合物の金属
塩としては、該化合物のアルカリ金属塩、アルカリ土類
金属塩、その他A1.8n、Pb、Niなどの金属塩が
例示される。2-phenylamino group, 2-phenylbenzylamino group, 2-methylphenylamino group, 2-anilino group, 2-
Diphenylamino group, 2-α-naphthylamino group, 2-
Examples include compounds such as a β-naphthylamino group, a 2-pentylthio group, a 2-ethoxy group, and a 2-phenoxy group. Examples of the metal salt of the dithiol-8-)riazine compound include alkali metal salts, alkaline earth metal salts, and other metal salts such as A1.8n, Pb, and Ni.
上記ジチオール−8−)リアジン化合物もしくはその金
属塩の配合量は、塩化ビニル系樹脂100重量部に対し
て0.2〜10重量部好ましくは0.5〜5重量部の範
囲とすることがよい。The amount of the dithiol-8-)riazine compound or its metal salt to be blended is preferably in the range of 0.2 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. .
上記ジチオール−8−)リアジン化合物が塩化ビニル樹
脂に対し架橋剤的効果を示すことはすでに知られている
が、このものを塩化ビニル樹脂に添加し、たとえばロー
ル成形、加圧成形、押出成形した場合には、成形時のせ
ん断発熱によって架橋反応が進行するので、その架橋反
応のコントロールが難しく、塩化ビニル系樹脂の熱分解
が促進され、実用に供する成形品が得難いという問題が
あった。It is already known that the above-mentioned dithiol-8-) riazine compound exhibits a crosslinking effect on vinyl chloride resin. In this case, the crosslinking reaction progresses due to shear heat generation during molding, making it difficult to control the crosslinking reaction, which accelerates thermal decomposition of the vinyl chloride resin, making it difficult to obtain molded products for practical use.
しかるシニ、おどろくべきことi二は、ジチオール−8
−)リアジン化合物と結晶性けい酸カルシウムとを併用
することl二よって、塩化ビニル系樹脂の架橋反応が良
好に進行し、この熱架橋反応時(二塩化ビニル系樹脂の
分解が生じないことが確認された。そして本発明の架橋
性塩化ビニル系樹脂組成物から得られる成形品は、燃焼
時C:も軟化流動することなく、元の形状を保持したま
ま燃焼炭化するという特徴を有するほか、燃焼時に発生
する塩酸ガスを捕捉する効果を有する。However, the second surprising thing is dithiol-8.
-) By using a riazine compound and crystalline calcium silicate in combination, the crosslinking reaction of the vinyl chloride resin progresses favorably, and during this thermal crosslinking reaction (no decomposition of the vinyl dichloride resin occurs). The molded product obtained from the crosslinkable vinyl chloride resin composition of the present invention has the following characteristics: C: does not soften or flow during combustion, and burns and carbonizes while retaining its original shape. It has the effect of capturing hydrochloric acid gas generated during combustion.
なお、本発明においては、塩化ビニル系樹脂の架橋f二
連常用いられている少なくとも2個の重合可能な不飽和
結合を有する反応性可塑剤を併用すること、そのほか一
般の可塑剤、充填剤、安定剤。In addition, in the present invention, a reactive plasticizer having at least two polymerizable unsaturated bonds, which is commonly used for crosslinking of vinyl chloride resin, is used in combination, and other general plasticizers and fillers are also used. , stabilizer.
滑材、紫外線吸収剤、顔料等を配合することは自由であ
る。It is free to add lubricants, ultraviolet absorbers, pigments, etc.
架橋反応を進行させるには1通常の熱架橋方式によるの
が一般的であるが、α線、β線、r線、紫外線、高周波
等の活性エネルギー線を使用してもよい。To advance the crosslinking reaction, a normal thermal crosslinking method is generally used, but active energy rays such as alpha rays, beta rays, r rays, ultraviolet rays, and high frequency waves may also be used.
本発明(−よって得られた架橋性便質成形品は、すぐれ
た耐熱性、寸法安定性、剛性、耐燃焼性を有することか
ら、建築材料、構造部材としての使用に適しており、特
には窓枠材、化粧材、側壁板等の用途C:最適である。The crosslinkable fecal matter molded product obtained according to the present invention has excellent heat resistance, dimensional stability, rigidity, and flame resistance, and is therefore suitable for use as a building material or a structural member. Application C: Optimal for window frame materials, decorative materials, side wall boards, etc.
また軟質成形品にあっては、長尺タイル、耐熱性シート
等の用途に適している。In addition, for soft molded products, it is suitable for applications such as long tiles and heat-resistant sheets.
つぎC二具体的実施例をあげる。Next, C2 concrete examples will be given.
実施例(実験11〜隘5) 第1表に示す5種類のコンパウンドを調製した。Examples (Experiments 11 to 5) Five types of compounds shown in Table 1 were prepared.
′#g 1 表 (配合0重量部)
TK−1000: 信越化学工業■製、塩化ビニル樹脂
、平均重合度 1050
PE−520: ヘキスト社製、ポリエチレンワックス
0P−Wax: ヘキスト社製、エステルワックスTM
−181FB、T : 勝山化工■製、メチルすずメル
カプタイド系安定剤
品性けい酸カルシウム
上記組成の配合物を6インチロールぽ二て185℃で5
分間混練しロールシートを作製後、これを積み重ねて1
90℃にて圧力60KP/cdで加圧成形し厚さ1」の
プレス成形品を得た。'#g 1 Table (Blend 0 parts by weight) TK-1000: Shin-Etsu Chemical Co., Ltd., vinyl chloride resin, average degree of polymerization 1050 PE-520: Hoechst Co., Ltd., polyethylene wax 0P-Wax: Hoechst Co., Ltd., Ester Wax TM
-181FB, T: Manufactured by Katsuyama Kako ■, methyl tin mercaptide stabilizer Product properties Calcium silicate A blend of the above composition was rolled in a 6-inch roll at 185°C for 5 minutes.
After kneading for a minute to make a roll sheet, stack it up and
Pressure molding was performed at 90° C. and a pressure of 60 KP/cd to obtain a press molded product with a thickness of 1”.
JIS K6745 C準じて20℃にて物性試験及び
プレス板の外観(N色性)及び架橋度をTHF不溶分測
定によって行い次の結果を得た。A physical property test was conducted at 20° C. in accordance with JIS K6745 C, and the appearance (N color) and degree of crosslinking of the pressed plate were measured by THF insoluble content measurement, and the following results were obtained.
第 2 表
=β−トリアジV化合物を併用した塩化ビニル系樹脂組
成物は、架橋剤を単独で用いた場合(実験−3)、無機
質i二次酸カルシウムを用いた場合(実験遅4)、ケイ
酸カルシウムを単独で用いた場合(実験1’11IX5
)に較べて樹脂の着色分解がなく、架橋効率が高(剛性
、耐熱性1:優れている。Table 2 = Vinyl chloride resin compositions using a β-triazid V compound in combination, when the crosslinking agent was used alone (Experiment 3), when the inorganic secondary acid calcium was used (Experiment 4), When using calcium silicate alone (Experiment 1'11IX5
), there is no coloring and decomposition of the resin, and the crosslinking efficiency is high (rigidity, heat resistance 1: excellent).
Claims (1)
ジチオール−8−)リアジン化合物からなる架橋性塩化
ビニル系樹脂組成物 2、塩化ビニル系樹脂100重酸部、結晶性けい酸カル
シウム5−200重量部およびジチオール−8−)リア
ジン化合物0.2〜10重量部からなる特許請求の範囲
第1項記載の架橋性塩化ビニル系樹脂組成物 3、前記結晶性けい酸カルシウムがシーツドライド、ト
バモライトまたはウオラストナイトである特許請求の範
囲$1項記載の架橋性塩化ビニル系樹脂組成物 4、前記ジチオール−8−)リアジン化合物が、一般式 (式中のRはOR” 、 SR” 、 NR” R’で
示される基、またはフェニル基、ナフチル基1モルホリ
ル基であり、ここにR1、R1、ulおよびR4は各個
に水素原子または一価炭化水素基である)で示される化
合物ならびにその金属塩である特許請求の範囲第1項記
載の架橋性塩化ビニル系樹脂組成物[Scope of Claims] 1. A crosslinkable vinyl chloride resin composition comprising a vinyl chloride resin, crystalline calcium silicate and a dithiol-8-)riazine compound. 2. A vinyl chloride resin with 100 parts of heavy acid, crystalline silica. The crosslinkable vinyl chloride resin composition 3 according to claim 1, comprising 5 to 200 parts by weight of calcium silicate and 0.2 to 10 parts by weight of a dithiol-8-)riazine compound, wherein the crystalline calcium silicate is The crosslinkable vinyl chloride resin composition 4 according to claim 1, which is Sheetdryde, tobermorite or wollastonite, wherein the dithiol-8-)riazine compound has the general formula (wherein R is OR"), a group represented by SR'', NR''R', or a phenyl group, a naphthyl group, a morpholyl group, where R1, R1, ul and R4 are each a hydrogen atom or a monovalent hydrocarbon group) The crosslinkable vinyl chloride resin composition according to claim 1, which is a compound and a metal salt thereof.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17783083A JPS6069149A (en) | 1983-09-26 | 1983-09-26 | Crosslinkable vinyl chloride resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17783083A JPS6069149A (en) | 1983-09-26 | 1983-09-26 | Crosslinkable vinyl chloride resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6069149A true JPS6069149A (en) | 1985-04-19 |
JPS6322221B2 JPS6322221B2 (en) | 1988-05-11 |
Family
ID=16037851
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17783083A Granted JPS6069149A (en) | 1983-09-26 | 1983-09-26 | Crosslinkable vinyl chloride resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6069149A (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5266574A (en) * | 1975-12-01 | 1977-06-02 | Nippon Zeon Co | Process for manufacture of polyvinyl chloride foam |
JPS52142754A (en) * | 1976-05-25 | 1977-11-28 | Norio Nakamura | Crossslinking agent for soft or paste polyvinyl chlorides |
JPS5545735A (en) * | 1978-09-26 | 1980-03-31 | Osaka Soda Co Ltd | Halogen-containing polymer vulcanizing composition |
-
1983
- 1983-09-26 JP JP17783083A patent/JPS6069149A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5266574A (en) * | 1975-12-01 | 1977-06-02 | Nippon Zeon Co | Process for manufacture of polyvinyl chloride foam |
JPS52142754A (en) * | 1976-05-25 | 1977-11-28 | Norio Nakamura | Crossslinking agent for soft or paste polyvinyl chlorides |
JPS5545735A (en) * | 1978-09-26 | 1980-03-31 | Osaka Soda Co Ltd | Halogen-containing polymer vulcanizing composition |
Also Published As
Publication number | Publication date |
---|---|
JPS6322221B2 (en) | 1988-05-11 |
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