JPS58154748A - Crosslinkable paste vinyl chloride resin composition - Google Patents
Crosslinkable paste vinyl chloride resin compositionInfo
- Publication number
- JPS58154748A JPS58154748A JP3781682A JP3781682A JPS58154748A JP S58154748 A JPS58154748 A JP S58154748A JP 3781682 A JP3781682 A JP 3781682A JP 3781682 A JP3781682 A JP 3781682A JP S58154748 A JPS58154748 A JP S58154748A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- paste vinyl
- resin composition
- crosslinkable
- 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
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は架橋性塩化ビニルペースト樹脂組成物に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a crosslinkable vinyl chloride paste resin composition.
塩化ビニルペースト樹脂はその加工性の良さからクッシ
ョンフロア−１壁装材、その他インテリア製品として近
年ますます広範囲に使用されている。Vinyl chloride paste resin has been used more and more widely in recent years as a cushion floor-1 wall covering material and other interior products because of its good processability.
これらの用途において要求される耐熱軟化性、耐シガレ
ット性及び耐油性などの特性は樹脂を架橋することによ
って付与することができる。Properties such as heat softening resistance, cigarette resistance, and oil resistance required in these uses can be imparted by crosslinking the resin.
従来からの塩化ビニル樹脂の架橋方法としてはオニウム
塩、特に第４級アンモニウム塩の存在下にポリカルボン
酸の金属塩（特にアルカリ金属）を反応させる方法（例
えば、特公昭４８−３３６２３゜−３３６２４，特公昭
４９−４８２３）がある。しかしながらこれらの方法で
は、不透明化や分解着色を避けて架橋性を充分に上げる
ことが困難であったり、設備費が高価になるという欠点
がある。これに代る方法としてトリチオシアヌル酸及び
その誘導体による方法（例えば特公昭５２−９４６３．
特開昭５２＝２１０５２゜特開昭５２−１５０４６０
）が見い出された。しかしこの方法をもちいても、促進
剤（架橋助剤、受酸剤）としてジフェニルグアニジン、
ＭｇＯ，ＣａＯ，ＳｒＯ，ｔｂＺｏ。A conventional crosslinking method for vinyl chloride resin is a method in which a metal salt (especially an alkali metal) of a polycarboxylic acid is reacted in the presence of an onium salt, especially a quaternary ammonium salt (for example, Japanese Patent Publication No. 48-33623-33624). , Special Publication No. 49-4823). However, these methods have drawbacks such as difficulty in sufficiently increasing crosslinking properties while avoiding opacity and decomposition and coloring, and high equipment costs. An alternative method is a method using trithiocyanuric acid and its derivatives (for example, Japanese Patent Publication No. 52-9463.
Japanese Patent Publication No. 52 = 21052゜ Japanese Patent Publication No. 52-150460
) was found. However, even with this method, diphenylguanidine is used as an accelerator (crosslinking aid, acid acceptor).
MgO, CaO, SrO, tbZo.
Ｍ９（ＯＨ）２．ＣＪＯＨ）２．ＭｙＣＯ３，ＣａＣＯ
３，Ｂａ−８ｔ、Ｃａ−８ｔ等の有機塩基或いは塩基性
の強い金属塩を使用せざるを得ず、この場合に、
！イ）ペーストゾルの安定性
（ロ）成形品の透明性
（ハ）加工耐熱性
等が低下するという問題がある。M9(OH)2. CJOH)2. MyCO3, CaCO
3. Organic bases such as Ba-8t and Ca-8t or highly basic metal salts must be used, and in this case,! B) Stability of the paste sol (B) Transparency of the molded product (C) Processing heat resistance etc. are reduced.
本発明者等は架橋性を損なうことなく、ゾル加工性が容
易であり、加工耐熱の改良された、透明性Ｉ好な塩化ビ
ニルペースト樹脂組成物を開発すべく、これまで幾多の
研究を行って来たが、チオールＳ −） ＩＪアジンに
着目して鋭意研究検討を重ねた結果、塩化ビニルペース
ト樹脂にＣＰ−２８０（大人化学工業所製品の商品名
主成分２ジプチルアミノ−４ｆｉジチオールＳトリアジ
ン２０チを含む、分散性の改良された架橋剤）、／’ｔ
イドロタルサイト類の二成分を添加することにより所期
の目的が達成されることを見い出し、本発明に到達した
。The present inventors have conducted numerous studies in order to develop a vinyl chloride paste resin composition that is easily sol-processable, has improved processing heat resistance, and has good transparency without impairing crosslinking properties. However, as a result of intensive research and study focusing on thiol S-) IJ azine, CP-280 (trade name of Otona Kagaku Kogyo product) was added to vinyl chloride paste resin.
A cross-linking agent with improved dispersibility containing the main components 2 diptylamino-4 dithiol S triazine), /'t
It has been discovered that the desired objective can be achieved by adding two components of hydrotalcites, and the present invention has been achieved.
本発明で用いられる塩化ビニルペースト樹脂としては塩
化ビニルの単独重合体のほかに塩化ビニルト酢酸ヒニル
ナトのビニルエステル、ビニルエーテル、アクリル酸又
はメタクリル酸のエステルマレイン酸、フマール酸、ア
クリロニトリル、塩化ビニリデン、エチレン又はプロピ
レンなどとの共重合体などが用いられる。又２−ジブチ
ルアミノ−４，６−シチオールーＳ−） ’Ｊアジンの
金属塩としては、リチウム、ナトリウム、カリウムなど
のアルカリ金属塩、カルシウム、マグネノウム、バリウ
ム、ストロンチウムなどのアルカリ土類金属塩、カドミ
ウム、亜鉛、アルミニウム、錫、鉛ニッケルなどの塩、
さらにはジプチル錫、トリブチル錫塩を掲げることが出
来る。In addition to vinyl chloride homopolymers, vinyl chloride paste resins used in the present invention include vinyl esters of vinyl chloride and vinyl acetate, vinyl ethers, esters of acrylic acid or methacrylic acid, maleic acid, fumaric acid, acrylonitrile, vinylidene chloride, ethylene or A copolymer with propylene or the like is used. Metal salts of 2-dibutylamino-4,6-sithio-S-)'J azine include alkali metal salts such as lithium, sodium, and potassium, alkaline earth metal salts such as calcium, magnenoum, barium, and strontium, and cadmium. , salts of zinc, aluminum, tin, lead nickel, etc.
Further examples include diptyltin and tributyltin salts.
本発明で用いるハイドロタルサイト類とは、一般式ＸＡ
Ｊ２０３−ＹＭ、＠０−Ｃ０３−Ｚ（Ｈ２Ｏ） １７）
組成を持った無機化合物であり′、一般にＡ１２ｏ３と
Ｍｇｏの比率により特性が異なる。本発明を完成するに
当り、協和化学工業株式会社より市販されているＤＨ］
ｉ！４Ａ（Ａ１２０３とＭｇＯの比は１対４とされてい
る）及びキョーワード５００（Ａ７？２０．とＭｇＯの
比は１対６とされている）を用いた。The hydrotalcites used in the present invention have the general formula
J203-YM, @0-C03-Z(H2O) 17)
It is an inorganic compound with a specific composition, and its properties generally vary depending on the ratio of A12o3 and Mgo. In completing the present invention, DH commercially available from Kyowa Chemical Industry Co., Ltd.]
i! 4A (the ratio of A1203 to MgO is said to be 1:4) and Kyoward 500 (the ratio of A7?20. to MgO is said to be 1:6).
また本発明は塩化ビニルペースト樹脂配合の非発泡、透
明配合に最適であるばかりでなく、機械的及び化学的な
発泡配合、不透明配合においてもその協果を妨げるもの
ではない、
発泡配合、不透明配合組成物としては上記本発明の組成
物である架橋剤、ノ・イドロタルサイト類のほか、可塑
剤、発泡剤、セル調整剤（整泡剤）充てん剤、顔料、加
工助剤、安定剤等の配合剤を添加することが出来る。Furthermore, the present invention is not only optimal for non-foaming and transparent formulations of vinyl chloride paste resin formulations, but also does not hinder its cooperative effects in mechanically and chemically foaming formulations and opaque formulations. The composition includes, in addition to the crosslinking agent and hydrotalcites of the above-mentioned composition of the present invention, a plasticizer, a foaming agent, a cell regulator (foam stabilizer), a filler, a pigment, a processing aid, a stabilizer, etc. Compounding agents can be added.
可塑剤として例えばジオクチルフタレート、ジブチルフ
タレート、ブチルベンジルフタレート、ジオクチルアジ
ペート等の二塩基性エステル、トリクレジルフォスフェ
ート、ジフェニルオクチルフォスフェート等のリン酸エ
ステルの一種又はそれ以上、
発泡剤として例えばアゾシカ−ボンアミド、ジニトロン
ベンタメチレン、テトラミントルエ２スルホニルヒ下ラ
ジド、ベンゼンスルホニルヒドラジド、アゾビスイソブ
チルニトリル、Ｎ−Ｎ’ −ジメチル−Ｎ−Ｎ’−ジニ
トロテレフタルアミド、炭酸水素ナトリウム、炭酸アン
モニウム、炭酸水素アンモニウム等がある。As a plasticizer, for example, one or more dibasic esters such as dioctyl phthalate, dibutyl phthalate, butylbenzyl phthalate, and dioctyl adipate, and phosphoric acid esters such as tricresyl phosphate and diphenyl octyl phosphate; As a blowing agent, for example, Azoshika Bonamide, dinitrone bentamethylene, tetramintoluene di-sulfonylhydrazide, benzenesulfonyl hydrazide, azobisisobutylnitrile, N-N'-dimethyl-N-N'-dinitroterephthalamide, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, etc. There is.
セル調整剤（整泡剤）としては各種アニオン系界面活性
剤、ノ・ニオン系界面活性剤、アクリル酸用される。As cell regulators (foam stabilizers), various anionic surfactants, non-ionic surfactants, and acrylic acid are used.
本発明において用いられる添加剤の使用量は、塩化ビニ
ルペースト樹脂１００重量部当たりＣＰ−２８０又はそ
の金属塩は０１〜３０重量部、好ましくは０．５〜１０
重量部、ハイドロタルサイト類０１〜５．０重量部好ま
しくは０１〜１．０重量部である。The amount of additive used in the present invention is 01 to 30 parts by weight, preferably 0.5 to 10 parts by weight of CP-280 or its metal salt per 100 parts by weight of vinyl chloride paste resin.
Parts by weight, preferably 01 to 5.0 parts by weight of hydrotalcites, preferably 01 to 1.0 parts by weight.
次に実施例により本発明を具体的に説明する。Next, the present invention will be specifically explained with reference to Examples.
その結果を表−１に示す。The results are shown in Table-1.
実施例１及び２は次の手順によりおこなった。Examples 1 and 2 were carried out according to the following procedure.
架橋条件第１表の各配合ゾルをポリエステルシートに０
．２〜０．４１１１厚さに塗布し、熱風循還式オープン
乾燥器に入れ２２０℃、１分生で加熱加工を行なう。Crosslinking conditions Each blended sol in Table 1 was applied to a polyester sheet.
．． It is coated to a thickness of 2 to 0.4111 mm, placed in a hot air circulation open dryer, and heat-processed at 220°C for 1 minute.
架橋性組成物をテトラヒドロフランに浸漬し、。Soaking the crosslinkable composition in tetrahydrofuran.
膨潤率（原の容積に対する容積増加率）及び形状を調べ
た。膨潤率の小さいもの程架橋性がよい。The swelling rate (volume increase rate relative to the original volume) and shape were investigated. The smaller the swelling ratio, the better the crosslinkability.
浸漬条件は常温で４時間実施した。粘度測定は、ＢＬ型
粘度計ＮＱ４今ロー ター ６ＯＲＰＭを用い、２０℃
でおごなった。The immersion conditions were 4 hours at room temperature. The viscosity was measured using a BL type viscometer NQ4 Ima rotor 6ORPM at 20°C.
I was relieved.
実施例３は各配合ゾルを家庭用ミキサーによって空気を
導入後、ガラス板に約２′酊の厚さで塗布し２２０℃、
１分生で加熱加工をおこなった。In Example 3, each blended sol was applied to a glass plate to a thickness of about 2' after introducing air using a household mixer, and heated at 220°C.
Heat processing was performed after 1 minute.
実施例２（化学発泡） 実施例３（機械発泡）Example 2 (chemical foaming) Example 3 (mechanical foaming)
Claims (2)
アジン誘導体又はその金属塩 （２〕 ハイドロタルサイト類の少なくとも１種又は
それ等の混合物 を含有させてなる架橋性塩化ビニルペースト樹脂組成物(1) A crosslinkable chloride paste resin containing (1'j) a triazine derivative having at least two mercapto groups or a metal salt thereof (2) at least one type of hydrotalcite or a mixture thereof Vinyl paste resin composition
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3781682A JPS58154748A (en) | 1982-03-10 | 1982-03-10 | Crosslinkable paste vinyl chloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3781682A JPS58154748A (en) | 1982-03-10 | 1982-03-10 | Crosslinkable paste vinyl chloride resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58154748A true JPS58154748A (en) | 1983-09-14 |
| JPH0157135B2 JPH0157135B2 (en) | 1989-12-04 |
Family
ID=12508043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3781682A Granted JPS58154748A (en) | 1982-03-10 | 1982-03-10 | Crosslinkable paste vinyl chloride resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58154748A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2566415A1 (en) * | 1984-06-26 | 1985-12-27 | Centre Nat Rech Scient | PROCESS FOR CROSSLINKING VINYL POLYHLORIDE USING A MULTI-FUNCTIONAL COUPLING AGENT |
| CN113150467A (en) * | 2021-04-23 | 2021-07-23 | 贵州理工学院 | Micro-foaming PVC sol and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5144151A (en) * | 1974-10-11 | 1976-04-15 | Nippon Zeon Co | HASHIKAKEENKABINIRUJUSHINO SEIZOHO |
| JPS5221052A (en) * | 1976-07-01 | 1977-02-17 | Nippon Zeon Co Ltd | Crosslinkable vinyl chloride paste resin composition |
| JPS5580445A (en) * | 1978-12-14 | 1980-06-17 | Kyowa Chem Ind Co Ltd | Thermoplastic resin composition and prevention of deterioration |
-
1982
- 1982-03-10 JP JP3781682A patent/JPS58154748A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5144151A (en) * | 1974-10-11 | 1976-04-15 | Nippon Zeon Co | HASHIKAKEENKABINIRUJUSHINO SEIZOHO |
| JPS5221052A (en) * | 1976-07-01 | 1977-02-17 | Nippon Zeon Co Ltd | Crosslinkable vinyl chloride paste resin composition |
| JPS5580445A (en) * | 1978-12-14 | 1980-06-17 | Kyowa Chem Ind Co Ltd | Thermoplastic resin composition and prevention of deterioration |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2566415A1 (en) * | 1984-06-26 | 1985-12-27 | Centre Nat Rech Scient | PROCESS FOR CROSSLINKING VINYL POLYHLORIDE USING A MULTI-FUNCTIONAL COUPLING AGENT |
| CN113150467A (en) * | 2021-04-23 | 2021-07-23 | 贵州理工学院 | Micro-foaming PVC sol and preparation method thereof |
| CN113150467B (en) * | 2021-04-23 | 2022-05-24 | 贵州理工学院 | Micro-foaming PVC sol and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0157135B2 (en) | 1989-12-04 |
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