JP2566773B2 - Process for producing modified vinyl chloride resin with excellent processability - Google Patents
Process for producing modified vinyl chloride resin with excellent processabilityInfo
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- JP2566773B2 JP2566773B2 JP11498487A JP11498487A JP2566773B2 JP 2566773 B2 JP2566773 B2 JP 2566773B2 JP 11498487 A JP11498487 A JP 11498487A JP 11498487 A JP11498487 A JP 11498487A JP 2566773 B2 JP2566773 B2 JP 2566773B2
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- vinyl chloride
- chloride resin
- monomer
- monomer mixture
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Description
【発明の詳細な説明】 「産業上の利用分野」 本発明は耐衝撃性、耐熱強度を低下させることなく加
工性を改善した改質塩化ビニル樹脂の製造方法に関す
る。TECHNICAL FIELD The present invention relates to a method for producing a modified vinyl chloride resin having improved processability without lowering impact resistance and heat resistance strength.
「従来技術と問題点」 塩化ビニル樹脂は優れた化学的、機械的性質を有し且
つ安価のために工業的に大量に使用されてきた。しかし
乍ら、塩化ビニル樹脂は加工性、耐衝撃性に劣るという
欠点を有する。"Prior Art and Problems" Vinyl chloride resins have been used industrially in large quantities because of their excellent chemical and mechanical properties and their low cost. However, vinyl chloride resins have the drawback of being inferior in processability and impact resistance.
これらの欠点を改善するために、従来一般的に用いら
れてきた塩化ビニル樹脂の改質方法としては、重合体と
した場合の二次転移温度が低いアクリル酸エステルや、
ブタジエン等のジエン系ゴム、オレフィンモノマー等を
他の単量体とともに塩化ビニル樹脂の存在下に共重合す
る方法が知られている。例えば特公昭39−24718には塩
素化塩化ビニル樹脂にブチルアクリレートとスチレン
（以下、Stと略）、又は２−エチルヘキシルアクリレー
ト（以下、EHAと略）とスチレンを被覆重合する方法が
開示され、また、特公昭48−43955には多孔質塩化ビニ
ル樹脂にブタジエン、スチレン、メチルメタクリレート
（以下、MMAと略）を混合して共重合させる方法が開示
されている。In order to improve these drawbacks, as a method for modifying a vinyl chloride resin that has been generally used conventionally, an acrylic ester having a low second-order transition temperature when made into a polymer,
A method is known in which a diene rubber such as butadiene and an olefin monomer are copolymerized with other monomers in the presence of a vinyl chloride resin. For example, Japanese Patent Publication No. 39-24718 discloses a method of coating and polymerizing a chlorinated vinyl chloride resin with butyl acrylate and styrene (hereinafter, abbreviated as St) or 2-ethylhexyl acrylate (hereinafter, abbreviated as EHA) and styrene, and JP-B-48-43955 discloses a method in which butadiene, styrene and methyl methacrylate (hereinafter abbreviated as MMA) are mixed with a porous vinyl chloride resin and copolymerized.
しかし乍ら、前者の如くブチルアクリレート（以下、
BAと略）又はEHAとStの共重合体を被覆重合する方法で
は、加工性は改良されるが、耐衝撃性は改良されない。
一方、後者の如くブタジエン、MMA、Stの混合物を塩化
ビニル樹脂の存在下に共重合させた場合は、耐衝撃性は
改良されるが、加工性はあまり改良されない。However, like the former, butyl acrylate (hereinafter,
The process of coating and polymerizing a copolymer of BA) or EHA and St improves the processability but not the impact resistance.
On the other hand, when the mixture of butadiene, MMA and St is copolymerized in the presence of vinyl chloride resin as in the latter case, the impact resistance is improved, but the processability is not so improved.
上記の他に、アクリル酸エステルとアクリロニトリル
（以下、ANと略）及び／又はメタクリル酸エステルの混
合物を塩化ビニル樹脂の存在下に共重合する方法が知ら
れているが、いずれも加工性はあまり改良されず、耐熱
強度も悪くなる。In addition to the above, there is known a method of copolymerizing a mixture of an acrylic ester and acrylonitrile (hereinafter, abbreviated as AN) and / or a methacrylic ester in the presence of a vinyl chloride resin, but all of them have poor processability. It is not improved, and the heat resistance becomes worse.
「問題点を解決するための手段」 本発明者らはかかる実情に鑑み、上記従来技術の欠点
を改良すべく鋭意研究を重ねた結果、溶解性パラメータ
の低い単量体とメタクリル酸エステル、ビニル芳香族単
量体、架橋性単量体を塩化ビニル樹脂にあらかじめ含浸
させた後、共重合させることにより、耐衝撃性、耐熱強
度を低下させることなく加工性が大幅に改善された改質
塩化ビニル樹脂が得られることを見出した。“Means for Solving Problems” In view of the above circumstances, the present inventors have conducted intensive studies to improve the above-mentioned drawbacks of the prior art, and as a result, a monomer having a low solubility parameter, a methacrylic acid ester, and vinyl. Modified chloride with improved workability without impairing impact resistance and heat strength by pre-impregnating vinyl chloride resin with aromatic monomer and crosslinkable monomer and then copolymerizing It was found that a vinyl resin can be obtained.
即ち、本発明は、溶解性パラメータが8.0（Cal/cc）
1/2以下のアクリル酸エステル単量体10〜50重量％、ビ
ニル芳香族単量体40〜80重量％、メタクリル酸エステル
単量体５〜40重量％及び架橋性単量体0.01〜10.0重量％
とからなる単量体混合物を塩化ビニル樹脂に含浸させ、
次いで共重合させることを特徴とする加工性の優れた改
質塩化ビニル樹脂の製造方法を内容とするものである。That is, the present invention has a solubility parameter of 8.0 (Cal / cc).
Half or less acrylic ester monomer 10 to 50% by weight, vinyl aromatic monomer 40 to 80% by weight, methacrylic acid ester monomer 5 to 40% by weight and crosslinkable monomer 0.01 to 10.0% by weight %
Impregnate a vinyl chloride resin with a monomer mixture consisting of
The present invention is directed to a method for producing a modified vinyl chloride resin having excellent processability, which is characterized by copolymerization.
本発明に用いられる溶解性パラメータの低い単量体と
しては、EHA等のアクリル酸エステル、ブタジエン、オ
レフィン等が挙げられるが、塩化ビニル樹脂にあらかじ
め含浸させるためには、常圧で液状であるアクリル酸エ
ステルが工業的に好ましく、特に溶解性パラメータが8.
0（Cal/cc）1/2以下のもの、例えば7.8（Cal/cc）1/2の
EHAや、7.4（Cal/cc）1/2のステアリルアクリレートが
好ましい〔尚、溶解性パラメータは、例えば“Polymer
Hand Book"（John Wiley＆Sons発行）に記載されてい
る〕。また、ジエン系の単量体を使用すると耐候性が悪
いので、この点からもアクリル酸エステルが好ましい。Examples of the monomer having a low solubility parameter used in the present invention include acrylic acid esters such as EHA, butadiene, and olefins, but in order to pre-impregnate a vinyl chloride resin, an acrylic liquid which is liquid under normal pressure is used. Acid esters are industrially preferable, and especially the solubility parameter is 8.
0 (Cal / cc) 1/2 or less, eg 7.8 (Cal / cc) 1/2
EHA and 7.4 (Cal / cc) 1/2 stearyl acrylate are preferred [Note that the solubility parameter is
Hand Book "(published by John Wiley & Sons). In addition, since a diene-based monomer has poor weather resistance, acrylic ester is preferable also from this point.
本発明に用いられるメタクリル酸エステルとしては、
MMA、エチルメタクリレート等が挙げられるが、塩化ビ
ニル樹脂と相溶性のよいMMAが望ましい。As the methacrylic acid ester used in the present invention,
Examples thereof include MMA and ethyl methacrylate, and MMA having good compatibility with vinyl chloride resin is desirable.
本発明に用いられるビニル芳香族単量体としては、S
t、α−メチルスチレン、クロルスチレン等が挙げられ
るが、EHAやMMAと共重合可能なStやα−メチルスチレン
が望ましい。As the vinyl aromatic monomer used in the present invention, S
Examples include t, α-methylstyrene, chlorostyrene, etc., and St and α-methylstyrene copolymerizable with EHA and MMA are preferable.
本発明に用いられる架橋性単量体としては、ポリエチ
レングリコールジアクリレート（エチレングリコールの
繰り返し数２〜23）、ポリエチレングリコールジメタク
リレート（エチレングリコールの繰り返し数２〜23）、
ジメタクリル酸ブチレングリコール、ジビニルベンゼ
ン、ジアリルフタレート、ジアリルマレエート等が挙げ
られるが、架橋間距離の長いポリエチレングリコールジ
アクリレート（以下、PEGDAと略）、ポリエチレングリ
コールジメタクリレート（以下、PEGDMと略）、ジメタ
クリル酸ブチレングリコールが加工性の点から望まし
い。Examples of the crosslinkable monomer used in the present invention include polyethylene glycol diacrylate (ethylene glycol repeating number 2 to 23), polyethylene glycol dimethacrylate (ethylene glycol repeating number 2 to 23),
Examples include butylene glycol dimethacrylate, divinylbenzene, diallyl phthalate, and diallyl maleate, but polyethylene glycol diacrylate (hereinafter abbreviated as PEGDM), which has a long distance between crosslinks, polyethylene glycol dimethacrylate (hereinafter abbreviated as PEGDM), Butylene glycol dimethacrylate is preferred from the standpoint of processability.
本発明に用いられる塩化ビニル樹脂としては、塩化ビ
ニル単独重合体の他、酢酸ビニルやエチレン、プロピレ
ン、その他オレフィン等を共重合した塩化ビニル系樹脂
も含まれる。The vinyl chloride resin used in the present invention includes vinyl chloride homopolymers as well as vinyl chloride resins obtained by copolymerizing vinyl acetate, ethylene, propylene, and other olefins.
本発明において、アクリル酸エステルの使用量は、全
単量体に対して10〜50重量％が好ましい。10重量％未満
では加工性が改善されず、50重量％を越えると耐熱強度
が悪くなる。特に20重量％以上で加工性が良く、40重量
％以下で耐熱強度が良い。In the present invention, the amount of acrylic acid ester used is preferably 10 to 50% by weight based on all monomers. If it is less than 10% by weight, the processability is not improved, and if it exceeds 50% by weight, the heat resistance becomes poor. Particularly, if it is 20% by weight or more, the workability is good, and if it is 40% by weight or less, the heat resistance is good.
ビニル芳香族単量体は、加工性、耐熱強度の点から40
重量％以上が望ましく、耐衝撃性の点から80重量％以下
が望ましい。特に加工性の点から45重量％以上が良く、
耐衝撃性の点から75重量％以下が良い。Vinyl aromatic monomer is 40 in terms of processability and heat resistance.
% By weight, and preferably 80% by weight or less from the viewpoint of impact resistance. Especially from the viewpoint of workability, 45% by weight or more is good,
From the point of impact resistance, 75% by weight or less is preferable.
メタクリル酸エステルの使用量は、全単量体に対して
５〜40重量％が望ましい。５重量％未満では耐衝撃性が
改善されず、40重量％を越えると加工性が悪くなる。特
に15重量％以上で耐衝撃性が良く、30重量％以下で加工
性が良い。The amount of the methacrylic acid ester used is preferably 5 to 40% by weight based on all the monomers. If it is less than 5% by weight, the impact resistance will not be improved, and if it exceeds 40% by weight, the workability will be poor. Particularly, the impact resistance is good when the content is 15% by weight or more, and the workability is good when the content is 30% by weight or less.
架橋性単量体の使用量は耐衝撃性、耐熱強度の点から
0.01重量％以上が望ましく、加工性の点から10.0重量％
以下が望ましい。特に耐熱強度の点から0.1重量％以上
が良く、加工性の点から20重量％以下が良い。The amount of crosslinkable monomer used is impact resistance and heat resistance.
0.01 wt% or more is desirable, 10.0 wt% from the viewpoint of workability
The following is desirable. Particularly, 0.1 wt% or more is preferable from the viewpoint of heat resistance, and 20 wt% or less is preferable from the viewpoint of workability.
上記単量体混合物の全使用量は塩化ビニル樹脂100重
量部に対して、加工性、耐衝撃性の点から３重量部以上
が望ましく、耐熱強度、経済性の点から20重量部以下が
望ましい。特に加工性の点からは５重量部以上が良く、
耐熱強度の点からは10重量部以下が良い。The total amount of the above monomer mixture is preferably 3 parts by weight or more based on 100 parts by weight of the vinyl chloride resin in view of workability and impact resistance, and is preferably 20 parts by weight or less in view of heat resistance and economy. . Especially from the viewpoint of workability, 5 parts by weight or more is preferable,
From the viewpoint of heat resistance, 10 parts by weight or less is preferable.
本発明の改質塩化ビニル樹脂を得るためには、前記単
量体混合物を塩化ビニル樹脂にあらかじめ含浸せしめて
から共重合させる事が必須となるが、乾燥した塩化ビニ
ル樹脂に単量体混合物を15分以上、工業的には30分〜２
時間含浸せしめてから熱重合、放射線重合等により共重
合させる方法や、塩化ビニル樹脂の水性懸濁液中で単量
体混合物を塩化ビニル樹脂に含浸させてからそのまま懸
濁重合する方法等がある。懸濁重合の場合は、単量体混
合物中に重合開始剤を添加してから塩化ビニル樹脂に含
浸せしめる事により、均一な重合が可能となる。In order to obtain the modified vinyl chloride resin of the present invention, it is essential to impregnate the vinyl chloride resin with the monomer mixture in advance and then to copolymerize the monomer mixture. 15 minutes or more, 30 minutes to 2 industrially
There is a method of impregnating for a time and then copolymerizing by heat polymerization, radiation polymerization, etc., or a method of impregnating a vinyl chloride resin with a monomer mixture in an aqueous suspension of vinyl chloride resin and then performing suspension polymerization as it is. . In the case of suspension polymerization, uniform polymerization can be achieved by adding a polymerization initiator to the monomer mixture and then impregnating the vinyl chloride resin.
本発明に用いられる重合開始剤としてはベンゾイルパ
ーオキサイド、アセチルパーオキサイド、ラウロイルパ
ーオキサイド、ジイソプロピルパーオキシジカーボネー
ト、ジオクチルパーオキシジカーボネート等の過酸化物
開始剤や、2,2′−アゾビスイソブチロニトリル、2,2′
−アゾビス−2,4−ジメチルバレロニトリル等のアゾ系
開始剤及びレドックス系開始剤等が挙げられる。上記単
量体混合物を共重合させる際に、40〜70℃で３〜15時間
重合させた後、80〜110℃で１〜５時間熱処理して残存
単量体を重合させることが好ましく、従って、低温活性
の開始剤と高温活性の開始剤を組み合わせ、重合中は分
解温度の低い開始剤を用い、重合末期の熱処理において
は、それよりも分解温度の高い開始剤を用いるのが望ま
しい。Examples of the polymerization initiator used in the present invention include peroxide initiators such as benzoyl peroxide, acetyl peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, dioctyl peroxydicarbonate, and 2,2′-azobisisodiene. Butyronitrile, 2,2 '
Examples include azo-based initiators such as azobis-2,4-dimethylvaleronitrile and redox-based initiators. In copolymerizing the above monomer mixture, it is preferable to polymerize at 40 to 70 ° C for 3 to 15 hours and then heat at 80 to 110 ° C for 1 to 5 hours to polymerize the residual monomer. It is desirable that a low temperature active initiator and a high temperature active initiator are combined, an initiator having a low decomposition temperature is used during the polymerization, and an initiator having a higher decomposition temperature is used in the heat treatment at the final stage of the polymerization.
その他、単量体混合物とともに、連鎖移動剤、安定
剤、滑剤、酸化防止剤等塩化ビニル樹脂の製造に用いら
れる添加剤を添加しても良い。In addition to the monomer mixture, chain transfer agents, stabilizers, lubricants, antioxidants, and other additives used in the production of vinyl chloride resins may be added.
「実施例」 以下、実施例を挙げて本発明を更に詳細に説明する
が、本発明はこれらに限定されるものではない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
実施例１〜16、比較例１〜９ 懸濁重合法で得られた重合度680の塩化ビニル樹脂200
0gに、後述する単量体混合物及び重合開始剤としてジオ
クチルパーオキシジカーボネートを全単量体100重量部
に対して0.2重量部、1,1−ビス（ターシャリーブチルパ
ーオキシ）3,3,5−トリメチルシクロヘキサンを0.2重量
部添加したものを30分含浸させた後、攪拌機つきの10
オートクレーブにイオン交換水5000gとともに投入し、
窒素置換後60℃で５時間重合させ、更に90℃で２時間熱
処理し残存単量体を重合させた。Examples 1 to 16 and Comparative Examples 1 to 9 Vinyl chloride resin 200 having a polymerization degree of 680 obtained by the suspension polymerization method 200
In 0 g, 0.2 parts by weight of dioctyl peroxydicarbonate as a monomer mixture and a polymerization initiator described below based on 100 parts by weight of all monomers, 1,1-bis (tertiary butyl peroxy) 3,3, After impregnating for 30 minutes with 0.2 parts by weight of 5-trimethylcyclohexane added, 10 with a stirrer
Put 5000g of ion-exchanged water into the autoclave,
After substitution with nitrogen, polymerization was carried out at 60 ° C. for 5 hours, and further heat treatment was carried out at 90 ° C. for 2 hours to polymerize the residual monomer.
得られた改質塩化ビニル樹脂100重量部にステアリン
酸0.5重量部、三塩基性硫酸鉛2.0重量部を混合し、150
℃で10分間ロール加工後160℃で10分間プレスして作成
したシートから試験片をとり、物性試験を行った。To 100 parts by weight of the obtained modified vinyl chloride resin, 0.5 parts by weight of stearic acid and 2.0 parts by weight of tribasic lead sulfate were mixed,
A test piece was taken from a sheet prepared by rolling at 10 ° C. for 10 minutes and then pressing at 160 ° C. for 10 minutes to perform a physical property test.
加工性は高化式Ｂ法フロー（180℃で1mmφ×1mmLのダ
イスを用い、150kg/cm2荷重）で評価した。耐熱強度は
ビカットテスト（5kg荷重）で評価した。耐衝撃性はノ
ッチ付きアイゾットテストにより評価した。The workability was evaluated by the Koka type B method flow (using a die of 1 mmφ × 1 mmL at 180 ° C. and a load of 150 kg / cm 2 ). The heat resistance was evaluated by the Vicat test (5 kg load). Impact resistance was evaluated by a notched Izod test.
第１表は、単量体組成とＢ法フロー、ビカット温度、
アイゾット衝撃値の関係を示す。単量体量は塩化ビニル
樹脂100重量部に対して10重量部であり、PEGDMを0.2重
量％（対単量体）添加してある。Table 1 shows the monomer composition, the method B flow, the Vicat temperature,
The relation of Izod impact value is shown. The amount of the monomer was 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, and 0.2% by weight (to the monomer) of PEGDM was added.
第２表は、単量体量とＢ法フロー、ビカット温度、ア
イゾット衝撃値の関係を示す。単量体組成はEHA20重量
％、MMA29.8重量％、St50重量％、PEGDM0.2重量％であ
る。Table 2 shows the relationship between the amount of monomer and the B method flow, the Vicat temperature, and the Izod impact value. The monomer composition is EHA 20% by weight, MMA 29.8% by weight, St 50% by weight, PEGDM 0.2% by weight.
第３表は、架橋性単量体としてPEGDMを使用した場合
の組成とＢ法フロー、ビカット温度、アイゾット衝撃値
の関係を示す。単量体混合物は10重量部である。Table 3 shows the relationship between the composition when PEGDM is used as the crosslinkable monomer, the method B flow, the Vicat temperature, and the Izod impact value. The monomer mixture is 10 parts by weight.
第１表より、EHA10重量％未満ではフローが悪く、50
重量％を越えるとアイゾット衝撃値が悪くなる事が判
る。またMMAが５重量％未満ではやはりアイゾット衝撃
値が悪く、40重量％を越えるとＢ法フローが悪くなる。
更に、Stは40重量％未満ではビカット温度が低下し、80
重量％を越えるとアイゾット衝撃値が悪くなる事が判
る。 From Table 1, if the EHA is less than 10% by weight, the flow is poor and 50
It can be seen that the Izod impact value becomes worse when the weight% is exceeded. If the MMA is less than 5% by weight, the Izod impact value is still poor, and if it exceeds 40% by weight, the B method flow is deteriorated.
Furthermore, when St is less than 40% by weight, the Vicat temperature decreases,
It can be seen that the Izod impact value becomes worse when the weight% is exceeded.
また、第２表より、単量体が３重量部未満ではＢ法フ
ロー、アイゾット衝撃値が悪く、20重量部を越えると、
ビカット温度が低下する事が判る。尚、20重量部より多
くなると、重合の際に塩化ビニル樹脂から独立した共重
合体が生成するため効率が悪くなる。Further, from Table 2, when the amount of the monomer is less than 3 parts by weight, the B method flow and Izod impact value are poor, and when it exceeds 20 parts by weight,
It can be seen that the Vicat temperature decreases. If the amount is more than 20 parts by weight, the efficiency is deteriorated because an independent copolymer is produced from the vinyl chloride resin during the polymerization.
更に第３表からは、架橋性単量体が0.01重量％未満で
はビカット温度、アイゾット衝撃値が悪く、10重量％を
越えるとＢ法フローが悪くなる事が判る。Further, it can be seen from Table 3 that when the crosslinkable monomer is less than 0.01% by weight, the Vicat temperature and Izod impact value are poor, and when it exceeds 10% by weight, the B method flow is deteriorated.
「作用・効果」 本発明により、耐熱強度や耐衝撃性を低下させること
なく加工性が改善される理由は必ずしも明らかでない
が、MMAや、St、α−メチルスチレン等の溶解性パラメ
ータの大きな単量体と溶解性パラメータの小さいEHA等
を共重合させる事により、共重合体の分子内反発力が発
生して低温では塩化ビニル樹脂との相溶性が良く、成形
時の高温下では共重合体の熱膨張係数が大きくなるた
め、塩化ビニル樹脂の流動性が良くなり加工性が改善さ
れるものと考えられる。EHAとSt及び／又はα−メチル
スチレンの単量体混合物にMMAを加える事によっても塩
化ビニル樹脂との相溶性は改良されるが、架橋性単量体
を加える事によって、相溶性は更に良くなり、耐衝撃
性、耐熱強度が改善される。[Operation / Effect] Although the reason why the present invention improves workability without lowering heat resistance and impact resistance, it is not always clear, but MMA, St, α-methylstyrene, etc. having a large solubility parameter are used. By copolymerizing the monomer and EHA, which has a small solubility parameter, the intramolecular repulsion of the copolymer occurs and the compatibility with vinyl chloride resin is good at low temperature, and the copolymer at high temperature during molding. It is considered that since the coefficient of thermal expansion of the vinyl chloride resin is increased, the flowability of the vinyl chloride resin is improved and the workability is improved. The compatibility with vinyl chloride resin is also improved by adding MMA to the monomer mixture of EHA and St and / or α-methylstyrene, but the compatibility is further improved by adding a crosslinkable monomer. The impact resistance and heat resistance are improved.
叙上の通り、本発明により得られる改質塩化ビニル樹
脂は、耐熱強度、耐衝撃性及び加工性のバランスが良好
で、また、単量体混合物を特別なものではなく通常の塩
化ビニル樹脂に常圧で含浸後重合すれば良いので、工業
的に有利に製造できる等の特徴を有する。As described above, the modified vinyl chloride resin obtained by the present invention has a good balance of heat strength, impact resistance and processability, and the monomer mixture is not a special one but a normal vinyl chloride resin. Since it suffices to carry out polymerization after impregnation at normal pressure, it has a feature that it can be produced industrially advantageously.
Claims (5)
のアクリル酸エステル単量体10〜50重量％と、ビニル芳
香族単量体40〜80重量％、メタクリル酸エステル単量体
５〜40重量％及び架橋性単量体0.01〜10.0重量％とから
なる単量体混合物を塩化ビニル樹脂に含浸させ、次いで
共重合させることを特徴とする加工性の優れた改質塩化
ビニル樹脂の製造方法。1. A solubility parameter of 8.0 (Cal / cc) 1/2 or less 10 to 50% by weight of an acrylic acid ester monomer, 40 to 80% by weight of a vinyl aromatic monomer, and a methacrylic acid ester unit amount. Modified vinyl chloride having excellent processability, characterized in that a vinyl chloride resin is impregnated with a monomer mixture consisting of 5 to 40% by weight of a polymer and 0.01 to 10.0% by weight of a crosslinkable monomer, and then copolymerized. Resin manufacturing method.
15分間以上含浸させる特許請求の範囲第１項記載の製造
方法。2. The monomer mixture is added to vinyl chloride resin under normal pressure.
The manufacturing method according to claim 1, wherein the impregnation is performed for 15 minutes or more.
合させた後、80〜110℃で１〜５時間熱処理して共重合
を完結させる特許請求の範囲第１項又は第２項記載の製
造方法。3. The method according to claim 1, wherein the monomer mixture is copolymerized at 40 to 70 ° C. for 3 to 15 hours and then heat-treated at 80 to 110 ° C. for 1 to 5 hours to complete the copolymerization. The manufacturing method according to item 2.
混合物３〜20重量部を含浸させ、共重合させる特許請求
の範囲第１項、第２項又は第３項記載の製造方法。4. The method according to claim 1, 2, or 3, wherein 100 parts by weight of vinyl chloride resin is impregnated with 3 to 20 parts by weight of a monomer mixture and copolymerized.
併用する特許請求の範囲第１項、第２項、第３項又は第
４項記載の製造方法。5. The method according to claim 1, 2, 3 or 4, wherein a low temperature active initiator and a high temperature active initiator are used in combination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11498487A JP2566773B2 (en) | 1987-05-11 | 1987-05-11 | Process for producing modified vinyl chloride resin with excellent processability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11498487A JP2566773B2 (en) | 1987-05-11 | 1987-05-11 | Process for producing modified vinyl chloride resin with excellent processability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63278919A JPS63278919A (en) | 1988-11-16 |
| JP2566773B2 true JP2566773B2 (en) | 1996-12-25 |
Family
ID=14651471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11498487A Expired - Fee Related JP2566773B2 (en) | 1987-05-11 | 1987-05-11 | Process for producing modified vinyl chloride resin with excellent processability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2566773B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2630958B2 (en) * | 1987-10-07 | 1997-07-16 | 鐘淵化学工業株式会社 | Γ-ray resistant vinyl chloride resin material |
| JP2630957B2 (en) * | 1987-10-07 | 1997-07-16 | 鐘淵化学工業株式会社 | Γ-ray resistant vinyl chloride resin material |
| JPH0481411A (en) * | 1990-07-06 | 1992-03-16 | Toli Corp Ltd | Crosslinkable polyvinyl chloride composition and crosslinked polyvinyl chloride sheet |
| KR100648130B1 (en) * | 1999-12-30 | 2006-11-24 | 주식회사 케이씨씨 | Acrylic resin composition for thermocuring |
| CN111116829A (en) * | 2020-01-07 | 2020-05-08 | 河南理工大学 | Polyvinyl chloride graft copolymer and preparation method thereof |
-
1987
- 1987-05-11 JP JP11498487A patent/JP2566773B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63278919A (en) | 1988-11-16 |
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