JPH062789B2 - Method for producing vinyl chloride copolymer - Google Patents
Method for producing vinyl chloride copolymerInfo
- Publication number
- JPH062789B2 JPH062789B2 JP12068385A JP12068385A JPH062789B2 JP H062789 B2 JPH062789 B2 JP H062789B2 JP 12068385 A JP12068385 A JP 12068385A JP 12068385 A JP12068385 A JP 12068385A JP H062789 B2 JPH062789 B2 JP H062789B2
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- monomer
- polymerization
- vinyl chloride
- weight
- vinyl
- 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.)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はイソシアネート等を硬化して被覆材としての改
良された塗膜を形成し得る塩化ビニル共重合体の製造法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a process for producing a vinyl chloride copolymer capable of curing an isocyanate or the like to form an improved coating film as a coating material.
塗料工業においては、架橋可能な塩化ビニル共重合体を
供給することは重要である。架橋可能な共重合体として
は遊離ヒドロキシル基を含有する共重合体が種々の方法
で架橋させることが可能なことで特に有利である。従来
はこの種の共重合体は大抵は塩化ビニル／酢酸ビニル共
重合体を部分的に鹸化して、重合体中に遊離ヒドロシキ
ル基を生じさせることにより作られた。しかしながらこ
の種の共重合体は鹸化工程による着色劣化やコストの上
昇という欠点を有する。In the paint industry, it is important to provide crosslinkable vinyl chloride copolymers. As the crosslinkable copolymer, a copolymer containing a free hydroxyl group is particularly advantageous because it can be crosslinked by various methods. In the past, copolymers of this type were mostly made by partially saponifying vinyl chloride / vinyl acetate copolymers, resulting in free hydroxyl groups in the polymer. However, this type of copolymer has drawbacks such as color deterioration and cost increase due to the saponification step.
ヒドロキシル基を含有する塩化ビニル共重合体を製造す
るための他の公知の方法は塩化ビニルをアクリル酸ヒド
ロキシアルキルエステルと共重合することである。しか
しながら、該共重合体はしばしば大部分が重合時に網状
化し、塗料原料として使用できないという欠点を有す
る。この欠点を改良する研究については、いくつかの文
献があり、例えば次のものを挙げることができる；日本
特許公告昭５１−1,７５７，同公告昭５１−1０，873お
よび、同公告昭５２−2４，558。Another known method for producing vinyl chloride copolymers containing hydroxyl groups is to copolymerize vinyl chloride with hydroxyalkyl acrylate. However, the copolymer often has a disadvantage that it is mostly reticulated during polymerization and cannot be used as a coating material. Regarding the research for improving this drawback, there are several documents, for example, the following can be mentioned: Japanese Patent Publication Nos. 51-1,757, 51-10,873 and 52. -24,558.
特許公告昭５１−1,７５７は塩化ビニルと２−ヒドロキ
シプロピルアクリレートとを水中乳化状態で連続的に重
合を行なう方法を開示している。しかし、２−ヒドロキ
シプロピルアクリレート以外のアクリル酸ヒドロキシア
ルキルエステル単量体、例えば２−ヒドロキシエチルア
クリレートを用いると、該共重合体は普通の溶剤に不溶
性であり、強い架橋が生じることを示唆している。Japanese Patent Publication No. 51-1,757 discloses a method of continuously polymerizing vinyl chloride and 2-hydroxypropyl acrylate in an emulsion state in water. However, the use of acrylic acid hydroxyalkyl ester monomers other than 2-hydroxypropyl acrylate, such as 2-hydroxyethyl acrylate, suggests that the copolymer is insoluble in common solvents, resulting in strong crosslinking. There is.
特許公告昭５１−１0,８７３および同昭５２−２4,５５
８は塩化ビニル，酢酸ビニルとアクリル酸ヒドロキシア
ルキルエステルとを溶液中連続的に重合を行なう方法を
開示している。しかしながら、塩化ビニルに比べて重合
性の大きく異なるアクリル酸ヒドロキシアクリルエステ
ルを均質的に共重合するには、単量体を単に連続的に供
給するだけでは不均質的重合を引き起し、しばしば濁り
を生じる。Japanese Patent Publication No. 51-10,873 and No. 52-24,55
No. 8 discloses a method of continuously polymerizing vinyl chloride, vinyl acetate and hydroxyalkyl acrylate in a solution. However, in order to homogenously copolymerize acrylic acid hydroxyacryl ester, which has a greatly different polymerizability compared to vinyl chloride, a simple continuous feeding of monomers causes heterogeneous polymerization and often results in turbidity. Cause
２−ヒドロキシエチルアクリレートを用いた塩化ビニル
共重合体は反応性の高い第一級のヒドロキシル基を持つ
ため、イソシアネート等との強い結合をもたらし、強靱
な塗膜を形成する。しかし、特許公告昭５１−1,７５７
にも述べられている様に、２−ヒドロキシエチルアクリ
レートは共重合中に不溶性物を生じ易く塗料原料として
良好な樹脂を得ることは難かしい。Since the vinyl chloride copolymer using 2-hydroxyethyl acrylate has a highly reactive primary hydroxyl group, it causes a strong bond with isocyanate or the like to form a tough coating film. However, the patent publication Sho 51-1,757
As described above, 2-hydroxyethyl acrylate is liable to form an insoluble substance during copolymerization, and it is difficult to obtain a good resin as a coating material.
本発明の目的は従来の技術では重合の段階で網状化し、
塗料原料として使用できないものしか得られない、２−
ヒドロキシエチルアクリレートの塩化ビニルとの共重合
に対しても同様な優れた溶解性をもち、イソシアネート
等と硬化して改良された被覆塗膜を形成し得る樹脂を製
造する方法を提供するものである。The object of the present invention is to reticulate at the stage of polymerization in the prior art,
Only the materials that cannot be used as paint materials can be obtained, 2-
Provided is a method for producing a resin having the same excellent solubility for copolymerization of hydroxyethyl acrylate with vinyl chloride, which can be cured with isocyanate or the like to form an improved coating film. .
即ち、本発明は単量体の全量あるいは一部を連続的に５
cm/sec以上の流速で供給し、且つ、重合系内液中に直接
挿入をすることを特徴とする製造法にあり、塩化ビニル
単量体５０〜８０重量％、α，βエチレン式不飽和カル
ボン酸のグリコールモノエステル単量体２〜３０重量％
および１〜６個の炭素原子を含む飽和カルボン酸のビニ
ルエステル単量体５〜４０重量％とからなる平均重合度
（JIS Ｋ ６７２１による測定）が１００〜５００の
均質なランダム共重合体を製造する方法に関する。That is, in the present invention, the whole amount or a part of the monomer is continuously added to
It is a production method characterized by supplying it at a flow rate of cm / sec or more and inserting it directly into the liquid inside the polymerization system. Vinyl chloride monomer 50 to 80% by weight, α, β ethylenic unsaturated 2-30% by weight of glycol monoester monomer of carboxylic acid
And a homogeneous random copolymer having an average degree of polymerization (measured by JIS K 6721) of 100 to 500 consisting of 5 to 40% by weight of a vinyl ester monomer of a saturated carboxylic acid containing 1 to 6 carbon atoms. On how to do.
以下にその詳細について説明する。The details will be described below.
本発明においては慣用のラジカル重合手法の懸濁、乳化
または溶液重合法を用いることができるが、望ましい方
法は溶液重合法である。溶液重合は、製造に用いられる
単量体および得られる共重合体に対する溶剤中で行われ
る。本発明で使用し得るこのような溶剤としては酢酸エ
チル，酢酸ブチル等のエステル類；メチルエチルケト
ン，メチルイソブチルケトン等のケトン類およびトルエ
ン，キシレン等の芳香族炭化水素類などの単独あるいは
混合物をあげることができる。In the present invention, a conventional radical polymerization technique such as suspension, emulsion or solution polymerization can be used, but the preferred method is solution polymerization. Solution polymerization is carried out in a solvent for the monomers used for production and the resulting copolymer. Examples of the solvent usable in the present invention include esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic hydrocarbons such as toluene and xylene, which may be used alone or in a mixture. You can
本発明においては単量体の少なくとも５０％以上が連続
的に重合系内に供給される。連続的に供給する単量体は
重合中の重合系内の単量体組成分布を一定に維持できる
組成であり、各単量体はその各々の重合速度に応じて供
給される。このことは共重合体の組成分布を均一にする
に必要なことであるが、さらに重要なことは重合系内へ
の単量体の供給方法である。すなわち重合系内液中に導
びかれた管を通して５cm/sec以上の流速で単量体組成物
を供給して行くことである。これにより単量体の重合系
内への素早い拡散を可能とし、常に重合系内の単量体組
成分布を均一にして重合を行なわしめることを可能にす
る。In the present invention, at least 50% or more of the monomers are continuously fed into the polymerization system. The monomer continuously supplied has a composition capable of maintaining a constant monomer composition distribution in the polymerization system during polymerization, and each monomer is supplied according to its respective polymerization rate. This is necessary to make the composition distribution of the copolymer uniform, but more important is the method of supplying the monomer into the polymerization system. That is, the monomer composition is supplied at a flow rate of 5 cm / sec or more through a tube guided into the liquid in the polymerization system. This enables quick diffusion of the monomer into the polymerization system, and makes it possible to always carry out the polymerization by making the monomer composition distribution in the polymerization system uniform.
特に、重合系内の溶液粘度が高くなると、攪拌の回転数
や羽の形状では捕えないほどの混合不良となり、液面上
からの滴下や、流速が５cm/sec未満の供給方法では濃度
異相が現われ、不均質重合体を生成する。流速は単量体
を供給する導入管の径によって定まれるが、前にも述べ
てあるように単量体の連続的供給速度（流量）は各々の
単量体の重合速度から決められるので重合条件により導
入管径は変動する。変動因子を考慮して例えば１の重
合釜をもって、当発明の組成の単量体を共重合する場合
に５cm/sec以上の流速を得るには管径を0.５mm以下にす
ればよい。本発明の方法は従来の技術では重合中に網状
化して好ましい塩化ビニル共重合体が得られない２−ヒ
ドロキシエチルアクリレートに対し特に有効であり、得
られた塩化ビニル共重合体は均質的ランダム性の高いも
のとなり、安価な塗料溶剤であるトルエンやキシレンな
どの芳香族炭化水素類、あるいはエタノールやメタノー
ルなどの脂肪族アルコール類による溶解性が良好であ
る。In particular, if the solution viscosity in the polymerization system becomes high, the mixing speed will not be caught by the number of revolutions of stirring and the shape of the blade, and if the solution is dropped on the liquid surface or the flow rate is less than 5 cm / sec, the concentration difference phase Appears and produces a heterogeneous polymer. The flow rate is determined by the diameter of the introducing pipe that supplies the monomer, but as described above, the continuous supply rate (flow rate) of the monomer is determined from the polymerization rate of each monomer. The diameter of the introducing pipe varies depending on the polymerization conditions. In consideration of the variable factors, for example, with a polymerization kettle of 1, in order to obtain a flow rate of 5 cm / sec or more when the monomer having the composition of the present invention is copolymerized, the tube diameter may be set to 0.5 mm or less. The process of the present invention is particularly effective for 2-hydroxyethyl acrylate, which in the prior art is not reticulated during polymerization to give the preferred vinyl chloride copolymers, and the resulting vinyl chloride copolymers are homogeneous and random. The solubility is good in an inexpensive coating solvent such as an aromatic hydrocarbon such as toluene or xylene, or an aliphatic alcohol such as ethanol or methanol.
本発明の重合は単量体、溶剤および重合開始剤を重合容
器に仕込み所定の温度で開始する。使用する温度，単量
体対溶剤比および溶剤の種類の組合せによって樹脂の分
子量が制御される。重合開始剤はラジカルを熱的に発生
する油溶性化合物、例えばジベンゾイルペルオキシド，
ジラウロイルペルオシキド，ジアセチルペルオキシド，
アゾビス（イソブチロニトリル），イソプロピルペルオ
キシジカーボネート，２−エチルヘキシルペルオキシジ
カーボネート等のいづれでも用いることができる。重合
開始剤の添加は初期に一括して行なうこともできるが、
好ましくは単量体と同様、連続的に供給して重合速度を
制御する。The polymerization of the present invention is started at a predetermined temperature by charging a monomer, a solvent and a polymerization initiator into a polymerization vessel. The combination of temperature, monomer-to-solvent ratio and solvent type used controls the molecular weight of the resin. The polymerization initiator is an oil-soluble compound that thermally generates radicals, such as dibenzoyl peroxide,
Dilauroyl peroxydide, diacetyl peroxide,
Any of azobis (isobutyronitrile), isopropyl peroxydicarbonate, 2-ethylhexyl peroxydicarbonate and the like can be used. The polymerization initiator can be added all at once at the beginning,
Preferably, like the monomer, it is continuously fed to control the polymerization rate.
塩化ビニル単量体は共重合体の重量を基にして５０〜８
０重量％、好ましくは６０〜７０重量％用いる。塩化ビ
ニル単量体が５０重量％未満であると塩化ビニル系塗料
としての特性、すなわち耐薬品，耐水性，耐候性が劣
る。また、８０重量％を超えると樹脂溶液の粘度が増大
し芳香族炭化水素類などの安価な溶剤に対する溶解性も
劣る。The vinyl chloride monomer is 50 to 8 based on the weight of the copolymer.
0% by weight, preferably 60 to 70% by weight is used. If the vinyl chloride monomer content is less than 50% by weight, the properties as a vinyl chloride-based paint, that is, chemical resistance, water resistance and weather resistance are poor. Further, if it exceeds 80% by weight, the viscosity of the resin solution increases and the solubility in an inexpensive solvent such as aromatic hydrocarbons is deteriorated.
本発明において用いられるα−βエチレン式不飽和カル
ボン酸のグリコールモノエステル単量体としてはアクリ
ル酸，メタクリル酸，マレイン酸，フマル酸，イタコン
酸等の不飽和カルボン酸とエチレングリコール，プロピ
レングリコール，ブタンジオール，ペンタンジオール，
ペンタンジオール等のグリコールとのモノエステルがあ
げられる。本発明における特に重要な単量体はアクリル
酸またはメタクリル酸のエチレングリコールまたはプロ
ピレングリコールモノエステルである。これらの単量体
は単独でまたは２種以上併せて、共重合体の重量を基に
して２〜３０重量％、好ましくは５〜２０重量％用いら
れる。２重量％未満ではイソシアネート等との良好な硬
化被膜を得るには不十分であり、エタノール等の脂肪族
アルコールによる希釈性に劣る。３０重量％を超えると
濁りの無い透明樹脂溶液を得るのは困難であり、またこ
の単量体の増加は価格上昇をもたらす点でも好ましくな
い。Examples of the glycol monoester monomer of α-β ethylenically unsaturated carboxylic acid used in the present invention include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, and ethylene glycol, propylene glycol, Butanediol, pentanediol,
Examples include monoesters with glycols such as pentanediol. A particularly important monomer in the present invention is ethylene glycol or propylene glycol monoester of acrylic acid or methacrylic acid. These monomers are used alone or in combination of two or more, and are used in an amount of 2 to 30% by weight, preferably 5 to 20% by weight based on the weight of the copolymer. If it is less than 2% by weight, it is insufficient to obtain a good cured coating with isocyanate or the like, and the dilutability with an aliphatic alcohol such as ethanol is poor. If it exceeds 30% by weight, it is difficult to obtain a transparent resin solution free from turbidity, and an increase in this monomer is not preferable because it also causes an increase in price.
本発明において用いられる１〜６個の炭素原子を含む飽
和カルボン酸のビニルエステル単量体としては、酢酸ビ
ニル，プロピオン酸ビニル，酪酸ビニル，バーサティッ
ク酸ビニル等があげられる。これらの単量体は単独で、
また２種以上併せて、共重合体の重量を基にして５〜４
０重量％、好ましくは２０〜３５重量％用いる。５重量
％未満でであると、芳香族炭化水素系の溶剤に対する溶
解性が劣る。また４０重量％を超えると塗膜の強度ある
いは耐水性，耐溶剤性が低下する。Examples of the vinyl ester monomer of saturated carboxylic acid containing 1 to 6 carbon atoms used in the present invention include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl versatate and the like. These monomers alone,
In addition, two or more types may be combined and, based on the weight of the copolymer, 5 to 4
0% by weight, preferably 20 to 35% by weight is used. If it is less than 5% by weight, the solubility in an aromatic hydrocarbon solvent is poor. If it exceeds 40% by weight, the strength, water resistance and solvent resistance of the coating film are deteriorated.
得られる塩化ビニル重合樹脂溶液はそのままあるいはイ
ソシアネート化合物，尿素−ホルムアルデヒド樹脂，メ
ラミン−ホルムアルデヒド樹脂，エポキシ樹脂等と共反
応させて硬化塗膜として使用される。The obtained vinyl chloride polymer resin solution is used as it is or as a cured coating film by co-reacting with an isocyanate compound, a urea-formaldehyde resin, a melamine-formaldehyde resin, an epoxy resin or the like.
以上の説明から明らかなように本発明によれば、 (1)従来技術では重合中に網状化し、塗料原料として使
用できない２−ヒドロキシエチルアクリレートの塩化ビ
ニル共重合に対しても優れた樹脂溶液をもたらす。As is apparent from the above description, according to the present invention, (1) a resin solution excellent in vinyl chloride copolymerization of 2-hydroxyethyl acrylate, which cannot be used as a coating material, is reticulated during polymerization in the prior art. Bring
(2)安価なトルエン，キシレン，エチルベンゼンなどの
芳香族炭化水素類や、エタノール，メタノールなどの脂
肪族アルコール類などを溶剤として用いられるため経済
的に有利である。(2) It is economically advantageous because inexpensive aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, and aliphatic alcohols such as ethanol and methanol are used as the solvent.
(3)共重合樹脂はヒドロキシル基を含有するため、尿素
−ホルムアルデヒド樹脂，メラミン−ホルムアルデヒド
樹脂，エポキシ樹脂あるいはイソシアネート含有樹脂と
共反応させて優秀な硬化塗膜を形成することができる。(3) Since the copolymer resin contains a hydroxyl group, it can be co-reacted with urea-formaldehyde resin, melamine-formaldehyde resin, epoxy resin or isocyanate-containing resin to form an excellent cured coating film.
(4)共重合樹脂はヒドロキシル基を含有するため、他の
ヒドロキシ含有樹脂との相溶性が優れている。(4) Since the copolymer resin contains a hydroxyl group, it has excellent compatibility with other hydroxy-containing resins.
〔実施例〕 次に実施例および比較例を挙げて本発明を具体的に説明
する。なお例文中「部」とあるのは「重合部」を意味す
る。EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, "part" in the example sentence means "overlapping part".
実施例１ １の重合容器に５０部の塩化ビニル，６０部のプロピ
オン酸ビニル，４部の２−ヒドロキシエチルアクリレー
トおよび１８０部の酢酸エチルを仕込み、そして温度を
６５℃に上昇させた。重合容器に２−エチレンヘキシル
ペルオキシジカーボネート触媒の５重量％酢酸エチル溶
液を１時間当り３部の速度で加えて重合を開始した。次
いで、重合容器に１３０部の塩化ビニル，３０部のプロ
ピオン酸ビニルと２６部の２−ヒドロキシエチルアクリ
レートとの混合物を径0.４mmの導入管を通じて連続的に
重合系内液中に供給した。そのときの流速は約８cm/sec
であり、供給に約６時間を費やした。単量体供給後も触
媒を加え続け重合を完結した。得られた樹脂は濁りの無
い透明溶液で、ゲル状物は見られなかった。樹脂の平均
重合度（JIS Ｋ ６７２１による測定）は２６０であ
った。Example 1 A polymerization vessel of 1 was charged with 50 parts of vinyl chloride, 60 parts of vinyl propionate, 4 parts of 2-hydroxyethyl acrylate and 180 parts of ethyl acetate, and the temperature was raised to 65 ° C. A 5 wt% ethyl acetate solution of 2-ethylenehexyl peroxydicarbonate catalyst was added to the polymerization vessel at a rate of 3 parts per hour to initiate polymerization. Then, a mixture of 130 parts of vinyl chloride, 30 parts of vinyl propionate and 26 parts of 2-hydroxyethyl acrylate was continuously fed into the polymerization vessel through a feed tube having a diameter of 0.4 mm. The flow velocity at that time is about 8 cm / sec
And spent about 6 hours on supply. After supplying the monomer, the catalyst was continuously added to complete the polymerization. The obtained resin was a transparent solution with no turbidity, and no gel-like substance was observed. The average degree of polymerization of the resin (measured by JIS K 6721) was 260.
実施例２ 実施例１のプロピオン酸ビニルの代りに酢酸ビニルを使
用して繰返した。濁りの無い透明溶液が得られ、平均重
合度は２４０であった。Example 2 Vinyl acetate was used in place of the vinyl propionate of Example 1 and repeated. A clear solution having no turbidity was obtained, and the average degree of polymerization was 240.
実施例３ 実施例１の重合容器に６０部の塩化ビニル，３０部のプ
ロピオン酸ビニル，６部の２−ヒドロキシエチルアクリ
レートおよび１８０部の酢酸エチルを仕込み、そして温
度を６５℃に上昇させた。重合容器にイソプロピルペル
オキシジカーボネート触媒の５重量％酢酸エチル溶液を
１時間当り３部の速度で加え重合を開始した。次いで、
重合容器に１５０部の塩化ビニル１５部のプロピオン酸
ビニルと３９部の２−ヒドロキシエチルアクリレートと
の混合物を実施例１の導入管を用いて連続的に重合系内
液中に供給した。そのときの流速は約７cm/secであり、
約７時間費して供給した。単量体添加終了後も触媒を加
え重合を完結した。平均重合度２５０の透明性良好な樹
脂溶液が得られた。Example 3 The polymerization vessel of Example 1 was charged with 60 parts vinyl chloride, 30 parts vinyl propionate, 6 parts 2-hydroxyethyl acrylate and 180 parts ethyl acetate, and the temperature was raised to 65 ° C. A 5 wt% ethyl acetate solution of isopropyl peroxydicarbonate catalyst was added to the polymerization vessel at a rate of 3 parts per hour to initiate polymerization. Then
A mixture of 150 parts of vinyl chloride, 15 parts of vinyl propionate, and 39 parts of 2-hydroxyethyl acrylate was continuously fed into the polymerization vessel using the introduction tube of Example 1 in a polymerization vessel. The flow velocity at that time is about 7 cm / sec,
It was supplied for about 7 hours. After the completion of the addition of the monomer, the catalyst was added to complete the polymerization. A resin solution having an average degree of polymerization of 250 and good transparency was obtained.
実施例４ 実施例１の２−ヒドロキシエチルアクリレートの代りに
２−ヒドロキシプロピルアクリレートを使用して繰返し
た。濁りの無い透明溶液が得られ、平均重合度は２５０
であった。Example 4 The procedure of Example 1 was repeated using 2-hydroxypropyl acrylate instead of 2-hydroxyethyl acrylate. A clear solution with no turbidity was obtained, and the average degree of polymerization was 250.
Met.
比較例１ 管径1.０mmの導入管を用い、約６時間連続的に単量体を
供給した以外は実施例１を繰返した。このときの流速は
約１cm/secであった。重合途中から単量体導入管が不溶
性の樹脂により閉塞し、重合溶液に濁りが認められた。Comparative Example 1 Example 1 was repeated except that an introduction tube having a tube diameter of 1.0 mm was used and the monomer was continuously supplied for about 6 hours. The flow velocity at this time was about 1 cm / sec. During the polymerization, the monomer introduction tube was blocked by the insoluble resin, and turbidity was observed in the polymerization solution.
比較例２ 実施例１において導入管の出口を重合系内液中ではな
く、液面上とし滴下するようにした以外は繰返した。液
の粘度上昇とともに後から供給される単量体が液面上部
に留まり混合不良の状態が見られた。重合溶液は濁りが
認められた。Comparative Example 2 The procedure of Example 1 was repeated except that the outlet of the introduction tube was placed not on the inside of the polymerization system liquid but on the liquid level and was dropped. As the viscosity of the liquid increased, the monomer supplied later remained on the upper part of the liquid surface, and a poor mixing condition was observed. Turbidity was observed in the polymerization solution.
実施例５ 〈イソシアネート硬化反応〉 実施例１および実施例４で得られた樹脂にイソシアネー
ト含有ウレタンプレポリマーのコロネートＨＬ（日本ポ
リウレタン NCO含量１３％）をOH/NCO比が１になるよ
うに配合した。Example 5 <Isocyanate Curing Reaction> The resins obtained in Examples 1 and 4 were compounded with an isocyanate-containing urethane prepolymer, Coronate HL (Japan polyurethane NCO content 13%) so that the OH / NCO ratio was 1. .
ポットライフ…溶液状態で試験管中で反転流動しなく
なる状態までに要する時間（２３℃） 塗膜強度…上記配合液を塗布し、フィルムを形成し
た。２３℃６０％ＲＨ恒温室に２週間放置後、引張試験
（島津製作所オートグラフＩＳ−５０００型、引張速度
１０mm/min）を行なった。Pot life: Time (23 ° C) required until the fluid does not reverse flow in a test tube in solution Coating strength: A film was formed by applying the above-mentioned compounded liquid. After standing in a thermostatic chamber at 23 ° C. and 60% RH for 2 weeks, a tensile test (Shimadzu Corporation Autograph IS-5000 type, tensile speed 10 mm / min) was performed.
塗膜の耐溶剤性，耐水性 耐溶剤性…２週間乾燥後のフィルムをメチルエチルケト
ン中に２４時間浸漬し、その後フィルムを６０℃，２４
時間真空乾燥を行い、次式より溶解率を求めた。 Solvent resistance and water resistance of coating film ... Solvent resistance ... After being dried for 2 weeks, the film is immersed in methyl ethyl ketone for 24 hours, and then the film is kept at 60 ° C. for 24 hours.
Vacuum drying was performed for an hour, and the dissolution rate was calculated from the following formula.
耐水性…２週間乾燥後のフィルムを蒸留水中に２週間浸
漬し次式により吸水率を求めた。 Water resistance: The film after drying for 2 weeks was immersed in distilled water for 2 weeks, and the water absorption rate was calculated by the following formula.
実施例６ 〈イソシアネート硬化塗膜物性〉 実施例１および実施例４の樹脂に酸化チタン（石原産
業；タイペーク Ｒ−８２０），安定剤（油化シエル；
エピコート８２８）およびシンナー（酢酸ブチル／キシ
レン＝１／１）を配合し、固形分４6.０重量％の塗料組
成物を得た。実施例５に用いたコロネートＨＬをOH/NCO
＝１／１で配合し、塗膜を形成した。２３℃，６０％Ｒ
Ｈ恒温室に１週間放置後、JIS Ｋ−５４００，Ｋ−５
５８２に従って各塗膜試験を行なった。 Example 6 <Physical Properties of Isocyanate-Cured Coating Film> Titanium oxide (Ishihara Sangyo; Taipaque R-820), a stabilizer (oil conversion shell;
Epicoat 828) and thinner (butyl acetate / xylene = 1/1) were blended to obtain a coating composition having a solid content of 46.0% by weight. Coronate HL used in Example 5 was OH / NCO
= 1/1 to form a coating film. 23 ° C, 60% R
After leaving for 1 week in a thermostatic chamber, JIS K-5400, K-5
Each coating test was conducted according to 582.
表中の比較樹脂は塩化ビニル，酢酸ビニルおよび無水マ
レイン酸を重量比、７０対３０対１で仕込み重合を行な
ったもので、平均重合度２７０であった。The comparative resin in the table was prepared by polymerizing vinyl chloride, vinyl acetate and maleic anhydride in a weight ratio of 70: 30: 1, and had an average degree of polymerization of 270.
Claims (1)
〜３０重量％のα，βエチレン式不飽和カルボン酸のグ
リコールモノエステル単量体および５〜４０重量％の１
〜６個の炭素原子を含む飽和カルボン酸のビニルエステ
ル単量体とからなる単量体の全量あるいは一部を連続的
に重合系内に供給して行う共重合法において、連続的に
供給する単量体を０．５mm以下の管径の導入管を通して
５cm/sec以上の流速で重合系内に直接挿入することを特
徴とする、平均重合度が１００〜５００である均質なラ
ンダム塩化ビニル共重合体の製造法。1. A vinyl chloride monomer of 50 to 80% by weight, 2
-30% by weight of α, β-ethylenically unsaturated carboxylic acid glycol monoester monomer and 5-40% by weight of 1
In a copolymerization method in which all or part of a monomer composed of a vinyl ester monomer of a saturated carboxylic acid containing 6 to 6 carbon atoms is continuously supplied into the polymerization system, the monomer is continuously supplied. A homogeneous random vinyl chloride copolymer having an average degree of polymerization of 100 to 500, characterized in that the monomer is directly inserted into the polymerization system at a flow rate of 5 cm / sec or more through an introduction tube having a tube diameter of 0.5 mm or less. Polymer production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12068385A JPH062789B2 (en) | 1985-06-05 | 1985-06-05 | Method for producing vinyl chloride copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12068385A JPH062789B2 (en) | 1985-06-05 | 1985-06-05 | Method for producing vinyl chloride copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61278512A JPS61278512A (en) | 1986-12-09 |
| JPH062789B2 true JPH062789B2 (en) | 1994-01-12 |
Family
ID=14792362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12068385A Expired - Lifetime JPH062789B2 (en) | 1985-06-05 | 1985-06-05 | Method for producing vinyl chloride copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH062789B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5627239B2 (en) * | 2006-12-06 | 2014-11-19 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Method for producing water-absorbing polymer particles by suspension polymerization |
-
1985
- 1985-06-05 JP JP12068385A patent/JPH062789B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61278512A (en) | 1986-12-09 |
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