JP2013177576A - Hydroxymethyl group-containing vinyl alcohol-based polymer - Google Patents
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Abstract
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本発明は、主鎖にビニリデン型の１，３−ジオール構造を有するヒドロキシメチル基含有ビニルアルコール系重合体に関する。 The present invention relates to a hydroxymethyl group-containing vinyl alcohol polymer having a vinylidene type 1,3-diol structure in the main chain.
ビニルアルコール系重合体は、数少ない結晶性の水溶性高分子である。その優れた水溶性、皮膜特性（強度、耐油性、造膜性、酸素ガスバリア性など）を利用して、ビニルアルコール系重合体は、乳化剤、懸濁剤、界面活性剤、繊維加工剤、各種バインダー、紙加工剤、接着剤、フィルムなどに広く用いられている。特殊な場合を除き、ビニルアルコール系重合体は使用に際して水溶液の状態を経るが、その際の取り扱い性に難点を有することがある。例えば、水溶液とした後、特に水温が低い冬期において時間とともに水溶液の粘度が上昇して流動性が低下し、極端な場合はゲル化により流動性を失うことがある。また、水溶液を調製する際の攪拌によって発泡し、生じた泡が消えにくい、すなわち泡切れが悪いこともある。 Vinyl alcohol polymers are a few crystalline water-soluble polymers. Utilizing its excellent water solubility and film properties (strength, oil resistance, film-forming property, oxygen gas barrier property, etc.), vinyl alcohol polymers are emulsifiers, suspending agents, surfactants, fiber processing agents, Widely used in binders, paper processing agents, adhesives, films, etc. Except for special cases, the vinyl alcohol polymer is in the form of an aqueous solution when used, but there are cases where the handling property at that time is difficult. For example, after preparing an aqueous solution, the viscosity of the aqueous solution increases with time, particularly in winter when the water temperature is low, and the fluidity decreases. In extreme cases, the fluidity may be lost due to gelation. Moreover, it foams by the stirring at the time of preparing aqueous solution, and the produced | generated bubble is hard to disappear, ie, a bubble breakage may be bad.
ビニルアルコール系重合体水溶液の粘度安定性を改善する方法として、ビニルアルコール系重合体に疎水基またはイオン性基を導入する方法が知られている。しかし、疎水基を導入する方法では、ビニルアルコール系重合体の水に対する溶解性が低下して、水溶液の調製に高温が必要となったり、調製した水溶液の曇点が低くなったりすることがある。イオン性基を導入する方法では、形成した皮膜の耐水性が低くなることがある。 As a method for improving the viscosity stability of an aqueous vinyl alcohol polymer solution, a method of introducing a hydrophobic group or an ionic group into the vinyl alcohol polymer is known. However, in the method of introducing a hydrophobic group, the solubility of the vinyl alcohol polymer in water is lowered, so that a high temperature is required for the preparation of the aqueous solution, and the cloud point of the prepared aqueous solution may be lowered. . In the method of introducing an ionic group, the water resistance of the formed film may be lowered.
特許文献１には、水溶液の泡立ちを抑えたヒドロキシアルキル基を側鎖に有するビニルアルコール系重合体が開示されている。しかしながら、低温における水溶液の粘度安定性についてはまだまだ満足のいくものではなく、更なる向上が求められている。特許文献２、３には、水溶液の粘度安定性を向上させた側鎖に１，２−グリコール結合を有するビニルアルコール系重合体が開示されている。しかしながら、該重合体は、吸湿性の影響により高湿度下では皮膜物性が低下する問題がある。 Patent Document 1 discloses a vinyl alcohol polymer having a hydroxyalkyl group in a side chain in which bubbling of an aqueous solution is suppressed. However, the viscosity stability of aqueous solutions at low temperatures is still not satisfactory, and further improvements are required. Patent Documents 2 and 3 disclose vinyl alcohol polymers having a 1,2-glycol bond in the side chain with improved viscosity stability of an aqueous solution. However, the polymer has a problem that physical properties of the film are lowered under high humidity due to the effect of hygroscopicity.
また、特許文献３に記載の重合体は、変性種として３，４−ジアセトキシ−１−ブテンなどの不飽和単量体を用いて製造するが、該変性種は共重合性比の観点から、変性に用いる不飽和単量体が選択的に重合せず、高重合率まで重合を追い込まない限り、重合後も変性に用いた不飽和単量体が残存するため、廃棄物が増加し、製造コストの面で課題を抱えていた。 Moreover, although the polymer of patent document 3 is manufactured using unsaturated monomers, such as 3, 4- diacetoxy-1-butene, as a modification | denaturation seed | species, this modification | denaturation seed | species is from a viewpoint of copolymerizability ratio, Unless the unsaturated monomer used for modification selectively polymerizes and the polymerization is not driven to a high degree of polymerization, the unsaturated monomer used for modification remains after polymerization, resulting in increased waste and production There was a problem in terms of cost.
本発明は、水に対する溶解性及び水溶液の粘度安定性に優れるとともに水溶液の発泡が少なく、かつ高湿度下での皮膜物性にも優れるビニルアルコール系重合体の提供を目的とする。 An object of the present invention is to provide a vinyl alcohol polymer that is excellent in solubility in water and viscosity stability of an aqueous solution, has little foaming of the aqueous solution, and is excellent in film physical properties under high humidity.
本発明者らが鋭意検討した結果、主鎖に１，３−ジオール構造を有するヒドロキシメチル基含有ビニルアルコール系重合体によって上記課題を解決できることを見出し、本発明を完成させた。 As a result of intensive studies by the present inventors, it has been found that the above problems can be solved by a hydroxymethyl group-containing vinyl alcohol polymer having a 1,3-diol structure in the main chain, and the present invention has been completed.
すなわち、本発明は、
［１］ビニルアルコール単位、及び下記式（１）で示される構造単位を含むヒドロキシメチル基含有ビニルアルコール系重合体；
That is, the present invention
[1] Hydroxymethyl group-containing vinyl alcohol polymer containing a vinyl alcohol unit and a structural unit represented by the following formula (1);
［２］前記式（１）で示される構造単位の含有率が０．１〜３０モル％である［１］に記載のヒドロキシメチル基含有ビニルアルコール系重合体；
［３］けん化度が８０〜９９．９モル％である［１］または［２］に記載のヒドロキシメチル基含有ビニルアルコール系重合体；
に関する。
[2] The hydroxymethyl group-containing vinyl alcohol polymer according to [1], wherein the content of the structural unit represented by the formula (1) is 0.1 to 30 mol%;
[3] The hydroxymethyl group-containing vinyl alcohol polymer according to [1] or [2], wherein the saponification degree is 80 to 99.9 mol%;
About.
本発明によれば、水への溶解性、水溶液の粘度安定性に優れ、水溶液の発泡が少なく、水溶液状態における取り扱い性に優れるビニルアルコール系重合体が提供される。また、当該ビニルアルコール系重合体は、高湿度下においても強靭な皮膜強度を維持し、皮膜物性にも優れる。 ADVANTAGE OF THE INVENTION According to this invention, the vinyl alcohol polymer which is excellent in the solubility in water, the viscosity stability of aqueous solution, there are few foaming of aqueous solution, and it is excellent in the handleability in aqueous solution state is provided. In addition, the vinyl alcohol polymer maintains tough film strength even under high humidity and is excellent in film physical properties.
本発明のヒドロキシメチル基含有ビニルアルコール系重合体は、下記式（１）に示される構造単位を有する。 The hydroxymethyl group-containing vinyl alcohol polymer of the present invention has a structural unit represented by the following formula (1).
本発明のヒドロキシメチル基含有ビニルアルコール系重合体は、上記式（１）に示される構造単位（つまり、重合体の主鎖に１，３−ジオール構造を有する構造）を有することにより、ビニルアルコール系重合体の結晶性を低下させ、溶解性や粘度安定性などの取り扱い性を向上させることができる。また、本発明のヒドロキシメチル基含有ビニルアルコール系重合体を皮膜に加工した際、当該皮膜は１，３−ジオール構造の高い水素結合力により、結晶性の低下に起因する皮膜強度の低下を軽減させることができ、高湿度下でも強靭性を維持することができる。 The hydroxymethyl group-containing vinyl alcohol polymer of the present invention has a structural unit represented by the above formula (1) (that is, a structure having a 1,3-diol structure in the main chain of the polymer). The crystallinity of the polymer can be lowered, and the handleability such as solubility and viscosity stability can be improved. In addition, when the hydroxymethyl group-containing vinyl alcohol polymer of the present invention is processed into a film, the film reduces the decrease in film strength due to the decrease in crystallinity due to the high hydrogen bonding force of the 1,3-diol structure. And toughness can be maintained even under high humidity.
本発明のヒドロキシメチル基含有ビニルアルコール系重合体における式（１）に示される構造単位の含有率は特に限定されないが、重合体中の全構造単位を１００モル％として、好ましくは０．１〜３０モル％であり、より好ましくは０．２〜２０モル％、さらに好ましくは０．３〜１０モル％である。含有率が０．１モル％未満であると、得られるビニルアルコール系重合体の水に対する溶解性、水溶液の粘度安定性、水溶液の発泡性の改善、高湿度下における皮膜強度が不十分となることがある。含有率が３０モル％を超えると、ビニルアルコール系重合体の結晶性が極度に低下し、高湿度下での皮膜の強靭性を維持できなくなる傾向がある。なお、本発明において重合体中の構造単位とは、重合体を構成する繰り返し単位のことをいう。 Although the content rate of the structural unit shown by Formula (1) in the hydroxymethyl group-containing vinyl alcohol polymer of the present invention is not particularly limited, the total structural unit in the polymer is 100 mol%, preferably 0.1 to 0.1%. It is 30 mol%, More preferably, it is 0.2-20 mol%, More preferably, it is 0.3-10 mol%. If the content is less than 0.1 mol%, the solubility of the resulting vinyl alcohol polymer in water, the viscosity stability of the aqueous solution, the improvement of the foaming property of the aqueous solution, and the film strength under high humidity will be insufficient. Sometimes. If the content exceeds 30 mol%, the crystallinity of the vinyl alcohol polymer is extremely lowered, and the toughness of the film under high humidity tends not to be maintained. In the present invention, the structural unit in the polymer refers to a repeating unit constituting the polymer.
本発明のヒドロキシメチル基含有ビニルアルコール系重合体のＪＩＳ Ｋ６７２６に準拠して測定した粘度平均重合度は特に限定されないが、好ましくは１００〜７，０００であり、より好ましくは２００〜５，０００であり、さらに好ましくは２００〜４，０００である。粘度平均重合度が１００未満になると、皮膜にした際に当該皮膜の皮膜強度が低下することがある。粘度平均重合度が７，０００を超えるヒドロキシメチル基含有ビニルアルコール系重合体は、工業的な製造が難しい。 The viscosity average degree of polymerization measured according to JIS K6726 of the hydroxymethyl group-containing vinyl alcohol polymer of the present invention is not particularly limited, but is preferably 100 to 7,000, more preferably 200 to 5,000. Yes, more preferably 200 to 4,000. When the viscosity average degree of polymerization is less than 100, the film strength of the film may be lowered when the film is formed. A hydroxymethyl group-containing vinyl alcohol polymer having a viscosity average degree of polymerization exceeding 7,000 is difficult to produce industrially.
本発明のヒドロキシメチル基含有ビニルアルコール系重合体のけん化度（すなわち、ヒドロキシメチル基含有ビニルアルコール系重合体における水酸基とエステル結合との合計に対する水酸基のモル分率）は特に限定されないが、高湿度下での皮膜強度の観点から、好ましくは８０〜９９．９モル％であり、より好ましくは９０〜９９．５モル％である。けん化度が８０モル％未満になると、皮膜にした際に当該皮膜が十分な皮膜強度を得られないことがある。けん化度が９９．９モル％より高いビニルアルコール系重合体は、一般に製造が難しい。 The saponification degree of the hydroxymethyl group-containing vinyl alcohol polymer of the present invention (that is, the mole fraction of hydroxyl groups relative to the total of hydroxyl groups and ester bonds in the hydroxymethyl group-containing vinyl alcohol polymer) is not particularly limited, but high humidity From a viewpoint of the film | membrane intensity | strength below, Preferably it is 80-99.9 mol%, More preferably, it is 90-99.5 mol%. If the degree of saponification is less than 80 mol%, the film may not have sufficient film strength when formed into a film. Vinyl alcohol polymers having a saponification degree higher than 99.9 mol% are generally difficult to produce.
本発明のヒドロキシメチル基含有ビニルアルコール系重合体の製造方法は特に限定されない。例えば、ビニルエステル系単量体と、それと共重合可能でありかつ式（１）で表される構造単位に変換可能な不飽和単量体とを共重合し、得られた共重合体のビニルエステル単位をビニルアルコール単位に変換し、一方で式（１）で表される構造単位に変換可能な不飽和単量体に由来する単位を式（１）で表される構造単位に変換する方法が挙げられる。式（１）で表される構造単位に変換可能な不飽和単量体の具体例を以下の式（２）に示す。 The method for producing the hydroxymethyl group-containing vinyl alcohol polymer of the present invention is not particularly limited. For example, a vinyl ester monomer is copolymerized with an unsaturated monomer that can be copolymerized therewith and that can be converted to the structural unit represented by the formula (1), and the resulting copolymer vinyl is obtained. A method for converting an ester unit into a vinyl alcohol unit, while converting a unit derived from an unsaturated monomer that can be converted into a structural unit represented by formula (1) into a structural unit represented by formula (1) Is mentioned. A specific example of the unsaturated monomer that can be converted into the structural unit represented by the formula (1) is shown in the following formula (2).
式（２）において、Ｒは炭素数１〜１０のアルキル基を示す。Ｒの構造としては特に限定されず、一部に分岐、環状構造を有していても良い。また、一部が他の官能基で置換されていてもよい。Ｒは好ましくは炭素数１〜５のアルキル基であり、該アルキル基の例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基などの直鎖または分岐を有するアルキル基が挙げられる。また、Ｒが有していてもよい置換基としては、アルコキシ基、ハロゲン原子、水酸基などが挙げられる。 In the formula (2), R represents an alkyl group having 1 to 10 carbon atoms. The structure of R is not particularly limited, and may partially have a branched or cyclic structure. Moreover, a part may be substituted with other functional groups. R is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, Examples thereof include a linear or branched alkyl group such as a pentyl group. Examples of the substituent that R may have include an alkoxy group, a halogen atom, and a hydroxyl group.
式（２）で示される不飽和単量体としては、例えばヒドロキシメチルビニリデンジアセテートが挙げられ、具体的には、１，３−ジアセトキシ−２−メチレンプロパン、１，３−ジプロピオニルオキシ−２−メチレンプロパン、１，３−ジブチロニルオキシ−２−メチレンプロパンなどが挙げられる。中でも、１，３−ジアセトキシ−２−メチレンプロパンが製造容易性の点で好ましく用いられる。 Examples of the unsaturated monomer represented by the formula (2) include hydroxymethylvinylidene diacetate, and specific examples thereof include 1,3-diacetoxy-2-methylenepropane and 1,3-dipropionyloxy-2. -Methylenepropane, 1,3-dibutyronyloxy-2-methylenepropane and the like. Among these, 1,3-diacetoxy-2-methylenepropane is preferably used in terms of ease of production.
式（２）で示されるビニリデン型不飽和単量体は、一般的にビニルアルコール系重合体の変性に用いられる他のアリル型不飽和単量体（例えば、アリルグリシジルエーテル等）に比べ、ビニルエステル系単量体との共重合反応が進行し易い。従って、本発明のヒドロキシメチル基含有ビニルアルコール系重合体は、重合時における変性量や重合度の制約が少なく、変性量及び重合度を高くすることができる。また、重合終了時に残留する未反応の当該不飽和単量体の量が少ないことから、本発明のヒドロキシメチル基含有ビニルアルコール系重合体は工業的な製造時における環境面及びコスト面においても優れている。 The vinylidene type unsaturated monomer represented by the formula (2) is more vinyl than other allyl type unsaturated monomers (for example, allyl glycidyl ether) generally used for modification of vinyl alcohol polymers. Copolymerization reaction with an ester monomer is likely to proceed. Therefore, the hydroxymethyl group-containing vinyl alcohol polymer of the present invention has few restrictions on the amount of modification and the degree of polymerization during polymerization, and can increase the amount of modification and the degree of polymerization. Further, since the amount of the unreacted unsaturated monomer remaining at the end of the polymerization is small, the hydroxymethyl group-containing vinyl alcohol polymer of the present invention is excellent in terms of environment and cost during industrial production. ing.
本発明のヒドロキシメチル基含有ビニルアルコール重合体の製造に用いられるビニルエステル系単量体は特に限定されないが、例えば、蟻酸ビニル、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、バーサチック酸ビニル、カプロン酸ビニル、カルリル酸ビニル、ラウリル酸ビニル、パルミチン酸ビニル、ステアリン酸ビニル、オレイン酸ビニル、安息香酸ビニルである。経済的観点からは酢酸ビニルが好ましい。 The vinyl ester monomer used in the production of the hydroxymethyl group-containing vinyl alcohol polymer of the present invention is not particularly limited. For example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate , Vinyl versatate, vinyl caproate, vinyl carlylate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, vinyl benzoate. From the economical viewpoint, vinyl acetate is preferred.
式（２）で示される不飽和単量体とビニルエステル系重合体とを共重合する重合方式は、回分重合、半回分重合、連続重合、半連続重合のいずれでもよく、重合方法には塊状重合法、溶液重合法、懸濁重合法、乳化重合法などの公知の方法を適用できる。無溶媒またはアルコールなどの溶媒中で重合を進行させる塊状重合法または溶液重合法が、通常採用される。高重合度のビニルエステル系共重合体を得る場合には、乳化重合法の採用が選択肢の一つとなる。溶液重合法の溶媒は特に限定されないが、例えばアルコールである。溶液重合法の溶媒に使用されるアルコールは、例えばメタノール、エタノール、プロパノールなどの低級アルコールである。重合系における溶媒の使用量は、目的とするビニルアルコール重合体の粘度平均重合度に応じて溶媒の連鎖移動を考慮して選択すればよく、例えば溶媒がメタノールの場合、溶媒と重合系に含まれる全単量体との重量比｛＝（溶媒）／（全単量体）｝にして０．０１〜１０の範囲、好ましくは０．０５〜３の範囲から選択される。 The polymerization method for copolymerizing the unsaturated monomer represented by the formula (2) and the vinyl ester polymer may be any of batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization. Known methods such as a polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method can be applied. A bulk polymerization method or a solution polymerization method in which polymerization is allowed to proceed in a solvent-free or solvent such as alcohol is usually employed. In order to obtain a vinyl ester copolymer having a high degree of polymerization, one of the options is to employ an emulsion polymerization method. Although the solvent of the solution polymerization method is not particularly limited, for example, alcohol. The alcohol used as the solvent for the solution polymerization method is, for example, a lower alcohol such as methanol, ethanol, or propanol. The amount of solvent used in the polymerization system may be selected in consideration of the chain transfer of the solvent according to the viscosity average degree of polymerization of the target vinyl alcohol polymer. For example, when the solvent is methanol, it is included in the solvent and the polymerization system. The weight ratio with respect to the total monomer {= (solvent) / (total monomer)} is selected in the range of 0.01 to 10, preferably 0.05 to 3.
式（２）で示される不飽和単量体とビニルエステル系重合体との共重合に使用される重合開始剤は、公知の重合開始剤、例えばアゾ系開始剤、過酸化物系開始剤、レドックス系開始剤から重合方法に応じて選択される。アゾ系開始剤は、例えば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）、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）である。過酸化物系開始剤は、例えばジイソプロピルパーオキシジカーボネート、ジ−２−エチルヘキシルパーオキシジカーボネート、ジエトキシエチルパーオキシジカーボネートなどのパーカーボネート系化合物；ｔ−ブチルパーオキシネオデカネート、α−クミルパーオキシネオデカネートなどのパーエステル化合物；アセチルシクロヘキシルスルホニルパーオキシド；２，４，４−トリメチルペンチル−２−パーオキシフェノキシアセテートである。過硫酸カリルム、過硫酸アンモニウム、過酸化水素などを上記開始剤に組み合わせて重合開始剤としてもよい。レドックス系開始剤は、例えば上記の過酸化物系開始剤と亜硫酸水素ナトリウム、炭酸水素ナトリウム、酒石酸、Ｌ−アスコルビン酸、ロンガリットなどの還元剤とを組み合わせた重合開始剤である。重合開始剤の使用量は、重合触媒により異なるために一概には決められないが、重合速度に応じて選択される。例えば重合開始剤にアゾビスイソブチロニトリルあるいは過酸化アセチルを用いる場合、ビニルエステル系単量体に対して０．０１〜０．２モル％が好ましく、０．０２〜０．１５モル％がより好ましい。重合温度は特に限定されないが、室温〜１５０℃程度が適当であり、好ましくは４０℃以上かつ使用する溶媒の沸点以下である。 The polymerization initiator used for copolymerization of the unsaturated monomer represented by the formula (2) and the vinyl ester polymer is a known polymerization initiator such as an azo initiator, a peroxide initiator, The redox initiator is selected according to the polymerization method. Examples of the azo initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile). Examples of the peroxide initiator include percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diethoxyethyl peroxydicarbonate; t-butyl peroxyneodecanate, α- Perester compounds such as cumylperoxyneodecanate; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate. Caryl persulfate, ammonium persulfate, hydrogen peroxide, or the like may be combined with the above initiator to form a polymerization initiator. The redox initiator is, for example, a polymerization initiator in which the peroxide initiator is combined with a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, or longalite. The amount of the polymerization initiator used varies depending on the polymerization catalyst and is not generally determined, but is selected according to the polymerization rate. For example, when azobisisobutyronitrile or acetyl peroxide is used as the polymerization initiator, 0.01 to 0.2 mol% is preferable with respect to the vinyl ester monomer, and 0.02 to 0.15 mol% is preferable. More preferred. The polymerization temperature is not particularly limited, but is suitably about room temperature to 150 ° C, preferably 40 ° C or higher and lower than the boiling point of the solvent used.
式（２）で示される不飽和単量体とビニルエステル系重合体との共重合は、本発明の効果が得られる限り、連鎖移動剤の存在下で行ってもよい。連鎖移動剤は、例えばアセトアルデヒド、プロピオンアルデヒドなどのアルデヒド類；アセトン、メチルエチルケトンなどのケトン類；２−ヒドロキシエタンチオールなどのメルカプタン類；ホスフィン酸ナトリウム一水和物などのホスフィン酸塩類などである。なかでもアルデヒド類及びケトン類が好適に用いられる。重合系への連鎖移動剤の添加量は、添加する連鎖移動剤の連鎖移動係数及び目的とするビニルアルコール系重合体の重合度に応じて決定されるが、一般にビニルエステル系単量体１００質量部に対して０．１〜１０質量部が好ましい。 The copolymerization of the unsaturated monomer represented by the formula (2) and the vinyl ester polymer may be performed in the presence of a chain transfer agent as long as the effect of the present invention is obtained. Examples of the chain transfer agent include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; phosphinic acid salts such as sodium phosphinate monohydrate and the like. Of these, aldehydes and ketones are preferably used. The amount of chain transfer agent added to the polymerization system is determined according to the chain transfer coefficient of the chain transfer agent to be added and the degree of polymerization of the target vinyl alcohol polymer, but generally 100 mass of vinyl ester monomer. 0.1-10 mass parts is preferable with respect to a part.
式（２）に示される不飽和単量体とビニルエステル系重合体との共重合により得られたビニルエステル系共重合体をけん化して、本発明のヒドロキシメチル基含有ビニルアルコール系重合体を得ることができる。該ビニルエステル系共重合体をけん化することによって、共重合体中のビニルエステル単位はビニルアルコール単位に変換される。また、式（２）で示される不飽和単量体に由来する単位のエステル結合も加水分解され、式（１）で表される１，３−ジオール構造に変換される。したがって、本発明のヒドロキシメチル基含有ビニルアルコール系重合体は、けん化後にさらに加水分解等の反応を行わなくても製造することができる。 By saponifying a vinyl ester copolymer obtained by copolymerization of an unsaturated monomer represented by the formula (2) and a vinyl ester polymer, the hydroxymethyl group-containing vinyl alcohol polymer of the present invention is obtained. Can be obtained. By saponifying the vinyl ester copolymer, the vinyl ester unit in the copolymer is converted to a vinyl alcohol unit. Moreover, the ester bond of the unit derived from the unsaturated monomer represented by the formula (2) is also hydrolyzed and converted into a 1,3-diol structure represented by the formula (1). Therefore, the hydroxymethyl group-containing vinyl alcohol polymer of the present invention can be produced without further reaction such as hydrolysis after saponification.
ビニルエステル系共重合体のけん化は、例えばビニルアルコールまたは含水アルコールに当該共重合体が溶解した状態で行う。けん化に使用するアルコールは、例えばメタノール、エタノールなどの低級アルコールであり、好ましくはメタノールである。けん化に使用するアルコールは、その重量の４０重量％以下であれば、アセトン、酢酸メチル、酢酸エチル、ベンゼンなどの溶媒を含んでもよい。けん化に使用する触媒は、例えば水酸化カリウム、水酸化ナトリウムなどのアルカリ金属の水酸化物、ナトリウムメチラートなどのアルカリ触媒、鉱酸などの酸触媒である。けん化を行う温度は限定されないが、２０〜６０℃の範囲が好適である。けん化の進行に従ってゲル状の生成物が析出してくる場合には、生成物を粉砕した後、洗浄、乾燥して、ヒドロキシメチル基含有ビニルアルコール系重合体を得ることができる。けん化方法は、前述した方法に限らず公知の方法を適用できる。 The saponification of the vinyl ester copolymer is performed, for example, in a state where the copolymer is dissolved in vinyl alcohol or hydrous alcohol. The alcohol used for saponification is, for example, a lower alcohol such as methanol or ethanol, preferably methanol. The alcohol used for saponification may contain a solvent such as acetone, methyl acetate, ethyl acetate, and benzene as long as it is 40% by weight or less of the weight. The catalyst used for saponification is, for example, an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an alkali catalyst such as sodium methylate, or an acid catalyst such as mineral acid. Although the temperature which performs saponification is not limited, the range of 20-60 degreeC is suitable. When a gel product precipitates as saponification proceeds, the product is pulverized, washed and dried to obtain a hydroxymethyl group-containing vinyl alcohol polymer. The saponification method is not limited to the method described above, and a known method can be applied.
本発明のヒドロキシメチル基含有ビニルアルコール系重合体は、本発明の効果が得られる限り、式（１）で示される構造単位、ビニルアルコール単位及びビニルエステル単位以外の構造単位をさらに有することができる。当該構造単位は、例えばビニルエステルと共重合可能でありかつ式（１）で示される構造単位に変換可能な不飽和単量体、及びビニルエステルと共重合可能なエチレン性不飽和単量体に由来する構造単位である。エチレン性不飽和単量体は、例えば、エチレン、プロピレン、ｎ−ブテン、イソブチレン、１−ヘキセンなどのα−オレフィン類；アクリル酸及びその塩；アクリル酸エステル基を有する不飽和単量体；メタクリル酸及びその塩；メタクリル酸エステル基を有する不飽和単量体；アクリルアミド、Ｎ−メチルアクリルアミド、Ｎ−エチルアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、ジアセトンアクリルアミド、アクリルアミドプロパンスルホン酸及びその塩、アクリルアミドプロピルジメチルアミン及びその塩（例えば４級塩）；メタクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ−エチルメタクリルアミド、メタクリルアミドプロパンスルホン酸及びその塩、メタクリルアミドプロピルジメチルアミン及びその塩（例えば４級塩）；メチルビニルエーテル、エチルビニルエーテル、ｎ−プロピルビニルエーテル、ｉ−プロピルビニルエーテル、ｎ−ブチルビニルエーテル、ｉ−ブチルビニルエーテル、ｔ−ブチルビニルエーテル、ドデシルビニルエーテル、ステアリルビニルエーテル、２，３−ジアセトキシ−１−ビニルオキシプロパンなどのビニルエーテル類；アクリロニトリル、メタクリロニトリルなどのシアン化ビニル類；塩化ビニル、フッ化ビニルなどのハロゲン化ビニル類；塩化ビニリデン、フッ化ビニリデンなどのハロゲン化ビニリデン類；酢酸アリル、２，３−ジアセトキシ−１−アリルオキシプロパン、塩化アリルなどのアリル化合物；マレイン酸、イタコン酸、フマル酸などの不飽和ジカルボン酸及びその塩またはエステル；ビニルトリメトキシシランなどのビニルシリル化合物、酢酸イソプロペニルである。 The hydroxymethyl group-containing vinyl alcohol polymer of the present invention can further have a structural unit other than the structural unit represented by the formula (1), the vinyl alcohol unit and the vinyl ester unit as long as the effects of the present invention are obtained. . The structural unit is, for example, an unsaturated monomer that can be copolymerized with a vinyl ester and that can be converted into a structural unit represented by the formula (1), and an ethylenically unsaturated monomer that can be copolymerized with a vinyl ester. It is a derived structural unit. Examples of the ethylenically unsaturated monomer include α-olefins such as ethylene, propylene, n-butene, isobutylene, and 1-hexene; acrylic acid and a salt thereof; an unsaturated monomer having an acrylate group; Acids and salts thereof; unsaturated monomers having methacrylic acid ester groups; acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulfonic acid and salts thereof, acrylamidepropyl Dimethylamine and its salts (for example, quaternary salts); methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidepropanesulfonic acid and its salts, methacrylamidepropyldimethylamine and its salts (for example, quaternary salts) ; Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether, 2,3-diacetoxy-1-vinyloxypropane, etc. Vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinyl fluoride; vinylidene halides such as vinylidene chloride and vinylidene fluoride; allyl acetate and 2,3-diacetoxy -1-Allyl compounds such as allyloxypropane and allyl chloride; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid and salts or esters thereof; vinyltrimethoxysila Vinyl silyl compounds such as ethylene, and isopropenyl acetate.
本発明のヒドロキシメチル基含有ビニルアルコール系重合体における式（１）で示される構造単位、ビニルアルコール単位及びその他任意の構成単位の配列順序には特に制限はなく、ランダム、ブロック、交互などのいずれであってもよい。 The arrangement order of the structural unit represented by the formula (1), the vinyl alcohol unit, and other arbitrary structural units in the hydroxymethyl group-containing vinyl alcohol polymer of the present invention is not particularly limited, and any of random, block, alternating, etc. It may be.
本発明のヒドロキシメチル基含有ビニルアルコール系重合体には、さらに、充填剤、銅化合物などの加工安定剤、耐候性安定剤、着色剤、紫外線吸収剤、光安定剤、酸化防止剤、帯電防止剤、難燃剤、可塑剤、他の熱可塑性樹脂、潤滑剤、香料、消泡剤、消臭剤、増量剤、剥離剤、離型剤、補強剤、架橋剤、防かび剤、防腐剤、結晶化速度遅延剤などの添加剤を、必要に応じて適宜配合できる。 The hydroxymethyl group-containing vinyl alcohol polymer of the present invention further includes a filler, a processing stabilizer such as a copper compound, a weather resistance stabilizer, a colorant, an ultraviolet absorber, a light stabilizer, an antioxidant, and an antistatic agent. Agent, flame retardant, plasticizer, other thermoplastic resin, lubricant, fragrance, defoaming agent, deodorant, extender, release agent, mold release agent, reinforcing agent, cross-linking agent, fungicide, preservative, Additives such as a crystallization rate retarder can be blended as needed.
本発明のヒドロキシメチル基含有ビニルアルコール系重合体は、その特性を利用して単独でまたは他の成分を添加した組成物として、成形、紡糸、エマルジョン化等の公知方法に従い、ビニルアルコール系重合体が用いられる各種用途に使用可能である。例えば各種用途の界面活性剤；各種のコーティング剤；紙用内添剤及び顔料バインダー；塗料；経糸糊剤；繊維加工剤；ポリエステルなどの疎水性繊維の糊剤；各種フィルム、シート、ボトル、繊維、増粘剤、凝集剤、土壌改質剤、イオン交換樹脂、イオン交換膜などに使用できる。 The hydroxymethyl group-containing vinyl alcohol polymer of the present invention is a vinyl alcohol polymer according to known methods such as molding, spinning, and emulsification, either alone or as a composition to which other components are added, utilizing its properties. Can be used for various purposes. For example, surfactants for various uses; various coating agents; paper additives and pigment binders; paints; warp pastes; fiber processing agents; pastes for hydrophobic fibers such as polyester; various films, sheets, bottles, fibers , Thickeners, flocculants, soil modifiers, ion exchange resins, ion exchange membranes and the like.
本発明のヒドロキシメチル基含有ビニルアルコール系重合体を成形する方法は限定されない。成形方法は、例えば当該重合体の溶媒である水またはジメチルスルホキシドなどに溶解した溶液の状態から成形する方法（例えばキャスト成形法）；加熱により当該重合体を可塑化して成形する方法（例えば押出成形法、射出成形法、インフレ成形法、プレス成形法、ブロー成形法）である。これらの成形方法により、フィルム、シート、チューブ、ボトルなどの任意の形状を有する成形体が得られる。 The method for molding the hydroxymethyl group-containing vinyl alcohol polymer of the present invention is not limited. The molding method is, for example, a method of molding from the state of a solution dissolved in water or dimethyl sulfoxide as a solvent of the polymer (for example, cast molding method); a method of plasticizing and molding the polymer by heating (for example, extrusion molding) Method, injection molding method, inflation molding method, press molding method, blow molding method). By these molding methods, a molded body having an arbitrary shape such as a film, a sheet, a tube, or a bottle can be obtained.
本発明のヒドロキシメチル基含有ビニルアルコール系重合体は、高湿度下における皮膜の強度が高いため、特に紙用内添剤や各種水溶性バインダーとしての用途に好適である。また、この用途での使用には、ビニルアルコール系重合体の水に対する溶解性がプロセスの簡略化に影響するため、本発明のヒドロキシメチル基含有ビニルアルコール系重合体が有する高い水溶性が有利に働き、有用である。 The hydroxymethyl group-containing vinyl alcohol polymer of the present invention is particularly suitable for use as an internal additive for paper and various water-soluble binders because of the high strength of the film under high humidity. Moreover, since the solubility of the vinyl alcohol polymer in water affects the simplification of the process, the high water solubility of the hydroxymethyl group-containing vinyl alcohol polymer of the present invention is advantageous. Working and useful.
以下、実施例により本発明をより詳細に説明するが、本発明はこれらの実施例により何ら限定されるものではない。以下、ビニルアルコール系重合体をＰＶＡと略記することがある。なお、実施例、比較例中の「％」及び「部」は特に断りのない限り、それぞれ「質量％」及び「質量部」を表す。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by these Examples. Hereinafter, the vinyl alcohol polymer may be abbreviated as PVA. In the examples and comparative examples, “%” and “parts” represent “% by mass” and “parts by mass”, respectively, unless otherwise specified.
ビニルアルコール系重合体の一次構造については、２７０ＭＨｚ １Ｈ−ＮＭＲにより定量した。１Ｈ−ＮＭＲ測定時のビニルアルコール系重合体の溶媒は重水素化ＤＭＳＯを用いた。ビニルアルコール系重合体の重合度を以下に示す方法で測定し、水溶液状態の粘度安定性及び発泡性、また、ビニルアルコール系重合体の水溶性及び高湿度下での皮膜強度を以下に示す方法で評価した。 The primary structure of the vinyl alcohol polymer was quantified by 270 MHz 1 H-NMR. Deuterated DMSO was used as the solvent for the vinyl alcohol polymer during 1 H-NMR measurement. The degree of polymerization of the vinyl alcohol polymer is measured by the following method, and the viscosity stability and foamability of the aqueous solution state, and the water solubility of the vinyl alcohol polymer and the film strength under high humidity are shown below. It was evaluated with.
［重合度］
けん化度が９９．５モル％未満の場合には、けん化度９９．５モル％以上になるまでけん化したビニルアルコール系重合体について、水中、３０℃で測定した極限粘度［η］（ｇ／ｄｌ）から次式により求めた粘度平均重合度（Ｐ）で表す。
Ｐ＝（［η］×１０３／８．２９）（１／０．６２）
[Degree of polymerization]
When the saponification degree is less than 99.5 mol%, the intrinsic viscosity [η] (g / dl) measured at 30 ° C. in water for the saponified vinyl alcohol polymer until the saponification degree is 99.5 mol% or more. ) From the viscosity average polymerization degree (P) determined by the following formula.
P = ([η] × 10 3 /8.29) (1 / 0.62)
［１０％水溶液の粘度安定性］
ビニルアルコール系重合体の５℃、１０％水溶液を調製して、１時間後及び１２時間後の粘度を測定し、増粘倍率を求め、以下の通り評価した。
Ａ：増粘倍率が６倍未満である。
Ｂ：増粘倍率が６倍以上である。
[Viscosity stability of 10% aqueous solution]
A 5% 10% aqueous solution of a vinyl alcohol polymer was prepared, the viscosity after 1 hour and after 12 hours was measured, the thickening factor was determined, and evaluated as follows.
A: The thickening factor is less than 6 times.
B: Thickening magnification is 6 times or more.
［４％水溶液の発泡性］
ビニルアルコール系重合体の４％水溶液を調製し、垂直に立てたガラス管（内径４．５ｃｍ、高さ１５０ｃｍ）に深さ１３ｃｍになるように仕込み、１．５Ｌ／ｍｉｎの速度で、１０分間のポンプ循環（ガラス管の下部から水溶液を抜き取りガラス管上部へ返送）を行った後、泡の発生した高さを測定した。その結果を以下の通り評価した。
Ａ：発泡した泡の高さが２７ｃｍ未満
Ｂ：発泡した泡の高さが２７ｃｍ以上４０ｃｍ未満
Ｃ：発泡した泡の高さが４０ｃｍ以上
[Foamability of 4% aqueous solution]
A 4% aqueous solution of a vinyl alcohol polymer was prepared and charged into a vertically standing glass tube (inner diameter 4.5 cm, height 150 cm) to a depth of 13 cm, and at a rate of 1.5 L / min for 10 minutes. After circulating the pump (removing the aqueous solution from the lower part of the glass tube and returning it to the upper part of the glass tube), the height at which bubbles were generated was measured. The results were evaluated as follows.
A: The height of the foamed foam is less than 27 cm B: The height of the foamed foam is 27 cm or more and less than 40 cm C: The height of the foamed foam is 40 cm or more
［皮膜の溶解性］
濃度４％のビニルアルコール系重合体水溶液を調製し、それをＰＥＴフィルム上に流延した後２０℃１週間乾燥させ、さらに真空乾燥機で一晩乾燥させることで、厚み４０μｍの皮膜を得た。１Ｌのイオン交換水を加えた１Ｌのビーカーを２０℃に温度制御したバスに浸し、長さ３０ｍｍのテフロン（登録商標）製マグネティックスターラーチップで３００ｒｐｍの回転速度で攪拌しているところに、金属枠で固定した上記皮膜（サイズ：４０ｍｍ×４０ｍｍ、厚み４０μｍ）を投入し、完全に溶解する時間を測定した。なお、皮膜の厚みが４０μｍとは異なる場合、以下の式に従って皮膜の厚み４０μｍの値に換算した。
換算溶解時間（秒）＝［４０／皮膜厚（μｍ）］２×サンプル溶解時間（秒）
測定結果は、以下の通り評価した。
Ａ：３０分以内に完全溶解する。
Ｂ：３０分以上経過しても完全溶解しない。
[Solubility of film]
A vinyl alcohol polymer aqueous solution having a concentration of 4% was prepared, cast on a PET film, dried at 20 ° C. for 1 week, and further dried overnight in a vacuum dryer to obtain a film having a thickness of 40 μm. . A 1 L beaker to which 1 L of ion exchange water has been added is immersed in a bath whose temperature is controlled at 20 ° C. and stirred at a rotational speed of 300 rpm with a 30 mm long Teflon (registered trademark) magnetic stirrer chip. The above-described film (size: 40 mm × 40 mm, thickness 40 μm) fixed in (1) was added, and the time for complete dissolution was measured. When the film thickness was different from 40 μm, the film thickness was converted to a value of 40 μm according to the following formula.
Equivalent dissolution time (seconds) = [40 / film thickness (μm)] 2 × sample dissolution time (seconds)
The measurement results were evaluated as follows.
A: Completely dissolves within 30 minutes.
B: Complete dissolution does not occur even after 30 minutes.
［高湿度下での皮膜の強度］
濃度４％のビニルアルコール系重合体水溶液を調製し、それをＰＥＴフィルム上に流延した後２０℃１週間乾燥させ、厚み約４０μｍの皮膜を得た。得られた皮膜を１０ｍｍ×８０ｍｍの短冊状にカットし、２０℃、湿度８０％にて一週間調湿した後、（株）島津製作所製ＡＧ−ＩＳを用いて、チャック間距離５０ｍｍ、引張り速度５００ｍｍ／分の条件で強伸度測定を行い、応力−ひずみ曲線から靭性を求めた。なお、測定は各サンプル５回測定し、その平均値を求め、以下の評価基準で評価した。
Ａ：２８０ｋｇｆ／ｍｍ以上
Ｂ：２４０ｋｇｆ／ｍｍ以上２８０ｋｇｆ／ｍｍ未満
Ｃ：２４０ｋｇｆ／ｍｍ未満
[Strength of film under high humidity]
A vinyl alcohol polymer aqueous solution having a concentration of 4% was prepared, cast on a PET film and dried at 20 ° C. for 1 week to obtain a film having a thickness of about 40 μm. The obtained film was cut into a 10 mm × 80 mm strip and conditioned for one week at 20 ° C. and 80% humidity, and then a distance between chucks of 50 mm and a pulling speed using AG-IS manufactured by Shimadzu Corporation. Strong elongation was measured under conditions of 500 mm / min, and toughness was determined from the stress-strain curve. In addition, the measurement measured each sample 5 times, calculated | required the average value, and evaluated it with the following evaluation criteria.
A: 280 kgf / mm or more B: 240 kgf / mm or more and less than 280 kgf / mm C: Less than 240 kgf / mm
［実施例１］
酢酸ビニル−１，３−ジアセトキシ−２−メチレンプロパン共重合体の合成
攪拌機、還流冷却管、アルゴン導入管、開始剤の添加口を備えた反応器に、酢酸ビニル６４０質量部、メタノール質量部、コモノマーとして１，３−ジアセトキシ−２−メチレンプロパン（ＤＡＭＰ）６．４３質量部を仕込み、アルゴンバブリングをしながら３０分間系内をアルゴン置換した。反応器の昇温を開始し、内温が６０℃となったところで、２，２’−アゾビスイソブチロニトリル（ＡＩＢＮ）０．１５ｇを添加し重合を開始した。６０℃で２１８分重合した後、冷却して重合を停止した。重合停止時の重合率は４０％であった。続いて、３０℃、減圧下でメタノールを時々添加しながら未反応のモノマーの除去を行い、酢酸ビニル−１，３−ジアセトキシ−２−メチレンプロパン共重合体（ＤＡＭＰ変性ＰＶＡｃ）のメタノール溶液（濃度３３．５％）を得た。次に、このメタノール溶液１４９質量部にメタノール９５．８質量部を加え（溶液中のＤＡＭＰ変性ＰＶＡｃ５０質量部）、さらに、４．７２ｇの水酸化ナトリウムメタノール溶液（濃度１３．３％）を添加して、４０℃でけん化を行った（けん化溶液のＤＡＭＰ変性ＰＶＡｃ濃度２０％、ＤＡＭＰ変性ＰＶＡｃ中の酢酸ビニル単位に対する水酸化ナトリウムのモル比０．０３）。水酸化ナトリウムメタノール溶液を添加後約７分でゲル化物が生成したので、これを粉砕機にて粉砕し、さらに４０℃で５３分間放置してけん化を進行させた後、酢酸メチル２００質量部を加えて残存するアルカリを中和した。フェノールフタレイン指示薬を用いて中和が終了したことを確認した後、濾別して白色固体を得、これにメタノール５００ｇを加えて１時間加熱還流した。上記の洗浄操作を３回繰り返した後、遠心脱水して得られた白色固体を真空乾燥機にて、４０℃で２４時間乾燥させ、一般式（１）で示される構造単位を含むヒドロキシメチル基含有ビニルアルコール系重合体を得た。重合度は１８００、けん化度は９８．７モル％、変性量（すなわち、ヒドロキシメチル基含有ビニルアルコール系重合体における式（１）に示される構造単位の含有率）は０．９モル％であった。物性を表２に示す。
[Example 1]
In a reactor equipped with a vinyl acetate-1,3-diacetoxy-2-methylenepropane copolymer synthesis stirrer, reflux condenser, argon inlet, and initiator addition port, 640 parts by mass of vinyl acetate, parts by mass of methanol, As a comonomer, 6.43 parts by mass of 1,3-diacetoxy-2-methylenepropane (DAMP) was charged, and the system was purged with argon for 30 minutes while performing argon bubbling. The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.15 g of 2,2′-azobisisobutyronitrile (AIBN) was added to initiate polymerization. After polymerization at 60 ° C. for 218 minutes, the polymerization was stopped by cooling. The polymerization rate when the polymerization was stopped was 40%. Subsequently, unreacted monomers were removed while adding methanol occasionally at 30 ° C. under reduced pressure, and a methanol solution (concentration of vinyl acetate-1,3-diacetoxy-2-methylenepropane copolymer (DAMP-modified PVAc)) 33.5%). Next, 95.8 parts by mass of methanol was added to 149 parts by mass of this methanol solution (50 parts by mass of DAMP-modified PVAc in the solution), and 4.72 g of sodium hydroxide methanol solution (concentration: 13.3%) was further added. Then, saponification was performed at 40 ° C. (concentration of DAMP-modified PVAc in the saponification solution was 20%, molar ratio of sodium hydroxide to vinyl acetate units in DAMP-modified PVAc was 0.03). A gelled product was formed in about 7 minutes after the addition of the sodium hydroxide methanol solution, and this was pulverized by a pulverizer and further allowed to stand at 40 ° C. for 53 minutes to proceed saponification, and then 200 parts by mass of methyl acetate was added. In addition, the remaining alkali was neutralized. After confirming the completion of neutralization using a phenolphthalein indicator, a white solid was obtained by filtration, 500 g of methanol was added thereto, and the mixture was heated to reflux for 1 hour. After repeating the above washing operation three times, the white solid obtained by centrifugal dehydration was dried in a vacuum dryer at 40 ° C. for 24 hours, and the hydroxymethyl group containing the structural unit represented by the general formula (1) A vinyl alcohol polymer was obtained. The degree of polymerization was 1800, the degree of saponification was 98.7 mol%, and the amount of modification (that is, the content of the structural unit represented by the formula (1) in the hydroxymethyl group-containing vinyl alcohol polymer) was 0.9 mol%. It was. The physical properties are shown in Table 2.
［実施例２〜６］
酢酸ビニル及びメタノールの仕込み量、重合時に使用するコモノマーの種類や添加量等の重合条件、けん化時における変性ＰＶＡｃの濃度、酢酸ビニル単位に対する水酸化ナトリウムのモル比等のけん化条件を表１に示すように変更したこと以外は、実施例１と同様の方法により各種変性ＰＶＡを製造した。各ＰＶＡの物性を表２に示す。
[Examples 2 to 6]
Table 1 shows the saponification conditions such as the amount of vinyl acetate and methanol charged, the polymerization conditions such as the type and amount of comonomer used during polymerization, the concentration of modified PVAc during saponification, and the molar ratio of sodium hydroxide to vinyl acetate units. Various modified PVAs were produced in the same manner as in Example 1 except that the above changes were made. Table 2 shows the physical properties of each PVA.
［比較例１］
攪拌機、還流冷却管、アルゴン導入管、開始剤の添加口を備えた反応器に、酢酸ビニル７００質量部、メタノール３００質量部を仕込み、アルゴンバブリングをしながら３０分間系内をアルゴン置換した。反応器の昇温を開始し、内温が６０℃となったところで、ＡＩＢＮ０．２５ｇを添加し重合を開始した。６０℃で１８０分重合した後、冷却して重合を停止した。重合停止時の重合率は４０％であった。続いて、３０℃、減圧下でメタノールを時々添加しながら未反応のモノマーの除去を行い、ポリ酢酸ビニル（ＰＶＡｃ）のメタノール溶液（濃度３０％）を得た。次に、これにメタノールを加えて調製したＰＶＡｃのメタノール溶液４９７質量部（溶液中のＰＶＡｃ１００質量部）に、１４．０質量部の水酸化ナトリウムメタノール溶液（濃度１０．０％）を添加して、４０℃でけん化を行った（けん化溶液のＰＶＡｃ濃度２０％、ＰＶＡｃ中の酢酸ビニル単位に対する水酸化ナトリウムのモル比０．０３）。水酸化ナトリウムメタノール溶液を添加後約１分でゲル化物が生成したので、これを粉砕機にて粉砕し、さらに４０℃で５９分間放置してけん化を進行させた後、酢酸メチル５００質量部を加えて残存するアルカリを中和した。フェノールフタレイン指示薬を用いて中和が終了したことを確認した後、濾別して白色固体を得、これにメタノール２０００ｇを加えて１時間加熱還流した。上記の洗浄操作を３回繰り返した後、遠心脱水して得られた白色固体を真空乾燥機にて、４０℃で２４時間乾燥させ無変性のポリビニルアルコール（ＰＶＡ）を得た。重合度は１７００、けん化度は９８．５モル％であった。物性を表２に示す。
[Comparative Example 1]
A reactor equipped with a stirrer, a reflux condenser, an argon inlet, and an initiator addition port was charged with 700 parts by mass of vinyl acetate and 300 parts by mass of methanol, and the system was purged with argon for 30 minutes while bubbling with argon. The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of AIBN was added to initiate polymerization. After polymerization at 60 ° C. for 180 minutes, the polymerization was stopped by cooling. The polymerization rate when the polymerization was stopped was 40%. Subsequently, unreacted monomers were removed while sometimes adding methanol under reduced pressure at 30 ° C. to obtain a methanol solution (concentration 30%) of polyvinyl acetate (PVAc). Next, 14.0 parts by mass of sodium hydroxide methanol solution (concentration 10.0%) was added to 497 parts by mass of PVAc methanol solution prepared by adding methanol to this (100 parts by mass of PVAc in the solution). The saponification was carried out at 40 ° C. (PVAc concentration of saponification solution 20%, molar ratio of sodium hydroxide to vinyl acetate unit in PVAc 0.03). A gelled product was formed in about 1 minute after the addition of the sodium hydroxide methanol solution. This was pulverized with a pulverizer and allowed to stand at 40 ° C. for 59 minutes to proceed saponification, and then 500 parts by mass of methyl acetate was added. In addition, the remaining alkali was neutralized. After confirming that the neutralization was completed using a phenolphthalein indicator, a white solid was obtained by filtration, 2000 g of methanol was added thereto, and the mixture was heated to reflux for 1 hour. After the above washing operation was repeated three times, the white solid obtained by centrifugal dehydration was dried in a vacuum dryer at 40 ° C. for 24 hours to obtain unmodified polyvinyl alcohol (PVA). The degree of polymerization was 1700, and the degree of saponification was 98.5 mol%. The physical properties are shown in Table 2.
［比較例２］
酢酸ビニル及びメタノールの仕込み量、けん化時における変性ＰＶＡｃの濃度、酢酸ビニル単位に対する水酸化ナトリウムのモル比等のけん化条件を表１に示すように変更したこと以外は、比較例１と同様の方法により無変性ＰＶＡを製造した。物性を表２に示す。
[Comparative Example 2]
The same method as in Comparative Example 1 except that the saponification conditions such as the amounts of vinyl acetate and methanol, the concentration of modified PVAc during saponification, and the molar ratio of sodium hydroxide to vinyl acetate units were changed as shown in Table 1. To produce unmodified PVA. The physical properties are shown in Table 2.
［比較例３〜５］
酢酸ビニル及びメタノールの仕込み量、重合時に使用するコモノマーの種類や添加量等の重合条件、けん化時における変性ＰＶＡｃの濃度、酢酸ビニル単位に対する水酸化ナトリウムのモル比等のけん化条件を表１に示すように変更したこと以外は、実施例１と同様の方法により各種変性ＰＶＡを製造した。各ＰＶＡの物性を表２に示す。
[Comparative Examples 3 to 5]
Table 1 shows the saponification conditions such as the amount of vinyl acetate and methanol charged, the polymerization conditions such as the type and amount of comonomer used during polymerization, the concentration of modified PVAc during saponification, and the molar ratio of sodium hydroxide to vinyl acetate units. Various modified PVAs were produced in the same manner as in Example 1 except that the above changes were made. Table 2 shows the physical properties of each PVA.
実施例１〜６から明らかなように、本発明のヒドロキシメチル基含有ビニルアルコール系重合体（実施例１〜６）は、水への溶解性や水溶液の粘度安定性が高く、泡立ちが少ないなど水溶液状態における取り扱い性が改善されており、工業的に使用する際には有用である。さらに、皮膜は高湿度下でも高い強度を保持しており、皮膜物性も兼ね備えていることがわかる。一方、変性を実施していない場合（比較例１及び２）は、水溶液状態における取り扱い性が悪く、皮膜強度も十分ではない。他の変性種を用いた場合（比較例３〜５）は、高湿度下で十分な皮膜強度を示さなかった。また、構造によっては泡立ちが多く取り扱い難いものもあった。 As is apparent from Examples 1 to 6, the hydroxymethyl group-containing vinyl alcohol polymer (Examples 1 to 6) of the present invention has high solubility in water and viscosity stability of an aqueous solution, and less foaming. The handleability in an aqueous solution state is improved, which is useful for industrial use. Furthermore, it can be seen that the film retains high strength even under high humidity and also has film properties. On the other hand, when modification | denaturation is not implemented (comparative examples 1 and 2), the handleability in aqueous solution state is bad, and film | membrane intensity | strength is not enough. When other modified species were used (Comparative Examples 3 to 5), sufficient film strength was not exhibited under high humidity. In addition, there were some foams that were difficult to handle depending on the structure.
本発明によれば、水への溶解性に優れるにも関わらず、高湿度下での皮膜物性が良好であるという、相反する特長を有し、さらに水溶液の粘度安定性が良好、水溶液が泡立ち難いという性質も併せ持つビニルアルコール系重合体を提供することができる。本発明のヒドロキシメチル基含有ビニルアルコール系重合体は、例えば、紙用コーティング剤、紙用内添剤及び顔料バインダーなどの紙用改質剤、木材、紙、アルミ箔及び無機物などの接着剤、不織布バインダー、塗料、経糸糊剤、繊維加工剤、ポリエステルなどの疎水性繊維の糊剤、バリアフィルム及びバリアコーティング、その他各種フィルム、シート、ボトル、繊維、増粘剤、凝集剤、土壌改質剤、イオン交換樹脂、イオン交換膜などに使用できる。 According to the present invention, despite having excellent solubility in water, the film properties under high humidity are good, and there is a conflicting feature, the viscosity stability of the aqueous solution is good, and the aqueous solution is foamed. It is possible to provide a vinyl alcohol polymer having the property of being difficult. The hydroxymethyl group-containing vinyl alcohol polymer of the present invention includes, for example, paper coating agents, paper additives such as paper additives and pigment binders, adhesives such as wood, paper, aluminum foil and inorganic substances, Nonwoven fabric binder, paint, warp paste, fiber processing agent, hydrophobic fiber paste such as polyester, barrier films and barrier coatings, various other films, sheets, bottles, fibers, thickeners, flocculants, soil modifiers , Ion exchange resins, ion exchange membranes and the like.
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