JP6708088B2 - Resin composition and molded product - Google Patents
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本発明は、ポリビニルアルコール系樹脂を含有してなる樹脂組成物及び成形物に関し、更に詳しくは、高湿度下での強度及び低湿度下での耐ひび割れ性に優れる樹脂組成物及び成形物に関するものである。 The present invention relates to a resin composition and a molded product containing a polyvinyl alcohol-based resin, and more specifically, to a resin composition and a molded product which are excellent in strength under high humidity and crack resistance under low humidity. Is.
ポリビニルアルコール系樹脂（以下、ＰＶＡ系樹脂という。）及び糖類はそれぞれ水溶性の化合物として、その特性を活かして従来から様々な用途に用いられている。
例えば、接着剤、医薬品の結合剤、分散剤、フィルム、化粧品等が挙げられる。
中でも近年、包装材としての要望が高まっており、ＰＶＡ系樹脂や糖類を用いた包装材が各種の用途で用いられるようになった。
例えば、食品包装材、医薬品の包装材、農業用の包装材などで用いられるが、これらはいずれも雨天などの場合、高湿度下にさらされることもあり、その場合の包装材の強度が問題となっている。
Polyvinyl alcohol-based resins (hereinafter referred to as PVA-based resins) and saccharides have been conventionally used for various purposes as water-soluble compounds by taking advantage of their characteristics.
Examples thereof include adhesives, pharmaceutical binders, dispersants, films, cosmetics and the like.
Above all, in recent years, the demand for packaging materials has increased, and packaging materials using PVA-based resins and sugars have come to be used for various purposes.
For example, it is used in food packaging materials, pharmaceutical packaging materials, agricultural packaging materials, etc., but all of them may be exposed to high humidity in the case of rainy weather, and the strength of the packaging material in that case is a problem. Has become.
かかる問題に対し、フィラーを含有させるなどの検討が行われている（例えば、特許文献１参照。）。 With respect to such a problem, investigations such as inclusion of a filler have been conducted (for example, refer to Patent Document 1).
しかしながら、上記特許文献１の開示技術においても、高湿度下での包装材の強度はまだまだ満足のいくものではなく、また、冬場の乾燥や輸送時の安定性のため、低湿度下での耐ひび割れ性が求められており、かかる低湿度下での耐ひび割れ性の点でもまだまだ満足できるものが得られていないのが現状であり、近年の要求の高まりに伴って、成形品を成形する樹脂組成物の更なる改良が求められている。
そこで、本発明ではこのような背景下において、高湿度下での包装材の形状安定性に優れ、かつ低湿度下での耐ひび割れ性に優れるフィルム等の成形品を得る樹脂組成物を提供することを目的とするものである。
However, even in the technique disclosed in Patent Document 1, the strength of the packaging material under high humidity is still unsatisfactory, and due to the stability during winter drying and transportation, resistance to low humidity is low. The current situation is that cracking properties are required, and in terms of cracking resistance under such low humidity, satisfactory ones have not yet been obtained. Further improvements in the composition are sought.
Therefore, in the present invention, under such a background, a resin composition for obtaining a molded article such as a film having excellent shape stability of the packaging material under high humidity and excellent crack resistance under low humidity is provided. The purpose is that.
しかるに、本発明者等はかかる事情に鑑み鋭意研究を重ねた結果、ＰＶＡ系樹脂と糖類を含有してなる樹脂組成物において、糖類を従来よりも多く含有させ、更に、フィルムとした際の弾性率を高いものとすることにより、高湿度下での包装材の形状安定性に優れ、かつ低湿度下での耐ひび割れ性に優れるフィルム等の成形品を成形できる樹脂組成物が得られることを見出し、本発明を完成した。 However, as a result of intensive studies conducted by the present inventors in view of such circumstances, in a resin composition containing a PVA-based resin and a saccharide, the saccharide was contained in a larger amount than before, and further, elasticity when formed into a film. By making the rate high, it is possible to obtain a resin composition capable of forming a molded article such as a film having excellent shape stability of the packaging material under high humidity and excellent crack resistance under low humidity. Heading, completed the present invention.
即ち、本発明の第１の要旨は、Ｐポリビニルアルコール系樹脂（Ａ）と糖類（Ｂ）を含有する樹脂組成物において、
糖類（Ｂ）がマンニトールであり、
糖類（Ｂ）の含有量が、ポリビニルアルコール系樹脂（Ａ）１００重量部に対して、３０〜９０重量部であり、前記樹脂組成物からなるフィルムを２５℃、６５％ＲＨで１週間調湿した際の該フィルムの弾性率が６００Ｎ／ｍｍ2以上であることを特徴とする樹脂組成物に関するものである。
That is, the first gist of the present invention is a resin composition containing a P polyvinyl alcohol resin (A) and a saccharide (B),
Saccharide (B) is mannitol,
The content of the saccharide (B) is 30 to 90 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin (A), and the film made of the resin composition is conditioned at 25° C. and 65% RH for 1 week. The present invention relates to a resin composition, wherein the elastic modulus of the film is 600 N/mm 2 or more.
また、本発明では、前記の樹脂組成物からなる成形品も提供するものである。
Also, in the present invention, the molded article comprising the resin composition is also intended to provide.
本発明の樹脂組成物は、高湿度下での強度や低湿度下の耐ひび割れ性に優れていることから、高湿度低湿度両方の環境下で保存、使用される農業用フィルムや医薬用フィルム等、各種用途に用いることができる。
本発明においては、ＰＶＡ系樹脂及び糖類を、例えば水溶液として混合することにより、水に溶解した糖類は可塑剤として作用し、溶解しきれなかった糖類はフィラーとして作用することとなり、弾性率が向上し高湿度下では強度に優れ、一方、低湿度下ではひび割れが生じなかったものである。
The resin composition of the present invention is excellent in strength under high humidity and crack resistance under low humidity, so that it is stored in both high humidity and low humidity environments, and used as an agricultural film or a pharmaceutical film. Etc. can be used for various purposes.
In the present invention, by mixing the PVA-based resin and the saccharide, for example, as an aqueous solution, the saccharide dissolved in water acts as a plasticizer, and the saccharide that cannot be completely dissolved acts as a filler, which improves the elastic modulus. However, it has excellent strength under high humidity, while cracks did not occur under low humidity.
以下、本発明を詳細に説明するが、これらは望ましい実施態様の一例を示すものである。 BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below, but these show one example of preferred embodiments.
本発明の樹脂組成物は、ＰＶＡ系樹脂（Ａ）と糖類（Ｂ）を含有し、糖類（Ｂ）の含有量が、ＰＶＡ系樹脂（Ａ）１００重量部に対して、３０〜９０重量部であり、前記樹脂組成物からなるフィルムを２５℃、６５％ＲＨで１週間調湿した際の該フィルムの弾性率が６００Ｎ／ｍｍ2以上であることを特徴とする樹脂組成物である。
また、本発明の樹脂組成物は、ＰＶＡ系樹脂（Ａ）と糖類（Ｂ）を含有し、糖類（Ｂ）の含有量が、ＰＶＡ系樹脂（Ａ）１００重量部に対して、３０〜９０重量部であり、かつ糖類（Ｂ）の吸水率が１．００３以下であることを特徴とする樹脂組成物である。
The resin composition of the present invention contains the PVA-based resin (A) and the saccharide (B), and the content of the saccharide (B) is 30 to 90 parts by weight with respect to 100 parts by weight of the PVA-based resin (A). The resin composition has a modulus of elasticity of 600 N/mm 2 or more when the film made of the resin composition is conditioned at 25° C. and 65% RH for 1 week.
The resin composition of the present invention contains the PVA-based resin (A) and the saccharide (B), and the content of the saccharide (B) is 30 to 90 with respect to 100 parts by weight of the PVA-based resin (A). The resin composition is characterized in that it is parts by weight and the water absorption of the saccharide (B) is 1.003 or less.
〔ＰＶＡ系樹脂（Ａ）〕
まず、本発明で用いられるＰＶＡ系樹脂（Ａ）について説明する。
ＰＶＡ系樹脂（Ａ）は、ビニルエステル系単量体を共重合して得られるポリビニルエステル系樹脂をケン化して得られる、ビニルアルコール構造単位を主体とする樹脂であり、ケン化度相当のビニルアルコール構造単位とビニルエステル構造単位から構成される。
[PVA-based resin (A)]
First, the PVA-based resin (A) used in the present invention will be described.
The PVA-based resin (A) is a resin having a vinyl alcohol structural unit as a main component, which is obtained by saponifying a polyvinyl ester-based resin obtained by copolymerizing a vinyl ester-based monomer, and has a degree of saponification of vinyl. It is composed of alcohol structural units and vinyl ester structural units.
上記ビニルエステル系単量体としては、例えば、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、バレリン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、安息香酸ビニル、バーサチック酸ビニル等が挙げられるが、中でも経済的に酢酸ビニルが好ましく用いられる。 Examples of the vinyl ester-based monomer include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, and benzoate. Examples thereof include vinyl acid and vinyl versatate, and of these, vinyl acetate is preferably used economically.
本発明で用いられるＰＶＡ系樹脂（Ａ）の平均重合度（ＪＩＳ Ｋ６７２６に準拠して測定）は、通常、２００〜４０００であり、特に２３０〜３５００、さらに２５０〜３０００のものが好ましく用いられる。
かかる平均重合度が小さすぎると成形品の強度が低下する傾向があり、大きすぎると水溶液の安定性、及びハンドリング性が低下する傾向がある。
The PVA-based resin (A) used in the present invention has an average degree of polymerization (measured in accordance with JIS K6726) of usually 200 to 4000, particularly preferably 230 to 3500, and more preferably 250 to 3000.
If the average degree of polymerization is too small, the strength of the molded product tends to decrease, and if it is too large, the stability of the aqueous solution and the handling property tend to decrease.
また、本発明で用いられるＰＶＡ系樹脂（Ａ）のケン化度（ＪＩＳ Ｋ６７２６に準拠して測定）は、通常、６０〜１００モル％であり、特に７０〜９９．５モル％、さらに８０〜９５モル％のものが好適に用いられる。
かかるケン化度が低すぎると、結晶性、及び水素結合能力が低下する傾向がある。
The saponification degree (measured in accordance with JIS K6726) of the PVA-based resin (A) used in the present invention is usually 60 to 100 mol %, particularly 70 to 99.5 mol %, and further 80 to Those of 95 mol% are preferably used.
If the saponification degree is too low, the crystallinity and the hydrogen bonding ability tend to decrease.
また、本発明では、ＰＶＡ系樹脂（Ａ）として、ポリビニルエステル系樹脂の製造時に各種単量体を共重合させ、これをケン化して得られたものや、ＰＶＡ系樹脂に後変性によって各種官能基を導入した各種変性ＰＶＡ系樹脂を用いることができる。かかる変性は、ＰＶＡ系樹脂の水溶性が失われない範囲で行うことができる。 Further, in the present invention, as the PVA-based resin (A), those obtained by copolymerizing various monomers at the time of producing a polyvinyl ester-based resin and saponifying the same, or various functionalities obtained by post-modifying the PVA-based resin. Various modified PVA-based resins having a group introduced can be used. Such modification can be performed within a range in which the water solubility of the PVA-based resin is not lost.
ビニルエステル系単量体との共重合に用いられる単量体としては、例えば、エチレンやプロピレン、イソブチレン、α−オクテン、α−ドデセン、α−オクタデセン等のオレフィン類、３−ブテン−１−オール、４−ペンテン−１−オール、５−ヘキセン−１−オール、３，４−ジヒドロキシ−１−ブテン等のヒドロキシ基含有α−オレフィン類およびそのアシル化物などの誘導体、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、無水マレイン酸、イタコン酸等の不飽和酸類、その塩、モノエステル、あるいはジアルキルエステル、アクリロニトリル、メタアクリロニトリル等のニトリル類、ジアセトンアクリルアミド、アクリルアミド、メタクリルアミド等のアミド類、エチレンスルホン酸、アリルスルホン酸、メタアリルスルホン酸等のオレフィンスルホン酸類あるいはその塩、アルキルビニルエーテル類、ジメチルアリルビニルケトン、Ｎ−ビニルピロリドン、塩化ビニル、ビニルエチレンカーボネート、２，２−ジアルキル−４−ビニル−１，３−ジオキソラン、グリセリンモノアリルエーテル、３，４−ジアセトキシ−１−ブテン、等のビニル化合物、酢酸イソプロペニル、１−メトキシビニルアセテート等の置換酢酸ビニル類、塩化ビニリデン、１，４−ジアセトキシ−２−ブテン、ビニレンカーボネート、等が挙げられる。 Examples of the monomer used for copolymerization with the vinyl ester-based monomer include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, and α-octadecene, and 3-buten-1-ol. , 4-Penten-1-ol, 5-hexen-1-ol, 3,4-dihydroxy-1-butene and other hydroxy group-containing α-olefins and their derivatives such as acyl compounds, acrylic acid, methacrylic acid, croton Unsaturated acids such as acids, maleic acid, maleic anhydride, itaconic acid, etc., their salts, monoesters, or nitriles such as dialkyl esters, acrylonitrile, methacrylonitrile, etc., amides such as diacetone acrylamide, acrylamide, methacrylamide, ethylene. Olefin sulfonic acids such as sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid or salts thereof, alkyl vinyl ethers, dimethylallyl vinyl ketone, N-vinyl pyrrolidone, vinyl chloride, vinyl ethylene carbonate, 2,2-dialkyl-4-vinyl Vinyl compounds such as -1,3-dioxolane, glycerin monoallyl ether, and 3,4-diacetoxy-1-butene; substituted vinyl acetates such as isopropenyl acetate and 1-methoxyvinyl acetate; vinylidene chloride; Examples thereof include diacetoxy-2-butene and vinylene carbonate.
また、共重合変性ＰＶＡとして、側鎖に一級水酸基を有するＰＶＡ系樹脂が挙げられる。かかるＰＶＡ系樹脂としては、例えば、３，４−ジアセトキシ−１−ブテン、ビニルエチレンカーボネート、グリセリンモノアリルエーテル等を共重合して得られる側鎖１，２ジオール変性ＰＶＡ系樹脂、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−メチレンプロパン等のヒドロキシメチルビニリデンジアセテート等を共重合して得られる側鎖にヒドロキシメチル基を有するＰＶＡ系樹脂が挙げられる。 Examples of the copolymer-modified PVA include PVA-based resins having a primary hydroxyl group on the side chain. Examples of the PVA-based resin include side chain 1,2-diol-modified PVA-based resin obtained by copolymerizing 3,4-diacetoxy-1-butene, vinylethylene carbonate, glycerin monoallyl ether, and 1,3- Side chains obtained by copolymerizing hydroxymethylvinylidene diacetate such as diacetoxy-2-methylenepropane, 1,3-dipropionyloxy-2-methylenepropane, and 1,3-dibutyronyloxy-2-methylenepropane. A PVA-based resin having a hydroxymethyl group may be mentioned.
また、後反応によって官能基が導入されたＰＶＡ系樹脂としては、ジケテンとの反応によるアセトアセチル基を有するもの、エチレンオキサイドとの反応によるポリアルキレンオキサイド基を有するもの、エポキシ化合物等との反応によるヒドロキシアルキル基を有するもの、あるいは各種官能基を有するアルデヒド化合物をＰＶＡと反応させて得られるものなどを挙げることができる。
かかる変性ＰＶＡ系樹脂中の変性種、すなわち共重合体中の各種単量体に由来する構成単位、あるいは後反応によって導入された官能基の含有量は、変性種によって特性が大きく異なるため一概には言えないが、通常、０．１〜２０モル％であり、特に０．５〜１２モル％、更に１〜１０モル％の範囲が好ましく用いられる。
Examples of the PVA-based resin having a functional group introduced by post-reaction include those having an acetoacetyl group by the reaction with diketene, those having a polyalkylene oxide group by the reaction with ethylene oxide, and those having a reaction with an epoxy compound. Examples thereof include those having a hydroxyalkyl group and those obtained by reacting an aldehyde compound having various functional groups with PVA.
The modified species in the modified PVA-based resin, that is, the content of the constituent units derived from various monomers in the copolymer, or the content of the functional group introduced by the post-reaction is largely different depending on the modified species. Although it cannot be said, it is usually 0.1 to 20 mol %, particularly 0.5 to 12 mol %, and more preferably 1 to 10 mol %.
〔糖類（Ｂ）〕
次に、本発明で用いられる糖類（Ｂ）について説明する。
糖類（Ｂ）としては、マンニトールが挙げられる。低吸湿性の点でマンニトールが特に好ましい。
[Sugar (B)]
Next, the saccharide (B) used in the present invention will be described.
The saccharide (B), include Ma N'nito Le. Mannitol is particularly preferable in terms of low hygroscopicity.
また、糖類（Ｂ）は、添加により弾性率を低下させないという点で、吸水率が１．００３重量％以下であることが好ましく、更に好ましくは１．００２重量％以下、特に好ましくは１．００１重量％以下である。吸水率が大きすぎると弾性率が低下する傾向がある。なお、下限値は通常１．０００１重量％程度である。
かかる吸水率は、３０℃、９０％ＲＨ下で糖類を保管し、1週間後の重量を測定し、保管前からの重量変化より求めるものとする。
吸水率(重量％)＝〔（Ｗ２−Ｗ１）／Ｗ１〕×１００
Ｗ１：吸水前の試料の重量
Ｗ２：吸水後の試料の重量
Further, the sugar (B) preferably has a water absorption of 1.003% by weight or less, more preferably 1.002% by weight or less, and particularly preferably 1.001, from the viewpoint of not reducing the elastic modulus by addition. It is less than or equal to weight %. If the water absorption is too large, the elastic modulus tends to decrease. The lower limit is usually about 1.0001% by weight.
The water absorption is determined by storing the saccharide at 30° C. and 90% RH, measuring the weight after one week, and measuring the weight change from before storage.
Water absorption rate (wt%) = [(W2-W1)/W1] x 100
W1: Weight of sample before water absorption W2: Weight of sample after water absorption
〔樹脂組成物〕
本発明においては、ＰＶＡ系樹脂（Ａ）と糖類（Ｂ）を含有するものであるが、糖類（Ｂ）の含有量は、ＰＶＡ系樹脂（Ａ）１００重量部に対して、３０〜９０重量部であり、好ましくは３５〜８０重量部、更に好ましくは４０〜７０重量部である。かかる含有量が多すぎても少なすぎても、得られる成形品、とりわけフィルムの形状安定性が低下することとなる。
[Resin composition]
In the present invention, the PVA-based resin (A) and the saccharide (B) are contained, but the content of the saccharide (B) is 30 to 90 parts by weight with respect to 100 parts by weight of the PVA-based resin (A). Parts, preferably 35 to 80 parts by weight, more preferably 40 to 70 parts by weight. If the content is too large or too small, the shape stability of the resulting molded article, especially the film, will be reduced.
本発明の樹脂組成物は、フィルムにした際の弾性率が６００Ｎ／ｍｍ2以上である。
かかる弾性率の測定方法は以下の通りである。
即ち、樹脂組成物から得られたフィルムに対して、オートグラフ（島津製作所社製、ＡＧ−ＩＳ）を用いて、幅１０ｍｍ、つかみ具間距離５０ｍｍ、引張速度１００ｍｍ/ｍiｎにて引張試験を行い、そのときの弾性率を算出するものである。
なお、弾性率の測定に当たっては、既にフィルムとして存在する場合は、そのまま該フィルムを用いて、上述の通り弾性率を測定することができ、樹脂組成物として存在する場合は、例えば、以下の（１）及び（２）の方法でフィルムとし弾性率を測定することができる。
（１）ＰＶＡ系樹脂（Ａ）と糖類（Ｂ）を水に溶解させ、樹脂組成物水溶液を作製する。
（２）得られた樹脂組成物水溶液を１００μｍのＰＥＴ基材に塗工し、８０℃で２時間乾燥して、膜厚１００μｍのフィルムとし、その後２５℃、６５％ＲＨで１週間調湿し、フィルムを得る。
The resin composition of the present invention has an elastic modulus of 600 N/mm 2 or more when formed into a film.
The method of measuring the elastic modulus is as follows.
That is, a film obtained from the resin composition was subjected to a tensile test using an autograph (manufactured by Shimadzu Corporation, AG-IS) at a width of 10 mm, a distance between grips of 50 mm, and a pulling speed of 100 mm/min. The elastic modulus at that time is calculated.
In the measurement of the elastic modulus, when it is already present as a film, the film can be used as it is to measure the elastic modulus as described above, and when it is present as a resin composition, for example, the following ( The elastic modulus can be measured as a film by the methods 1) and 2).
(1) The PVA-based resin (A) and the saccharide (B) are dissolved in water to prepare an aqueous resin composition solution.
(2) The obtained resin composition aqueous solution was applied to a PET substrate having a thickness of 100 μm and dried at 80° C. for 2 hours to give a film having a thickness of 100 μm, and then the humidity was adjusted at 25° C. and 65% RH for 1 week. , Get the film.
上記の測定方法で得られたフィルムの弾性率が６００Ｎ／ｍｍ2以上であることが必要であり、好ましくは７００Ｎ／ｍｍ2以上、特に好ましくは１０００Ｎ／ｍｍ2以上である。かかる弾性率が小さすぎると高湿度下での強度が低下する傾向がある。更に、かかる弾性率の上限としては通常３０００Ｎ／ｍｍ2、好ましくは２８００Ｎ／ｍｍ2、特に好ましくは２５００Ｎ／ｍｍ2である。 The elastic modulus of the film obtained by the above measuring method needs to be 600 N/mm 2 or more, preferably 700 N/mm 2 or more, and particularly preferably 1000 N/mm 2 or more. If the elastic modulus is too small, the strength under high humidity tends to decrease. Furthermore, normal 3000N / mm 2 is the upper limit of such elastic modulus, it is preferably 2800N / mm 2, particularly preferably 2500N / mm 2.
本発明において、上記フィルムの弾性率を調整するに際しては、例えば、（１）糖類の吸湿性（吸水率）を調整する、（２）ＰＶＡ系樹脂のケン化度を調整する、（３）フィルムの含水率を調整する等の方法が挙げられ、中でもフィルム作製時の簡便性の点で（１）の方法が好ましい。 In the present invention, when adjusting the elastic modulus of the film, for example, (1) adjust hygroscopicity (water absorption) of sugars, (2) adjust saponification degree of PVA-based resin, (3) film The method (1) is preferable from the viewpoint of the convenience of film production.
本発明の樹脂組成物には、本発明の効果を阻害しない範囲で、ＰＶＡ系樹脂（Ａ）及び糖類（Ｂ）とは異なる他の水溶性高分子を含有していてもよい。他の水溶性高分子としては、例えば、澱粉、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース等を挙げることができる。
上記の他の水溶性高分子の含有量としては、樹脂組成物に対して、１０重量％以下、特には５重量％以下が好ましい。
The resin composition of the present invention may contain another water-soluble polymer different from the PVA-based resin (A) and the saccharide (B) within a range that does not impair the effects of the present invention. Examples of other water-soluble polymers include starch, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose and the like.
The content of the above other water-soluble polymer is preferably 10% by weight or less, and particularly preferably 5% by weight or less based on the resin composition.
また、本発明の樹脂組成物には、本発明の効果を阻害しない範囲で、必要に応じて、補強剤、充填剤、可塑剤、顔料、染料、滑剤、酸化防止剤、帯電防止剤、紫外線吸収剤、熱安定剤、光安定剤、界面活性剤、抗菌剤、帯電防止剤、乾燥剤、アンチブロッキング剤、難燃剤、架橋剤、硬化剤、発泡剤、結晶核剤などが含有されてもよい。 Further, in the resin composition of the present invention, a reinforcing agent, a filler, a plasticizer, a pigment, a dye, a lubricant, an antioxidant, an antistatic agent, an ultraviolet ray, if necessary, within a range that does not impair the effects of the present invention. Even if it contains an absorbent, a heat stabilizer, a light stabilizer, a surfactant, an antibacterial agent, an antistatic agent, a drying agent, an antiblocking agent, a flame retardant, a crosslinking agent, a curing agent, a foaming agent, a crystal nucleating agent, etc. Good.
本発明の樹脂組成物は公知の混合方法により水溶液に調製することができる。例えば、（ｉ）ＰＶＡ系樹脂（Ａ）の粉末と糖類（Ｂ）の粉末とを混合し、水溶液とする方法、（ｉｉ）ＰＶＡ系樹脂（Ａ）の水溶液に糖類（Ｂ）の粉末を添加し、水溶液とする方法、（ｉｉｉ）糖類（Ｂ）の水溶液にＰＶＡ系樹脂（Ａ）の粉末を添加し、水溶液とする方法、（ｉｖ）ＰＶＡ系樹脂（Ａ）の水溶液と糖類（Ｂ）の水溶液を混合する等が挙げられる。中でも製造効率の点から（ｉ）と（ｉｉｉ）の方法が好ましい。 The resin composition of the present invention can be prepared into an aqueous solution by a known mixing method. For example, (i) PVA-based resin (A) powder and saccharide (B) powder are mixed to form an aqueous solution, and (ii) saccharide (B) powder is added to the PVA-based resin (A) aqueous solution. And (iii) an aqueous solution of the saccharide (B) is added to the aqueous solution of the saccharide (B) to form an aqueous solution, (iv) an aqueous solution of the PVA resin (A) and the saccharide (B) And the like. Among them, the methods (i) and (iii) are preferable from the viewpoint of production efficiency.
本発明の樹脂組成物の水溶液としては、作業性の点から、樹脂濃度が５〜３０重量％であることが好ましく、特には１０〜２５重量％、更には１５〜２３重量％であることが好ましい。 From the viewpoint of workability, the aqueous solution of the resin composition of the present invention preferably has a resin concentration of 5 to 30% by weight, particularly 10 to 25% by weight, and further 15 to 23% by weight. preferable.
本発明の樹脂組成物は、高湿度下及び低湿度下の環境下でも使用できるので、種々の用途に有効に用いられる。
本発明の樹脂組成物の用途としては、例えば、下記の（１）〜（１０）に示すような各種用途が挙げられる。
（１）成形品関係：繊維、フィルム、シート、パイプ、チューブ、防漏膜、暫定皮膜、ケミカルレース用、水溶性繊維等。
（２）接着剤関係：錠剤のバインダー、木材、紙、アルミ箔、プラスチック等の接着剤、粘着剤、再湿剤、不織布用バインダー、石膏ボードや繊維板等の各種建材用バインダー、各種粉体造粒用バインダー、セメントやモルタル用添加剤、ホットメルト型接着剤、感圧接着剤、アニオン性塗料の固着剤等。
（３）被覆剤関係：錠剤のコーティング剤、紙の顔料コーティング剤、紙の内添サイズ剤、繊維製品用サイズ剤、経糸糊剤、繊維加工剤、皮革仕上げ剤、塗料、防曇剤、金属腐食防止剤、亜鉛メッキ用光沢剤、帯電防止剤、導電剤、暫定塗料等。
（４）疎水性樹脂用ブレンド剤関係：疎水性樹脂の帯電防止剤、および親水性付与剤、複合繊維、フィルムその他成形物用添加剤等。
（５）増粘剤関係：各種水溶液やエマルジョンや食料品や医薬品の増粘剤等。
（６）凝集剤関係：水中懸濁物及び溶存物の凝集剤、パルプ、スラリーの濾水性等。
（７）交換樹脂等関係：イオン交換樹脂、キレート交換樹脂、イオン交換膜等。
（８）その他：土壌改良剤、感光剤、感光性レジスト樹脂等。
上記の中でも特に、本発明の樹脂組成物は、フィルムやシート等の成形品やコーティング剤として有用であり、特にフィルムや容器等の成形品として有用である。
Since the resin composition of the present invention can be used under the environment of high humidity and low humidity, it is effectively used for various purposes.
Examples of the use of the resin composition of the present invention include various uses shown in the following (1) to (10).
(1) Molded products: fibers, films, sheets, pipes, tubes, leak-proof films, temporary films, chemical laces, water-soluble fibers, etc.
(2) Adhesives: Binders for tablets, adhesives for wood, paper, aluminum foil, plastics, etc., adhesives, rewetting agents, binders for non-woven fabrics, binders for various building materials such as gypsum board and fiber board, various powders Binders for granulation, additives for cement and mortar, hot melt adhesives, pressure sensitive adhesives, fixing agents for anionic paints, etc.
(3) Coating agents: Tablet coating agents, paper pigment coating agents, paper internal sizing agents, textile product sizing agents, warp sizing agents, fiber processing agents, leather finishing agents, paints, anti-fog agents, metals Corrosion inhibitors, brighteners for zinc plating, antistatic agents, conductive agents, temporary paints, etc.
(4) Blending agent for hydrophobic resin: Antistatic agent for hydrophobic resin, hydrophilicity-imparting agent, composite fiber, film and other additives for molded articles.
(5) Thickener-related: Thickeners for various aqueous solutions, emulsions, foodstuffs and pharmaceuticals.
(6) Flocculant-related: Flocculant of suspended solids and dissolved substances in water, pulp, drainage of slurry, etc.
(7) Exchange resin, etc.: Ion exchange resin, chelate exchange resin, ion exchange membrane, etc.
(8) Others: Soil conditioner, photosensitizer, photosensitive resist resin, etc.
Among the above, the resin composition of the present invention is particularly useful as a molded product such as a film or sheet or a coating agent, and particularly useful as a molded product such as a film or a container.
次に本発明の樹脂組成物の好ましい使用形態について詳細に説明する。
〔成形品〕
本発明においては、上記樹脂組成物を用いて成形品が得られる。かかる成形品の形状としては、例えば、フィルム状、カップ状、チューブ状、中空状などが挙げられ、特にフィルム状のものが好適に用いられる。
Next, a preferred usage of the resin composition of the present invention will be described in detail.
〔Molding〕
In the present invention, a molded product is obtained using the resin composition. Examples of the shape of such a molded product include a film shape, a cup shape, a tube shape, and a hollow shape, and a film shape is particularly preferably used.
以下に、フィルムを作製する(製膜)方法について詳細に説明する。フィルムを作製するには、例えば、流延法等の方法を採用することができる。
流延法の方法にて製膜する際の樹脂組成物の固形分濃度は、通常５〜３０重量％、好ましくは８〜２０重量％、特に好ましくは１０〜１５重量％である。かかる樹脂組成物の固形分濃度が低すぎると生産性が低下する傾向があり、高すぎると高粘度となってドープの脱泡に時間を要したり、フィルム製膜時にダイラインが発生する傾向がある。
The method for producing a film (film formation) will be described in detail below. For producing the film, for example, a method such as a casting method can be adopted.
The solid content concentration of the resin composition when the film is formed by the casting method is usually 5 to 30% by weight, preferably 8 to 20% by weight, and particularly preferably 10 to 15% by weight. If the solid content of the resin composition is too low, the productivity tends to decrease, and if it is too high, the viscosity becomes high and it takes time to defoam the dope, or a die line tends to occur during film formation. is there.
又、アプリケーターを用いて、上記樹脂組成物の水溶液をポリエチレンテレフタレートフィルムやポリエチレンフィルム等のプラスチック基材あるいは金属基材上にキャストして、乾燥させてフィルムを得ることができる。
また、乾燥温度としては、通常５０〜１４０℃、好ましくは６０〜１２０℃、特に好ましくは８０〜１００℃である。かかる温度が低すぎると乾燥に時間を要してしまう傾向があり、高すぎると製膜時に発泡してしまう傾向がある。
また乾燥時間は、通常０．１〜６時間、好ましくは１〜４時間、特に好ましくは２〜３時間である。
Further, an aqueous solution of the above resin composition can be cast on a plastic substrate or a metal substrate such as a polyethylene terephthalate film or a polyethylene film using an applicator and dried to obtain a film.
The drying temperature is usually 50 to 140°C, preferably 60 to 120°C, and particularly preferably 80 to 100°C. If the temperature is too low, drying tends to take time, and if it is too high, foaming tends to occur during film formation.
The drying time is usually 0.1 to 6 hours, preferably 1 to 4 hours, particularly preferably 2 to 3 hours.
上記の方法で得られたフィルムにおいては、その厚みは、用途により適宜選択されるが、通常５〜１００μｍ、特には１０〜８０μｍであることが好ましく、かかる厚みが薄すぎるとフィルムの機械的強度が低下する傾向があり、逆に厚すぎると製膜効率が低下し、製造効率が低下する傾向がある。
又、該フィルムの表面はプレーンであってもよいが、ブロッキング性、加工時の滑り性、製品同士の密着性軽減の点から、該フィルムの片面或いは両面にエンボス模様や梨地模様等を施しておくこともできる。
In the film obtained by the above method, the thickness is appropriately selected depending on the application, but is usually 5 to 100 μm, particularly preferably 10 to 80 μm, and if the thickness is too thin, the mechanical strength of the film On the contrary, if it is too thick, on the other hand, the film-forming efficiency tends to decrease and the production efficiency tends to decrease.
Further, the surface of the film may be plain, but from the viewpoint of blocking properties, slipperiness during processing, and reduction of adhesion between products, one side or both sides of the film may be embossed or satin finished. You can also leave it.
本発明の樹脂組成物からなる成形品の用途としては上記の用途以外にも、下記の用途が挙げられる。
例えば、飲食品用包装材、薬剤（農薬、医薬）の包装材、繊維、シート、パイプ、チューブ、防漏膜、暫定皮膜、ケミカルレース用繊維、水溶性繊維、容器、バッグインボックス用内袋、容器用パッキング、医療用輸液バッグ、有機液体用容器、有機液体輸送用パイプ、各種ガスの容器（チューブ、ホース）などが挙げられる。また、各種電気部品、自動車部品、工業用部品、レジャー用品、スポーツ用品、日用品、玩具、医療器具などに用いることも可能である。
In addition to the above applications, the molded articles made of the resin composition of the present invention include the following applications.
For example, packaging materials for food and drink, packaging materials for drugs (agricultural chemicals, pharmaceuticals), fibers, sheets, pipes, tubes, leak-proof films, temporary films, fibers for chemical lace, water-soluble fibers, containers, inner bags for bag-in-boxes , Container packings, medical infusion bags, organic liquid containers, organic liquid transport pipes, various gas containers (tubes, hoses) and the like. Further, it can be used for various electric parts, automobile parts, industrial parts, leisure goods, sports goods, daily necessities, toys, medical instruments and the like.
以下、実施例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。なお、例中「％」及び「部」とあるのは重量基準を意味する。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the examples, “%” and “part” mean weight basis.
実施例１
［樹脂組成物水溶液（１）の作製］
マンニトール（和光純薬社製）７．５部を８５部の水に添加後、室温で１０分撹拌し完全に溶解させ、８．１％水溶液を得た。得られたマンニトール水溶液にＰＶＡ系樹脂（未変性、ケン化度８８モル％、平均重合度２４００）１５部を添加後、８５℃に昇温させＰＶＡ系樹脂を溶解し、樹脂組成物水溶液（１）を作製した。
Example 1
[Preparation of Resin Composition Aqueous Solution (1)]
After adding 7.5 parts of mannitol (manufactured by Wako Pure Chemical Industries, Ltd.) to 85 parts of water, the mixture was stirred at room temperature for 10 minutes and completely dissolved to obtain an 8.1% aqueous solution. After adding 15 parts of PVA-based resin (unmodified, saponification degree 88 mol%, average degree of polymerization 2400) to the obtained mannitol aqueous solution, the temperature is raised to 85° C. to dissolve the PVA-based resin, and the resin composition aqueous solution (1 ) Was produced.
［フィルム（１）の作製］
上記で得られた樹脂組成物水溶液（１）を１００μｍのＰＥＴ基材に塗工し、８０℃で２時間乾燥して、膜厚１００μｍのフィルムとして、２５℃、６５％ＲＨで１週間調湿し、フィルム（１）を得た。
得られたフィルム（１）について、以下の評価を行った。
[Production of film (1)]
The resin composition aqueous solution (1) obtained above is applied to a PET substrate having a thickness of 100 μm and dried at 80° C. for 2 hours to prepare a film having a thickness of 100 μm at 25° C. and 65% RH for 1 week. Then, a film (1) was obtained.
The following evaluation was performed about the obtained film (1).
［弾性率評価］
２５℃、６５％ＲＨの環境下で、上記で得られたフィルム（１）の引張試験を実施した。引張試験は、オートグラフ（島津製作所社製、ＡＧ−ＩＳ）を用いて、幅１０ｍｍ、つかみ具間距離５０ｍｍ、引張速度１００ｍｍ/ｍiｎで行い、弾性率を算出した。
[Evaluation of elastic modulus]
The tensile test of the film (1) obtained above was carried out in an environment of 25° C. and 65% RH. The tensile test was performed using an autograph (manufactured by Shimadzu Corporation, AG-IS) at a width of 10 mm, a distance between grips of 50 mm, and a pulling speed of 100 mm/min to calculate the elastic modulus.
[耐ひび割れ性評価]
上記で得られたフィルム（１）を幅１０ｍｍ、長さ１００ｍｍに裁断し、短冊フィルムを作製し、２５℃、２０％ＲＨで１週間調湿した。得られた短冊フィルムの真ん中を中心に二つ折りにし、目視でひび割れの有無を確認した。
[Crack resistance evaluation]
The film (1) obtained above was cut into a width of 10 mm and a length of 100 mm to prepare a strip film, and the humidity was adjusted at 25° C. and 20% RH for 1 week. The obtained strip-shaped film was folded in half around the center and visually checked for cracks.
実施例２
実施例１において、マンニトールの含有量を６部にした以外は、実施例１と同様にしてフィルム（２）を得て、実施例１と同様に評価した。
Example 2
In Example 1, a film (2) was obtained in the same manner as in Example 1 except that the content of mannitol was changed to 6 parts, and evaluated in the same manner as in Example 1.
実施例３
実施例１において、マンニトールの含有量を４．５部にした以外は、実施例１と同様にしてフィルム（３）を得て、実施例１と同様に評価した。
Example 3
A film (3) was obtained in the same manner as in Example 1 except that the content of mannitol was changed to 4.5 parts in Example 1, and the same evaluation as in Example 1 was performed.
比較例５
実施例１において、マンニトールをイソマルツロース（東京化成工業社製）に変えて、イソマルツロースの含有量を７．５部にした以外は、実施例１と同様にしてフィルム（４）を得て、実施例１と同様に評価した。
Comparative Example 5
A film (4) was obtained in the same manner as in Example 1 except that mannitol was changed to isomaltulose (manufactured by Tokyo Chemical Industry Co., Ltd.) and the content of isomaltulose was changed to 7.5 parts. And evaluated in the same manner as in Example 1.
比較例１
実施例１において、マンニトールを含有しなかった以外は、実施例１と同様にしてフィルム（５）を得て、実施例１と同様に評価した。
Comparative Example 1
A film (5) was obtained in the same manner as in Example 1 except that mannitol was not contained, and the same evaluation as in Example 1 was carried out.
比較例２
実施例１において、マンニトールの含有量を３部とした以外は、実施例１と同様にしてフィルム（６）を得て、実施例１と同様に評価した。
Comparative example 2
In Example 1, a film (6) was obtained in the same manner as in Example 1 except that the content of mannitol was changed to 3 parts, and evaluated in the same manner as in Example 1.
比較例３
実施例１において、マンニトールの含有量を１５部とした以外は、実施例１と同様にしてフィルム（７）を得て、実施例１と同様に評価した。
Comparative Example 3
A film (7) was obtained in the same manner as in Example 1 except that the content of mannitol was changed to 15 parts in Example 1 and evaluated in the same manner as in Example 1.
比較例４
実施例１において、マンニトールをエリスリトール（東京化成工業社製）に変えた以外は、実施例１と同様にしてフィルム（８）を得て、実施例１と同様に評価した。
Comparative Example 4
A film (8) was obtained in the same manner as in Example 1 except that erythritol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of mannitol in Example 1, and the same evaluation as in Example 1 was performed.
実施例及び比較例の結果を表１に示す。
The results of Examples and Comparative Examples are shown in Table 1.
本発明の樹脂組成物を用いた実施例１〜４においては、高湿度下においては、弾性率が高く強度に優れるものであり、低湿度下では割れがなかった。一方、糖類を配合しなかった又は配合量が少なかった比較例１及び２の樹脂組成物では、弾性率が低く、形状安定性に劣るものであった。また糖類の含有量が多い比較例３では、弾性率が高かったものの低湿度下ではひび割れが生じた。更に、吸水率の高い糖類を配合した比較例４でも弾性率が低く、形状安定性に劣るものであった。 In Examples 1 to 4 using the resin composition of the present invention, the elastic modulus was high and the strength was excellent under high humidity, and there was no cracking under low humidity. On the other hand, in the resin compositions of Comparative Examples 1 and 2 in which the saccharide was not mixed or the compounding amount was small, the elastic modulus was low and the shape stability was poor. Further, in Comparative Example 3 in which the content of saccharides was large, although the elastic modulus was high, cracking occurred under low humidity. Further, in Comparative Example 4 in which a saccharide having a high water absorption rate was blended, the elastic modulus was low and the shape stability was poor.
本発明の水溶性樹脂組成物からなる成形品は、湿度下の形状安定性に優れるため、包装材、特に農薬や肥料、医薬品の包装材料として有用である。 The molded article comprising the water-soluble resin composition of the present invention is excellent in shape stability under humidity, and thus is useful as a packaging material, particularly as a packaging material for agricultural chemicals, fertilizers, and pharmaceuticals.
Claims (5)
糖類（Ｂ）がマンニトールであり、
糖類（Ｂ）の含有量が、ポリビニルアルコール系樹脂（Ａ）１００重量部に対して、３０〜９０重量部であり、前記樹脂組成物からなるフィルムを２５℃、６５％ＲＨで１週間調湿した際の該フィルムの弾性率が６００Ｎ／ｍｍ2以上であることを特徴とする樹脂組成物。 A resin composition containing a polyvinyl alcohol resin (A) and a saccharide (B),
Saccharide (B) is mannitol,
The content of the saccharide (B) is 30 to 90 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin (A), and the film made of the resin composition is conditioned at 25° C. and 65% RH for 1 week. A resin composition characterized in that the elastic modulus of the film is 600 N/mm 2 or more.
とする請求項１記載の樹脂組成物。 The resin composition according to claim 1, wherein the polyvinyl alcohol resin (A) has a saponification degree of 60 to 100 mol %.
とする請求項１又は２記載の樹脂組成物。 The average degree of polymerization of the polyvinyl alcohol-based resin (A) is 200 to 4000, and the resin composition according to claim 1 or 2.
糖類（Ｂ）の含有量が、ポリビニルアルコール系樹脂（Ａ）１００重量部に対して、３０〜９０重量部であり、かつ糖類（Ｂ）の吸水率が１．００３重量％以下であることを特徴とする樹脂組成物。 A resin composition containing a polyvinyl alcohol resin (A) and a saccharide (B),
The content of the saccharide (B) is 30 to 90 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin (A), and the water absorption of the saccharide (B) is 1.003% by weight or less. A characteristic resin composition.
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| IT1140254B (en) * | 1981-10-30 | 1986-09-24 | Pietro Cattaneo | THERMOPLASTIC COMPOSITION BASED ON POLYVINYL ALCOHOL SUITABLE TO BE SUBJECTED AS SUCH TO THE COMMON HOT FORMING METHODS OF THERMOPLASTIC MATERIALS, SUCH AS MOLDING AND EXTRUSION, FOR THE PRODUCTION OF MANUFACTURED, AND MANUFACTURED SUCH PRODUCTS |
| EP0635545A3 (en) * | 1993-07-21 | 1995-07-12 | Air Prod & Chem | Injection molded articles from extrudable polyvinyl alcohol compositions. |
| JP3365669B2 (en) * | 1994-02-07 | 2003-01-14 | 日本合成化学工業株式会社 | Resin composition |
| JPH09316006A (en) * | 1996-05-29 | 1997-12-09 | Yatsuken:Kk | Intraoral dissolvable solid pharmaceutical preparation |
| JP4472100B2 (en) * | 2000-04-03 | 2010-06-02 | 株式会社クラレ | Polyvinyl alcohol resin composition |
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