JP2017082172A - Molding - Google Patents
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- JP2017082172A JP2017082172A JP2015214757A JP2015214757A JP2017082172A JP 2017082172 A JP2017082172 A JP 2017082172A JP 2015214757 A JP2015214757 A JP 2015214757A JP 2015214757 A JP2015214757 A JP 2015214757A JP 2017082172 A JP2017082172 A JP 2017082172A
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Abstract
Description
本発明は、水溶性樹脂組成物からなる成形品に関し、更に詳しくは、高湿度下での形状安定性に優れる成形品に関するものである。 The present invention relates to a molded article made of a water-soluble resin composition, and more particularly to a molded article having excellent shape stability under high humidity.
ポリビニルアルコール系樹脂（以下、ＰＶＡ系樹脂という。）及びポリビニルピロリドン系樹脂（以下、ＰＶＰ系樹脂という。）はそれぞれ水溶性樹脂として、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ＰＶＰ系樹脂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、いずれも高湿度に置かれることもあり、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 polyvinylpyrrolidone-based resins (hereinafter referred to as PVP-based resins) have been used for various applications as water-soluble resins, taking advantage of their properties.
Examples include adhesives, pharmaceutical binders, dispersants, films, cosmetics, and the like.
Among them, in recent years, there has been an increasing demand for packaging materials, and packaging materials using PVA-based resins and PVP-based resins have come to be used in various applications.
For example, they are used in food packaging materials, pharmaceutical packaging materials, agricultural packaging materials, etc., all of which are placed in high humidity, and the strength of the packaging material in that case is a problem.
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。）。 In order to solve such a problem, studies have been made to contain a filler (for example, see Patent Document 1).
しかしながら、上記特許文献１の技術においても、高湿度下での包装材の強度の点で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対して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るフィルム等の成形品を提供することを目的とするものである。
However, even in the technique of the above-mentioned Patent Document 1, there is still no satisfactory product in terms of the strength of the packaging material under high humidity, and further improvements have been made against the recent increase in demand. It has been demanded.
Therefore, an object of the present invention is to provide a molded article such as a film having excellent shape stability of a packaging material under high humidity under such a background.
しかるに、本発明者等は、ＰＶＡ系樹脂とＰＶＰ系樹脂とを特定比率で混合すること、すなわち、ＰＶＡ系樹脂を主体成分として、これにＰＶＰ系樹脂を配合することにより、ＰＶＡ系樹脂単体又はＰＶＰ系樹脂単体のものよりも高湿度下での形状安定性に優れる成形品が得られることを見出し、本発明を完成するに至った。 However, the present inventors mixed the PVA resin and the PVP resin at a specific ratio, that is, by using the PVA resin as a main component and blending the PVP resin therein, the PVA resin alone or The present inventors have found that a molded product that is more excellent in shape stability under high humidity than that of a single PVP resin can be obtained, and the present invention has been completed.
すなわち、本発明の要旨は、ＰＶＡ系樹脂（Ａ）とＰＶＰ系樹脂（Ｂ）を含有し、ＰＶＡ系樹脂（Ａ）１００重量部に対して、ＰＶＰ系樹脂（Ｂ）の含有量が１〜６０重量部である水溶性樹脂組成物からなることを特徴とする成形品に関するものである。 That is, the gist of the present invention includes the PVA resin (A) and the PVP resin (B), and the PVP resin (B) content is 1 to 100 parts by weight of the PVA resin (A). The present invention relates to a molded product comprising a water-soluble resin composition in an amount of 60 parts by weight.
本発明の水溶性樹脂組成物からなる成形品は、両樹脂の分子間水素結合により、それぞれを単独で用いた場合に比べて、優れた形状安定性が得られるものと推測される。 The molded product comprising the water-soluble resin composition of the present invention is presumed to have excellent shape stability as compared to the case where each is used alone due to intermolecular hydrogen bonding between both resins.
本発明の水溶性樹脂組成物からなる成形品は、高湿度下での形状安定性に優れていることから、高湿度下で保存、使用される農業用フィルムや医薬用フィルム等、各種用途に使用することができる。 The molded article comprising the water-soluble resin composition of the present invention is excellent in shape stability under high humidity, so it can be stored and used under high humidity for various uses such as agricultural films and pharmaceutical films. Can be used.
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。 The present invention will be described in detail below, but these show examples of desirable embodiments.
本発明の成形品は、ＰＶＡ系樹脂（Ａ）とＰＶＰ系樹脂（Ｂ）を含有してなる水溶性樹脂組成物からなるものである。 The molded article of the present invention is composed of a water-soluble resin composition containing a PVA resin (A) and a PVP resin (B).
〔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 resin (A)]
First, the PVA resin (A) used in the present invention will be described.
The PVA resin (A) is a resin mainly composed of a vinyl alcohol structural unit obtained by saponification of a polyvinyl ester resin obtained by copolymerizing a vinyl ester monomer. Consists of alcohol structural units and vinyl ester structural units.
上記ビニルエステル系モノマーとしては、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、経済的に酢酸ビニルが好ましく用いられる。 Examples of the vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, versatic. Although vinyl acid acid etc. are mentioned, 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 average degree of polymerization (measured in accordance with JIS K6726) of the PVA resin (A) used in the present invention is usually 200 to 4000, particularly 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 and handling properties of the aqueous solution 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。
Further, the degree of saponification (measured in accordance with JIS K6726) of the PVA resin (A) used in the present invention is usually 60 to 100 mol%, particularly 70 to 99.5 mol%, and more preferably 80 to A 95 mol% thing is used suitably.
If the degree of saponification is too low, the crystallinity and 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、未変性ＰＶＡ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。 In the present invention, as the PVA-based resin (A), various monomers are copolymerized at the time of producing the polyvinyl ester-based resin and saponified, and various functionalities are obtained by post-modifying unmodified PVA. Various modified PVA-based resins into which groups are introduced can be used. Such modification can be performed as long as the water solubility of the PVA resin is not lost.
ビニルエステル系モノマー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 monomer include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, α-octadecene, 3-buten-1-ol, 4 -Derivatives such as hydroxy group-containing α-olefins such as penten-1-ol, 5-hexen-1-ol, 3,4-dihydroxy-1-butene and acylated products thereof, acrylic acid, methacrylic acid, crotonic acid, Unsaturated acids such as maleic acid, maleic anhydride, itaconic acid, salts thereof, monoesters or dialkyl esters, nitriles such as acrylonitrile and methacrylonitrile, amides such as diacetone acrylamide, acrylamide and methacrylamide, ethylene sulfonic acid , Allyl sulfonic acid, methallyl sulfo Olefin sulfonic acids such as acids or salts thereof, alkyl vinyl ethers, dimethylallyl vinyl ketone, N-vinyl pyrrolidone, vinyl chloride, vinyl ethylene carbonate, 2,2-dialkyl-4-vinyl-1,3-dioxolane, glycerin monoallyl Ethers, vinyl compounds such as 3,4-diacetoxy-1-butene, substituted vinyl acetates such as isopropenyl acetate and 1-methoxyvinyl acetate, vinylidene chloride, 1,4-diacetoxy-2-butene, vinylene carbonate, etc. Is mentioned.
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、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。 Moreover, PVA-type resin which has a primary hydroxyl group in a side chain as copolymerization modified PVA is mentioned. Examples of such PVA include side chain 1,2-diol-modified PVA obtained by copolymerizing 3,4-diacetoxy-1-butene, vinylethylene carbonate, glyceryl monoallyl ether, and the like, 1,3-diacetoxy-2- Hydroxymethyl group on the side chain obtained by copolymerizing hydroxymethylvinylidene diacetate such as methylenepropane, 1,3-dipropionyloxy-2-methylenepropane, 1,3-dibutyronyloxy-2-methylenepropane PVA-based resin having
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が有するもの、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た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％の範囲が好ましく用いられる。
In addition, PVA resins having a functional group introduced by a post-reaction include those having an acetoacetyl group by reaction with diketene, those having a polyalkylene oxide group by reaction with ethylene oxide, reaction with an epoxy compound, etc. Examples thereof include those having a hydroxyalkyl group or 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 constituent units derived from various monomers in the copolymer, or the content of the functional group introduced by the post-reaction is generally different depending on the modified species. Although it cannot be said, it is usually 0.1 to 20 mol%, and a range of 0.5 to 12 mol% is particularly preferably used.
〔ＰＶＰ系樹脂（Ｂ）〕
次に、本発明で用いられるＰＶＰ系樹脂（Ｂ）について説明する。
ＰＶＰ系樹脂（Ｂ）は、Ｎ−ビニル−２−ピロリドンの重合体であり、一般式（Ｃ6Ｈ9ＮＯ）nで表される。
ＰＶＰ系樹脂（Ｂ）の平均重合度（上記一般式のｎ）は、好ましくは５０〜１０００００、より好ましくは１００〜８００００であり、更に好ましくは１００００〜５００００である。
上記ＰＶＰ系樹脂（Ｂ）の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、平均重合度が大きすぎると、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。
[PVP resin (B)]
Next, the PVP resin (B) used in the present invention will be described.
The PVP resin (B) is a polymer of N-vinyl-2-pyrrolidone and is represented by the general formula (C 6 H 9 NO) n .
The average degree of polymerization (n in the above general formula) of the PVP-based resin (B) is preferably 50 to 100,000, more preferably 100 to 80000, and further preferably 10,000 to 50,000.
If the average degree of polymerization of the PVP-based resin (B) is too small, the strength of the molded product tends to decrease, and if the average degree of polymerization is too large, the stability of the aqueous solution and the handling property tend to decrease.
ＰＶＰ系樹脂（Ｂ）は、従来公知の方法で製造することができ、例えば、アセチレン、アンモニアおよびホルムアルデヒドからＮ−ビニル−２−ピロリドンを合成し、これを酸化剤などの存在下で重合させることにより製造される。 The PVP resin (B) can be produced by a conventionally known method. For example, N-vinyl-2-pyrrolidone is synthesized from acetylene, ammonia and formaldehyde, and this is polymerized in the presence of an oxidizing agent or the like. Manufactured by.
〔水溶性樹脂組成物〕
本発明で用いられる水溶性樹脂組成物は、ＰＶＡ系樹脂（Ａ）とＰＶＰ系樹脂（Ｂ）を含有し、ＰＶＡ系樹脂（Ａ）を主体成分とするものである。
[Water-soluble resin composition]
The water-soluble resin composition used in the present invention contains a PVA resin (A) and a PVP resin (B), and contains the PVA resin (A) as a main component.
本発明において、ＰＶＰ系樹脂（Ｂ）の含有量は、ＰＶＡ系樹脂（Ａ）１００重量部に対して、１〜６０重量部であり、好ましくは５〜５５重量部、更に好ましくは８〜５０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、とりわけ乾燥して得られるフィルムの形状安定性が低下することとなる。 In this invention, content of PVP-type resin (B) is 1-60 weight part with respect to 100 weight part of PVA-type resin (A), Preferably it is 5-55 weight part, More preferably, it is 8-50. Parts by weight. If the content is too large or too small, the shape stability of the resulting molded product, particularly a film obtained by drying, is lowered.
本発明で用いられる水溶性樹脂組成物には、本発明の効果を阻害しない範囲で、ＰＶＡ系樹脂（Ａ）及びＰＶＰ系樹脂（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。
上述の他の水溶性高分子の含有量としては、水溶性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 water-soluble resin composition used in the present invention contains another water-soluble polymer different from the PVA-based resin (A) and the PVP-based resin (B) as long as the effects of the present invention are not impaired. Also good. Examples of other water-soluble polymers include starch, carboxymethyl cellulose, methyl cellulose, and hydroxymethyl cellulose.
The content of the other water-soluble polymer is preferably 10% by weight or less, particularly preferably 5% by weight or less, based on the water-soluble resin composition.
また、本発明の水溶性樹脂組成物には、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。 In addition, the water-soluble resin composition of the present invention includes a reinforcing agent, a filler, a plasticizer, a pigment, a dye, a lubricant, an antioxidant, and an antistatic agent as necessary, as long as the effects of the present invention are not impaired. Contains UV absorbers, heat stabilizers, light stabilizers, surfactants, antibacterial agents, antistatic agents, drying agents, antiblocking agents, flame retardants, crosslinking agents, curing agents, foaming agents, crystal nucleating agents, etc. May be.
本発明の水溶性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ＰＶＰ系樹脂（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ＰＶＰ系樹脂（Ｂ）の粉末を添加し、水溶液とする方法、（ｉｉｉ）ＰＶＰ系樹脂（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ＰＶＰ系樹脂（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）及び（ｉｖ）の
方法が好ましい。
The water-soluble resin composition of the present invention can be prepared into an aqueous solution by a known mixing method. For example, (i) a method in which a powder of PVA resin (A) and a powder of PVP resin (B) are mixed to form an aqueous solution, (ii) a PVP resin (B) in an aqueous solution of PVA resin (A) (Iii) A method of adding a powder of PVA resin (A) to an aqueous solution of PVP resin (B) to make an aqueous solution, (iv) A method of adding PVA resin (A) For example, an aqueous solution and an aqueous solution of the PVP resin (B) are mixed. Among these, the methods (i) and (iv) are preferable from the viewpoint of production efficiency.
〔成形品〕
本発明においては、上記水溶性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、カプセル状、錠剤用フィルムコーティング、錠剤用バインダーなどが挙げられ、特にフィルム状のものが好適に用いられる。
〔Molding〕
In the present invention, a molded product is obtained using the water-soluble resin composition. Examples of the shape of the molded product include a film shape, a cup shape, a tube shape, a capsule shape, a tablet film coating, a tablet binder, and the like, 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水溶性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。かかる水溶性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。
Hereinafter, a method for producing a film (film formation) will be described in detail. In order to produce the film, for example, a method such as a casting method can be employed.
The solid content concentration of the water-soluble resin composition when forming a film 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 concentration of the water-soluble 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 is generated during film formation. Tend.
又、アプリケーターを用いて、上記水溶性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。
Moreover, using an applicator, the aqueous solution of the water-soluble resin composition can be cast on a plastic substrate such as a polyethylene terephthalate film or a polyethylene film or a metal substrate and dried to obtain a film.
Moreover, as drying temperature, it is 50-140 degreeC normally, Preferably it is 60-120 degreeC, Most preferably, it is 80-100 degreeC. 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、用途により一概に言えないが、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、逆に厚すぎると水への溶解速度が大幅に遅くなり、又製膜時の効率も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 cannot be generally specified depending on the use, but it is preferably 5 to 100 μm, particularly preferably 10 to 80 μm. If the thickness is too thin, the mechanical strength of the film is low. On the contrary, if it is too thick, the dissolution rate in water is significantly slowed, and the efficiency at the time of film formation also tends to be lowered.
In addition, the surface of the film may be plain, but from the viewpoint of blocking properties, slipperiness during processing, and reduced adhesion between products, embossed pattern or satin pattern is applied on one or both sides of the film. It can also be left.
本発明の水溶性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 uses, the following uses are listed as uses of the molded article comprising the water-soluble resin composition of the present invention.
For example, food and beverage packaging materials, pharmaceutical (agrochemicals, pharmaceutical) packaging materials, fibers, sheets, pipes, tubes, leak-proof membranes, temporary coatings, chemical lace fibers, water-soluble fibers, containers, inner bags for bag-in-boxes Container packing, medical infusion bag, organic liquid container, organic liquid transport pipe, 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 goods, toys, medical equipment, 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。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the examples, “%” and “parts” mean weight basis.
製造例１
［ＰＶＡ系樹脂水溶液（ａ１）の作製］
ＰＶＡ系樹脂１（未変性、ケン化度８８モル％、重合度１３００、４％水溶液粘度１８ｍＰａ・ｓ）２０部を８０部の水に添加後、８５℃に昇温させＰＶＡ系樹脂１を溶解し、２０％水溶液を得て、ＰＶＡ系樹脂水溶液（ａ１）とした。
Production Example 1
[Preparation of PVA-based resin aqueous solution (a1)]
After adding 20 parts of PVA resin 1 (unmodified, saponification degree 88 mol%, polymerization degree 1300, 4% aqueous solution viscosity 18 mPa · s) to 80 parts of water, the temperature is raised to 85 ° C. to dissolve PVA resin 1 Then, a 20% aqueous solution was obtained and used as a PVA resin aqueous solution (a1).
［成形品（フィルム）（Ａ１）の作製］
得られたＰＶＡ系樹脂水溶液（ａ１）１００部をＰＥＴフィルム状に塗工し、８０℃で２時間乾燥して、膜厚１００μｍのフィルムとし、２５℃、５５％ＲＨの環境下で１日間調湿し、フィルム（Ａ１）を得た。
[Production of Molded Product (Film) (A1)]
100 parts of the obtained PVA-based resin aqueous solution (a1) was applied to a PET film and dried at 80 ° C. for 2 hours to form a film with a film thickness of 100 μm, which was prepared for 1 day in an environment of 25 ° C. and 55% RH Wet and film (A1) was obtained.
［弾性率評価］
上記で得られたフィルム（Ａ１）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、サンプルサイズは幅１０ｍｍ、つかみ具間距離５０ｍｍ、引張速度１００ｍｍ/ｍiｎで行い、弾性率を算出したところ２４０５Ｎ／ｍｍ2であった。かかる弾性率を基準値１とした。
[Elastic modulus evaluation]
A tensile test was performed on the film (A1) obtained above. The tensile test was performed using an autograph (manufactured by Shimadzu Corporation, AG-IS) with a sample size of 10 mm in width, a distance between grips of 50 mm, and a tensile speed of 100 mm / min, and the elastic modulus was calculated to be 2405 N / mm 2. Met. This elastic modulus was taken as the reference value 1.
実施例１
［水溶性樹脂組成物水溶液（１）の作製］
ＰＶＰ系樹脂（ＢＡＳＦ社製、Ｋｏｌｌｉｄｏｎ３０ 平均分子量４００００）２０部を８０部の水に添加後、室温で３０分撹拌させ溶解し、ＰＶＰ系樹脂２０％水溶液（ｂ１）を得た。
上記で得られたＰＶＡ系樹脂２０％水溶液（ａ１）１００部とＰＶＰ系樹脂２０％水溶液（ｂ１）１０部を混合して、水溶性樹脂組成物水溶液（１）を作製した。
Example 1
[Production of water-soluble resin composition aqueous solution (1)]
After adding 20 parts of PVP resin (manufactured by BASF, Kollidon 30 average molecular weight 40000) to 80 parts of water, the mixture was stirred and dissolved at room temperature for 30 minutes to obtain a 20% PVP resin aqueous solution (b1).
100 parts of the PVA-based resin 20% aqueous solution (a1) obtained above and 10 parts of the PVP-based resin 20% aqueous solution (b1) were mixed to prepare a water-soluble resin composition aqueous solution (1).
［フィルム（１）の作製］
上記で得られた水溶性樹脂組成物水溶液（１）を塗工し、８０℃で２時間乾燥して、膜厚１００μｍのフィルムとして、２５℃、５５％ＲＨで１日調湿し、フィルム（１）を得た。
[Production of Film (1)]
The aqueous solution of water-soluble resin composition (1) obtained above was applied, dried at 80 ° C. for 2 hours, and conditioned for one day at 25 ° C. and 55% RH as a film with a film thickness of 100 μm. 1) was obtained.
［弾性率評価］
上記で得られたフィルム（１）の引張試験をフィルム（Ａ１）と同様に行い、下記式を用いて弾性比率を算出した。結果を表１に示す。
〔式１〕
弾性比率＝フィルム（１）の弾性率／基準値１
[Elastic modulus evaluation]
The tensile test of the film (1) obtained above was conducted in the same manner as the film (A1), and the elastic ratio was calculated using the following formula. The results are shown in Table 1.
[Formula 1]
Elasticity ratio = elastic modulus of film (1) / reference value 1
実施例２
実施例１において、ＰＶＰ系樹脂２０％水溶液（ｂ１）を３０部とした以外は、実施例１と同様にフィルム（２）を作製し、同様に評価した。結果を表１に示す。
Example 2
A film (2) was prepared in the same manner as in Example 1 except that 30 parts of the 20% PVP resin aqueous solution (b1) was used in Example 1, and evaluated in the same manner. The results are shown in Table 1.
製造例２
［成形品（フィルム）（Ａ２）の作製］
製造例１で得られたフィルム（Ａ１）の作製において、調湿条件を２５℃、５８％ＲＨに変えた以外は、同様にしてフィルム（Ａ２）を得た。
Production Example 2
[Production of molded product (film) (A2)]
In the production of the film (A1) obtained in Production Example 1, a film (A2) was obtained in the same manner except that the humidity control condition was changed to 25 ° C. and 58% RH.
［弾性率評価］
上記で得られたフィルム（Ａ２）の引張試験をフィルム（Ａ１）と同様に実施した結果、弾性率は１１２７Ｎ／ｍｍ2であった。かかる弾性率を基準値２とした。
[Elastic modulus evaluation]
As a result of conducting the tensile test of the film (A2) obtained above in the same manner as the film (A1), the elastic modulus was 1127 N / mm 2 . This elastic modulus was taken as the reference value 2.
実施例３
［フィルム（３）の作製］
実施例１において、ＰＶＰ系樹脂２０％水溶液（ｂ１）の配合量を５０部とし、調湿条件を２５℃、５８％ＲＨに変えた以外は、実施例１と同様にフィルム（３）を作製した。
Example 3
[Production of Film (3)]
In Example 1, a film (3) was prepared in the same manner as in Example 1 except that the blending amount of the 20% aqueous PVP resin solution (b1) was 50 parts and the humidity control conditions were changed to 25 ° C. and 58% RH. did.
［弾性率評価］
上記で得られたフィルム（３）の引張試験をフィルム（Ａ２）と同様に行い、下記式を用いて弾性比率を算出した。結果を表２に示す。
〔式２〕
弾性比率＝フィルム（３）の弾性率／基準値２
[Elastic modulus evaluation]
The tensile test of the film (3) obtained above was conducted in the same manner as the film (A2), and the elastic ratio was calculated using the following formula. The results are shown in Table 2.
[Formula 2]
Elasticity ratio = elastic modulus of film (3) / reference value 2
比較例１
実施例３において、ＰＶＰ系樹脂２０％水溶液（ｂ１）の配合量を１００部に変えた以外は、実施例３と同様にして、フィルムを作製し、同様に評価した。結果を表２に示す。
Comparative Example 1
In Example 3, a film was produced and evaluated in the same manner as in Example 3 except that the blending amount of the 20% aqueous PVP resin solution (b1) was changed to 100 parts. The results are shown in Table 2.
比較例２
実施例３において、ＰＶＡ系樹脂を配合しなかった以外は同様にフィルムを作製し、同様に評価した。結果を表２に示す。
Comparative Example 2
In Example 3, a film was prepared in the same manner except that the PVA resin was not blended, and evaluated in the same manner. The results are shown in Table 2.
比較例３
実施例１において、ＰＶＡ系樹脂２０％水溶液（ａ１）１０部とＰＶＰ系樹脂２０％水溶液（ｂ１）１００部を混合した以外は同様にフィルムを作製し、同様に評価した。結果を表２に示す。
Comparative Example 3
A film was prepared in the same manner as in Example 1 except that 10 parts of a 20% PVA resin aqueous solution (a1) and 100 parts of a 20% PVP resin aqueous solution (b1) were mixed, and evaluated in the same manner. The results are shown in Table 2.
製造例３
［成形品（フィルム）（Ａ３）の作製］
製造例２において、ＰＶＡ系樹脂１に変えて、ＰＶＡ系樹脂２（未変性、ケン化度８８モル％、重合度５００、４％水溶液粘度５ｍＰａ・ｓ）を用いた以外は、製造例２と同様にフィルム（Ａ３）を作製した。
Production Example 3
[Production of molded product (film) (A3)]
In Production Example 2, instead of PVA resin 1, PVA resin 2 (unmodified, saponification degree 88 mol%, polymerization degree 500, 4% aqueous solution viscosity 5 mPa · s) was used, and Production Example 2 Similarly, a film (A3) was produced.
［弾性率評価］
上記で得られたフィルム（Ａ３）の引張試験をフィルム（Ａ１）と同様に実施した結果、弾性率は１０６８Ｎ／ｍｍ2であった。かかる弾性率を基準値３とした。
[Elastic modulus evaluation]
As a result of conducting the tensile test of the film (A3) obtained above in the same manner as the film (A1), the elastic modulus was 1068 N / mm 2 . This elastic modulus was taken as the reference value 3.
実施例４
［フィルム（４）の作製］
実施例１において、ＰＶＡ系樹脂１に変えて、ＰＶＡ系樹脂２（未変性、ケン化度８８モル％、重合度５００、４％水溶液粘度５ｍＰａ・ｓ）を使用し、調湿条件を２５℃、５８％ＲＨに変えた以外は、実施例３と同様にフィルム（４）を作製した。
Example 4
[Production of Film (4)]
In Example 1, instead of PVA resin 1, PVA resin 2 (unmodified, saponification degree 88 mol%, polymerization degree 500, 4% aqueous solution viscosity 5 mPa · s) was used, and the humidity condition was 25 ° C. A film (4) was produced in the same manner as in Example 3 except that the content was changed to 58% RH.
［弾性率評価］
上記で得られたフィルム（４）の引張試験をフィルム（Ａ３）と同様に行い、下記式を用いて弾性比率を算出した。結果を表３に示す。
〔式３〕
弾性比率＝フィルム（４）の弾性率／基準値３
[Elastic modulus evaluation]
The film (4) obtained above was subjected to a tensile test in the same manner as the film (A3), and the elastic ratio was calculated using the following formula. The results are shown in Table 3.
[Formula 3]
Elasticity ratio = elastic modulus of film (4) / reference value 3
本発明の成形品を用いた実施例１〜４においては、調湿後の弾性率がいずれも大きくなっており、フィルム自体の強度もあり、形状安定性に優れるものであった。一方、ＰＶＡ系樹脂とＰＶＰ系樹脂を同量含有した比較例１の成形品では、弾性率が向上せず、形状安定性に劣るものであった。また、ＰＶＡ系樹脂を含有しない比較例２及び、ＰＶＡ系樹脂を少量しか含有しない比較例３においては、造膜不良により、フィルムを作製できなかった。 In Examples 1 to 4 using the molded article of the present invention, the elastic modulus after humidity control was increased, the film itself was strong, and the shape stability was excellent. On the other hand, in the molded product of Comparative Example 1 containing the same amount of PVA resin and PVP resin, the elastic modulus was not improved and the shape stability was inferior. In Comparative Example 2 that does not contain a PVA-based resin and Comparative Example 3 that contains only a small amount of a PVA-based resin, a film could not be produced due to poor film formation.
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。 Since the molded article comprising the water-soluble resin composition of the present invention is excellent in shape stability under humidity, it is useful as a packaging material, particularly as a packaging material for agricultural chemicals, fertilizers, and pharmaceuticals.
Claims (4)
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| WO2022044275A1 (en) * | 2020-08-28 | 2022-03-03 | オーウエル株式会社 | Transfer sheet for texturing formation, manufacturing method for transfer sheet for texturing formation, and texturing formation method |
| JP2022549789A (en) * | 2019-09-30 | 2022-11-29 | モノソル リミテッド ライアビリティ カンパニー | Water soluble unit dose film for packaging harsh chemicals |
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| JP7488889B2 (en) | 2019-09-30 | 2024-05-22 | モノソル リミテッド ライアビリティ カンパニー | Water-soluble unit dose films for packaging harsh chemicals |
| WO2022044275A1 (en) * | 2020-08-28 | 2022-03-03 | オーウエル株式会社 | Transfer sheet for texturing formation, manufacturing method for transfer sheet for texturing formation, and texturing formation method |
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