JP4854932B2 - Resin composition and moisture-permeable material - Google Patents
Resin composition and moisture-permeable material Download PDFInfo
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本発明は、成形性、耐ブロッキング性に優れ、透湿度の調節が容易な透湿性樹脂組成物及び透湿性材料に関する。 The present invention relates to a moisture-permeable resin composition and a moisture-permeable material that are excellent in moldability and blocking resistance and that allow easy adjustment of moisture permeability.
紙おむつや生理用品のような衛生材料、コートなどの衣料品、食品の鮮度保持包装材料などにおいて、湿分を選択的に透過せしめる透湿性材料が使用されつつある。その代表的なものが、微粉末状無機質充填剤を配合したポリオレフィンをシート成形した後延伸して得られる微多孔性フィルムである。このタイプの透湿性材料においては、透湿度を高くするため孔径を大きくしすぎると耐水性が低下するが、上記製法によれば透湿性の度合と耐水性の度合のバランスをとるための孔径の調節が難しく、往々にして耐水性が犠牲になることがあった。また無機質充填剤の配合量が多くなるとシート強度が弱くなり、成形加工性が損なわれた。さらに微多孔性であるため、臭気成分が殆ど通過することが衛生材料分野では嫌われていた。 Hygroscopic materials that allow moisture to permeate selectively are being used in sanitary materials such as disposable diapers and sanitary products, clothing such as coats, and food freshness-keeping packaging materials. A typical example is a microporous film obtained by sheet-molding a polyolefin containing a fine powdery inorganic filler and then stretching. In this type of moisture permeable material, if the pore diameter is too large to increase the moisture permeability, the water resistance decreases, but according to the above method, the pore diameter for balancing the degree of moisture permeability and the degree of water resistance is low. It was difficult to adjust, and water resistance was often sacrificed. Moreover, when the compounding quantity of the inorganic filler was increased, the sheet strength was weakened and the moldability was impaired. Furthermore, since it is microporous, it has been hated in the sanitary material field that almost all odor components pass through.
このような微多孔性型透湿性材料と異なるものとして、ポリエーテル単位を相当量で分子内に含有するポリエステルエラストマー、ポリアミドエラストマー、ウレタン系エラストマーなどのフィルムからなる透湿性材料が知られているが、これらは高価であり、また用途によっては柔軟すぎ、かつ粘着性が高くてブロッキングし易いなどの問題点があった。 As a material different from such a microporous moisture-permeable material, a moisture-permeable material comprising a film of a polyester elastomer, a polyamide elastomer, a urethane elastomer, or the like, containing a considerable amount of polyether units in the molecule is known. These are expensive, and have problems such as being too flexible and high in tackiness and easy to block depending on applications.
一方、フィルムに透湿性を付与する手段として、厚みを数ミクロンから数十ミクロンのように薄くする方法は知られている。この方法は安価なポリエチレンやポリプロピレンなどのポリオレフィンに対してはあまり有効でないが、エチレンと極性モノマーの共重合体に対しては効果的である。しかしながら該共重合体の薄いフィルムは、ブロッキングし易く、作業性や取扱い性に問題があった。 On the other hand, as a means for imparting moisture permeability to a film, a method of making the thickness as thin as several microns to several tens of microns is known. This method is not very effective for inexpensive polyolefins such as polyethylene and polypropylene, but is effective for copolymers of ethylene and polar monomers. However, the thin film of the copolymer is easy to block, and has a problem in workability and handleability.
そこで本発明の目的は、透湿度を容易に調節することができ、かつ成形性に優れ、ブロッキングトラブルのない、エチレン・極性モノマー共重合体からなる透湿性材料を提供することにある。 Accordingly, an object of the present invention is to provide a moisture-permeable material made of an ethylene / polar monomer copolymer that can easily adjust moisture permeability, has excellent moldability, and has no blocking trouble.
すなわち本発明によれば、極性モノマー含有量が5〜45重量%、透湿係数が5.5×10−4g/m/day以上のエチレン・極性モノマー共重合体100重量部当たり、化学発泡剤として0.1〜10重量部の重炭酸ナトリウムを配合してなる、透湿係数が1.0×10−3g/m/day以上で、肉厚が5〜70μmの薄肉成形体を成形するのに用いられる透湿性樹脂組成物であって、上記エチレン・極性モノマー共重合体が、エチレンと、不飽和カルボン酸エステル、不飽和カルボン酸、不飽和カルボン酸塩及び一酸化炭素から選ばれる少なくとも一種の極性モノマーとの共重合体である、透湿性樹脂組成物が提供される。 That is, according to the present invention, chemical foaming per 100 parts by weight of the ethylene / polar monomer copolymer having a polar monomer content of 5 to 45 % by weight and a moisture permeability coefficient of 5.5 × 10 −4 g / m / day or more. A thin molded article having a moisture permeability coefficient of 1.0 × 10 −3 g / m / day or more and a thickness of 5 to 70 μm is formed by blending 0.1 to 10 parts by weight of sodium bicarbonate as an agent. The ethylene / polar monomer copolymer is selected from ethylene, an unsaturated carboxylic acid ester, an unsaturated carboxylic acid, an unsaturated carboxylic acid salt, and carbon monoxide. There is provided a moisture permeable resin composition that is a copolymer with at least one polar monomer .
本発明によれば、ブロッキングがなく、作業性、取扱い性に優れた透湿材料を提供することができる。このような透湿材料は、紙おむつのギャザーやバックシート、生理用品、医療用ディスポーザルシート、手術用・処置用ガウン裏地、絆創膏などの医療衛生材料、コート、スポーツ衣料等の衣料品、結露防止フィルム、ルーフィング材、透湿壁紙、床材のような建材、土木用シート、農園芸用フィルムのような農業用資材などに使用することができる。
According to the present invention, it is possible to provide a moisture-permeable material that has no blocking and is excellent in workability and handling. Such a moisture-permeable material, disposable diapers of gather and back sheets, sanitary supplies, medical disposable sheets, surgical, treatment gowns lining, medical sanitary materials, such as adhesive plaster, coat, sports clothing, such as clothing, to prevent condensation It can be used for films, roofing materials, moisture permeable wallpaper, building materials such as flooring materials, civil engineering sheets, agricultural materials such as agricultural and horticultural films.
本発明において使用されるエチレン・極性モノマー共重合体は、極性モノマー含有量が2〜50重量%、好ましくは5〜45重量%、透湿係数が5.0×10−4g/m/day以上、好ましくは5.5×10−4g/m/day以上のものである。上記エチレン・極性モノマー共重合体においては、極性モノマーの種類によっても若干異なるが、極性モノマー含量が上記範囲より少ないものは一般に透湿係数が小さく、良好な透湿材料とするのは難しい。一方、極性モノマー含有量が多い共重合体は透湿性が良好であるが、あまりにその含有量が多いものは機械的強度が小さく、またブロッキングし易くなる傾向がある。尚、本発明における透湿係数は、膜厚50μmのフィルムを用い、カップ法(JIS Z0208に準拠、40℃、相対湿度90%)で測定した透湿度に膜厚を乗ずることにより求めたものである。したがってエチレン・極性モノマー共重合体の透湿係数については、膜厚50μmとして算出したものであるが、発泡製品である本発明の透湿材料の透湿係数については、50μm厚みの発泡製品中のエチレン・極性モノマー共重合体が占める実質厚みを目付けから計算して、それを膜厚として算出したものである。 The ethylene / polar monomer copolymer used in the present invention has a polar monomer content of 2 to 50% by weight, preferably 5 to 45% by weight, and a moisture permeability coefficient of 5.0 × 10 −4 g / m / day. As mentioned above, Preferably it is 5.5 * 10 < -4 > g / m / day or more. The ethylene / polar monomer copolymer is slightly different depending on the kind of the polar monomer, but those having a polar monomer content less than the above range generally have a small moisture permeability coefficient, and it is difficult to obtain a good moisture permeable material. On the other hand, a copolymer having a large polar monomer content has good moisture permeability, but a copolymer having a too large content tends to have a low mechanical strength and easily block. The moisture permeability coefficient in the present invention is determined by multiplying the moisture permeability measured by the cup method (conforming to JIS Z0208, 40 ° C., relative humidity 90%) by the film thickness using a film having a thickness of 50 μm. is there. Therefore, the moisture permeability coefficient of the ethylene / polar monomer copolymer was calculated as a film thickness of 50 μm, but the moisture permeability coefficient of the moisture permeable material of the present invention, which is a foamed product, in a 50 μm thick foamed product. The actual thickness occupied by the ethylene / polar monomer copolymer is calculated from the basis weight and is calculated as the film thickness.
上記エチレン・極性モノマー共重合体の極性モノマーとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸イソブチル、アクリル酸n−ブチル、アクリル酸イソオクチル、メタクリル酸メチル、メタクリル酸イソブチル、マレイン酸ジメチル等の不飽和カルボン酸エステル、アクリル酸、メタクリル酸、フマル酸、イタコン酸、マレイン酸モノメチル、マレイン酸モノエチル、無水マレイン酸、無水イタコン酸等の不飽和カルボン酸、これら不飽和カルボン酸の塩、一酸化炭素、二酸化硫黄などの一種又は二種以上などを例示することができる。 Examples of the polar monomer of the ethylene / polar monomer copolymer include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, methyl methacrylate, isobutyl methacrylate, and maleic acid. Unsaturated carboxylic acid esters such as dimethyl, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, itaconic anhydride and the like, and salts of these unsaturated carboxylic acids , One or more of carbon monoxide, sulfur dioxide and the like can be exemplified.
上記不飽和カルボン酸の塩としては、リチウム、ナトリウム、カリウムなどの1価金属、マグネシウム、カルシウム、亜鉛などの多価金属の塩などを挙げることができる。 Examples of the unsaturated carboxylic acid salt include monovalent metals such as lithium, sodium and potassium, and salts of polyvalent metals such as magnesium, calcium and zinc.
エチレン・極性モノマー共重合体としてより具体的には、エチレン・アクリル酸メチル共重合体、エチレン・アクリル酸エチル共重合体、エチレン・メタクリル酸メチル共重合体、エチレン・アクリル酸イソブチル共重合体、エチレン・アクリル酸n−ブチル共重合体のようなエチレン・不飽和カルボン酸エステル共重合体、エチレン・アクリル酸イソブチル・メタクリル酸共重合体のようなエチレン・不飽和カルボン酸エステル・不飽和カルボン酸共重合体、エチレン・酢酸ビニル・一酸化炭素共重合体、エチレン・アクリル酸n−ブチル・一酸化炭素共重合体のようなエチレン・不飽和エステル・一酸化炭素共重合体、エチレン・アクリル酸共重合体、エチレン・メタクリル酸共重合体のようなエチレン・不飽和カルボン酸共重合体の部分金属塩などを代表例として例示することができる。 More specifically, as ethylene / polar monomer copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / isobutyl acrylate copolymer, Ethylene / unsaturated carboxylic acid ester copolymer such as ethylene / n-butyl acrylate copolymer, ethylene / unsaturated carboxylic acid ester / unsaturated carboxylic acid such as ethylene / isobutyl acrylate / methacrylic acid copolymer Copolymers, ethylene / vinyl acetate / carbon monoxide copolymers, ethylene / unsaturated ester / carbon monoxide copolymers such as ethylene / n-butyl acrylate / carbon monoxide copolymers, ethylene / acrylic acid Copolymer, part of ethylene / unsaturated carboxylic acid copolymer such as ethylene / methacrylic acid copolymer It can be exemplified as a representative example of such metal salts.
このようなエチレン・極性モノマー共重合体としては、成形加工性、機械的強度などを考慮すると、JIS K7210−1999、190℃、2160g荷重におけるメルトフローレート(MFR、以下同じ)が0.05〜500g/10分、とくに0.1〜100g/10分のものを使用するのが好ましい。これらエチレン・極性モノマー共重合体の多くは、高温、高圧下のラジカル共重合により得ることができる。 Such an ethylene / polar monomer copolymer has a melt flow rate (MFR, the same applies hereinafter) at a load of 2160 g in accordance with JIS K7210-1999, 190 ° C. in view of molding processability and mechanical strength. It is preferable to use one of 500 g / 10 min, in particular 0.1-100 g / 10 min. Many of these ethylene / polar monomer copolymers can be obtained by radical copolymerization under high temperature and high pressure.
本発明の透湿性樹脂組成物は、上記エチレン・極性モノマー共重合体に、その100重量部当たり、0.1〜10重量部、好ましくは0.2〜5重量部の化学発泡剤を配合してなるものである。その好適な配合量は、化学発泡剤の種類によっても異なるが、透湿性、耐ブロッキング性、フィルム強度などを考慮すると、発泡倍率が1.1〜10倍、とくに1.2〜5倍となるような割合とするのが好ましい。化学発泡剤としては、加熱によってガスを発生することができる分解型のものであれば如何なるものでもよく、例えばアゾジカルボアミド、ジニトロソペンタメチレンジアミン、スルフォニルヒドラジッド、重炭酸ナトリウム(炭酸水素ナトリウム)、重炭酸アンモニウム(炭酸水素アンモニウム)などを使用することができる。これらの中では特に重炭酸ナトリウムが好ましい。尚、これらの化学発泡剤は、単独であるいは2種以上組合わせて使用することができる。 The moisture-permeable resin composition of the present invention comprises 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight of a chemical foaming agent per 100 parts by weight of the ethylene / polar monomer copolymer. It will be. The preferred blending amount varies depending on the type of chemical foaming agent, but considering the moisture permeability, blocking resistance, film strength, etc., the foaming ratio is 1.1 to 10 times, particularly 1.2 to 5 times. Such a ratio is preferable. The chemical foaming agent may be any decomposition type that can generate gas by heating, such as azodicarboxamide, dinitrosopentamethylenediamine, sulfonylhydrazide, sodium bicarbonate (sodium bicarbonate). ), Ammonium bicarbonate (ammonium bicarbonate), and the like can be used. Of these, sodium bicarbonate is particularly preferred. These chemical foaming agents can be used alone or in combination of two or more.
本発明の透湿性樹脂組成物には、必要に応じ、種々の添加剤を配合することができる。このような添加剤の例としては、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、顔料、染料、親水性化合物、滑剤、ブロッキング防止剤、帯電防止剤、防黴剤、抗菌剤、難燃剤、難燃助剤などを挙げることができる。 Various additives can be blended in the moisture-permeable resin composition of the present invention as necessary. Examples of such additives include antioxidants, heat stabilizers, light stabilizers, UV absorbers, pigments, dyes, hydrophilic compounds, lubricants, antiblocking agents, antistatic agents, antifungal agents, and antibacterial agents. And flame retardants and flame retardant aids.
本発明の透湿性材料は、上記透湿性樹脂組成物を、エチレン・極性モノマー共重合体の融点以上、化学発泡剤の分解温度以上の温度でフィルム、シート、中空容器などの薄肉成形体に成形することによって得ることができる。この場合、薄肉成形体の成形と発泡を同時に行なってもよく、あるいはエチレン・極性モノマー共重合体の融点以上、化学発泡剤の分解温度以下の温度で薄肉成形体を成形し、その後化学発泡剤の分解温度以上の温度で発泡させることによって行なうことができる。いずれにしても最終製品である発泡薄肉成形体状の透湿材料の透湿係数が1.0×10−3g/m/day以上、好ましくは1.2×10−3g/m/day以上となるものであり、そのためには発泡倍率が1.1〜10倍、とくに1.2〜5倍とし、その肉厚が好ましくは1〜100μm、とくに好ましくは5〜70μmの範囲のものとするのがよい。本発明の透湿材料は、発泡倍率によっても異なるが、通常、同一厚みの原料エチレン・極性モノマー共重合体の透湿度(g/m2/day)の2〜10倍の透湿度を示す。 The moisture-permeable material of the present invention forms the moisture-permeable resin composition into a thin-walled molded product such as a film, sheet or hollow container at a temperature not lower than the melting point of the ethylene / polar monomer copolymer and not lower than the decomposition temperature of the chemical foaming agent. Can be obtained. In this case, the thin molded article may be molded and foamed simultaneously, or the thin molded article is molded at a temperature not lower than the melting point of the ethylene / polar monomer copolymer and not higher than the decomposition temperature of the chemical foaming agent, and then the chemical foaming agent. It can carry out by making it foam at the temperature more than the decomposition temperature of this. In any case, the moisture permeability coefficient of the foamed thin-walled shaped moisture-permeable material as the final product is 1.0 × 10 −3 g / m / day or more, preferably 1.2 × 10 −3 g / m / day. For this purpose, the expansion ratio is 1.1 to 10 times, particularly 1.2 to 5 times, and the thickness is preferably 1 to 100 μm, particularly preferably 5 to 70 μm. It is good to do. The moisture-permeable material of the present invention usually shows a moisture permeability of 2 to 10 times the moisture permeability (g / m 2 / day) of the raw material ethylene / polar monomer copolymer having the same thickness, although it varies depending on the expansion ratio.
本発明の透湿性材料は、種々の基材に積層して使用することができる。このような基材の例としては、織布、不織布、紙、各種合成樹脂フィルム、アルミニウム箔のような金属箔、木材などを例示することができる。本発明の透湿性材料と基材からなる積層体を製造する方法としては、上記透湿性樹脂組成物を発泡させつつ基材に押出コーティングする方法、上記透湿性樹脂組成物の溶液又は分散液を基材上に塗布したのち発泡させる方法、フィルム状の透湿材料と基材を貼り合わせる方法などを採用することができる。 The moisture-permeable material of the present invention can be used by being laminated on various substrates. Examples of such a substrate include woven fabric, non-woven fabric, paper, various synthetic resin films, metal foil such as aluminum foil, and wood. As a method for producing a laminate comprising the moisture permeable material of the present invention and a substrate, a method of extrusion coating the substrate while foaming the moisture permeable resin composition, a solution or dispersion of the moisture permeable resin composition is used. A method of foaming after coating on a substrate, a method of bonding a film-like moisture-permeable material and a substrate, and the like can be employed.
基材との積層に際し、基材との接着性を向上させるために高温での加工が要求される場合には、エチレン・極性モノマー共重合体における極性モノマーとして不飽和カルボン酸エステル、不飽和カルボン酸または不飽和カルボン酸の塩を有するものを使用するのが好ましい。また基材がアルミニウム箔、金属箔のような極性を有する材料の場合は、極性モノマーとして不飽和カルボン酸または不飽和カルボン酸の塩を有するものを使用するのが好ましい。さらに用途において最終製品に柔軟な風合いが求められる場合には、不飽和カルボン酸エステルを極性モノマーとして有するエチレン・極性モノマー共重合体を用いることが望ましい。 When processing at a high temperature is required to improve the adhesion to the base material during lamination with the base material, unsaturated carboxylic acid ester or unsaturated carboxylic acid ester is used as the polar monomer in the ethylene / polar monomer copolymer. It is preferable to use one having a salt of an acid or an unsaturated carboxylic acid. When the substrate is a material having polarity such as an aluminum foil or metal foil, it is preferable to use a material having an unsaturated carboxylic acid or an unsaturated carboxylic acid salt as a polar monomer. Furthermore, when a soft texture is required for the final product in use, it is desirable to use an ethylene / polar monomer copolymer having an unsaturated carboxylic acid ester as a polar monomer.
以下、実施例により本発明をさらに詳細に説明する。尚、実施例及び比較例で用いた原料及び物性評価方法は、以下の通りである。 Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the raw material and the physical-property evaluation method which were used by the Example and the comparative example are as follows.
1.原料
Znアイオノマー:エチレン・メタクリル酸共重合体(メタクリル酸含有量9重量%)の亜鉛アイオノマー(中和度18%、MFR5.5g/10分)
EVA:エチレン・酢酸ビニル共重合体(酢酸ビニル含有量10重量%、MFR9g/10分)
LDPE:高圧法低密度ポリエチレン(密度923kg/m3、MFR3.7g/10分)
NaHCO3:ポリスレンE205(永和化成(株)製、NaHCO320%マスターバッチ)
1. Raw material Zn ionomer: Zinc ionomer of ethylene / methacrylic acid copolymer (methacrylic acid content 9% by weight) (degree of neutralization 18%, MFR 5.5 g / 10 min)
EVA: Ethylene / vinyl acetate copolymer (vinyl acetate content 10% by weight, MFR 9 g / 10 min)
LDPE: High-pressure method low-density polyethylene (density 923 kg / m 3 , MFR 3.7 g / 10 min)
NaHCO 3 : Polyslen E205 (manufactured by Eiwa Kasei Co., Ltd., NaHCO 3 20% masterbatch)
2.物性評価方法
(1)透湿度:50μm厚みのフィルムサンプルを用い、カップ法(JIS Z0208準拠、測定雰囲気:40℃×90%RH)により測定。
(2)透湿係数:透湿度×膜厚により算出。尚、発泡サンプルについては、目付けから実質膜厚を推定し、これを膜厚とした。
2. Physical property evaluation method (1) Water vapor permeability: Measured by a cup method (conforming to JIS Z0208, measurement atmosphere: 40 ° C. × 90% RH) using a film sample having a thickness of 50 μm.
(2) Moisture permeability coefficient: calculated by moisture permeability × film thickness. In addition, about the foam sample, the real film thickness was estimated from the fabric weight, and this was made into the film thickness.
[実施例1、比較例1]
上記Znアイオノマー100重量部に対し、ポリスレンE205をNaHCO3として0.5重量部配合し、インフレーション成形機にて加工温度180℃で膜厚50μmのフィルムを作成した。比較のためポリスレンE205を配合しないZnアイオノマーについても同様にして50μmのフィルムを作成した。これらフィルムについて透湿度を測定すると共に、透湿係数を算出した。結果を表1に示す。
[Example 1, Comparative Example 1]
0.5 parts by weight of Polysylene E205 as NaHCO 3 was blended with 100 parts by weight of the above Zn ionomer, and a film having a film thickness of 50 μm was formed at a processing temperature of 180 ° C. by an inflation molding machine. For comparison, a film having a thickness of 50 μm was similarly prepared for a Zn ionomer not containing Polyslene E205. The moisture permeability of these films was measured and the moisture permeability coefficient was calculated. The results are shown in Table 1.
[参考例2、比較例2] Znアイオノマーの代わりに上記EVAを用いた以外は、実施例1及び比較例1と同様にしてフィルム成形を行ない、その透湿度を測定すると共に、透湿係数を算出した。結果を表1に示す。 [ Reference Example 2, Comparative Example 2] Except that the EVA was used instead of the Zn ionomer, film formation was performed in the same manner as in Example 1 and Comparative Example 1, and the moisture permeability was measured and the moisture permeability coefficient was determined. Calculated. The results are shown in Table 1.
[比較例3〜4]
Znアイオノマーの代わりに上記LDPEを用いた以外は、実施例1及び比較例1と同様にしてフィルム成形を行ない、その透湿度を測定すると共に、透湿係数を算出した。結果を表1に示す。
[Comparative Examples 3 to 4]
A film was formed in the same manner as in Example 1 and Comparative Example 1 except that the LDPE was used instead of the Zn ionomer, and the moisture permeability was measured and the moisture permeability coefficient was calculated. The results are shown in Table 1.
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