JP6865959B2 - Transparent resin film - Google Patents
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- JP6865959B2 JP6865959B2 JP2017015280A JP2017015280A JP6865959B2 JP 6865959 B2 JP6865959 B2 JP 6865959B2 JP 2017015280 A JP2017015280 A JP 2017015280A JP 2017015280 A JP2017015280 A JP 2017015280A JP 6865959 B2 JP6865959 B2 JP 6865959B2
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- nepheline
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- 229920005989 resin Polymers 0.000 title claims description 39
- 239000011347 resin Substances 0.000 title claims description 39
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 25
- 229960001545 hydrotalcite Drugs 0.000 claims description 25
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 24
- 239000010434 nepheline Substances 0.000 claims description 22
- 229910052664 nepheline Inorganic materials 0.000 claims description 22
- 229920005672 polyolefin resin Polymers 0.000 claims description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 239000011342 resin composition Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229920001684 low density polyethylene Polymers 0.000 description 6
- 239000004702 low-density polyethylene Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XARHOZCQSBWPOC-UHFFFAOYSA-N Neferin Natural products COc1ccc(CC2N(C)CCc3cc(OC)c(Oc4ccc(CC5N(C)CCc6cc(OC)c(OC)cc56)cc4O)cc23)cc1 XARHOZCQSBWPOC-UHFFFAOYSA-N 0.000 description 1
- MIBATSHDJRIUJK-ROJLCIKYSA-N Neferine Chemical compound C1=CC(OC)=CC=C1C[C@@H]1C2=CC(OC=3C(=CC=C(C[C@@H]4C5=CC(OC)=C(OC)C=C5CCN4C)C=3)O)=C(OC)C=C2CCN1C MIBATSHDJRIUJK-ROJLCIKYSA-N 0.000 description 1
- MIBATSHDJRIUJK-UHFFFAOYSA-N Neferine Natural products C1=CC(OC)=CC=C1CC1C2=CC(OC=3C(=CC=C(CC4C5=CC(OC)=C(OC)C=C5CCN4C)C=3)O)=C(OC)C=C2CCN1C MIBATSHDJRIUJK-UHFFFAOYSA-N 0.000 description 1
- 229920003355 Novatec® Polymers 0.000 description 1
- -1 Polyethylene Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QANIADJLTJYOFI-UHFFFAOYSA-K aluminum;magnesium;carbonate;hydroxide;hydrate Chemical compound O.[OH-].[Mg+2].[Al+3].[O-]C([O-])=O QANIADJLTJYOFI-UHFFFAOYSA-K 0.000 description 1
- 229920006167 biodegradable resin Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010435 syenite Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、農業用樹脂フィルムなどとして用いて高い保温効果が得られる透明樹脂フィルムに関する。 The present invention relates to a transparent resin film that can be used as an agricultural resin film or the like to obtain a high heat retaining effect.
高い保温効果が得られる透明樹脂フィルムとして、ハイドロタルサイトの粉末をフィラーとして用いた農業用樹脂フィルムが知られている（特許文献１）。 As a transparent resin film capable of obtaining a high heat-retaining effect, an agricultural resin film using hydrotalcite powder as a filler is known (Patent Document 1).
しかしながら、ハイドロタルサイトは高価であることから、ハイドロタルサイトの量を少なくし、かつ高い保温効果が得られる透明樹脂フィルムが求められている。 However, since hydrotalcite is expensive, there is a demand for a transparent resin film that can reduce the amount of hydrotalcite and obtain a high heat-retaining effect.
本発明の目的は、ハイドロタルサイトの含有量を少なくしても、高い保温効果を得ることができる透明樹脂フィルムを提供することにある。 An object of the present invention is to provide a transparent resin film capable of obtaining a high heat retaining effect even if the content of hydrotalcite is reduced.
本発明の透明樹脂フィルムは、質量比（ネフェリンサイヤナイト：ハイドロタルサイト）で１０：９０〜９０：１０の範囲となるように、樹脂にネフェリンサイヤナイトとハイドロタルサイトが合計で０．５〜１０質量％含有されていることを特徴としている。 In the transparent resin film of the present invention, nepheline syanite and hydrotalcite are added to the resin in a total amount of 0.5 to 90 so that the mass ratio (nepheline syanite: hydrotalcite) is in the range of 10:90 to 90:10. It is characterized by containing 10% by mass.
本発明において、樹脂は、塩化ビニル系樹脂、ポリオレフィン系樹脂、またはエチレン−酢酸ビニル共重合樹脂であることが好ましい。 In the present invention, the resin is preferably a vinyl chloride resin, a polyolefin resin, or an ethylene-vinyl acetate copolymer resin.
本発明によれば、ハイドロタルサイトの含有量を少なくしても、高い保温効果を得ることができる。 According to the present invention, a high heat retention effect can be obtained even if the content of hydrotalcite is reduced.
以下、好ましい実施形態について説明する。但し、以下の実施形態は単なる例示であり、本発明は以下の実施形態に限定されるものではない。以下、本発明をさらに詳細に説明する。 Hereinafter, preferred embodiments will be described. However, the following embodiments are merely examples, and the present invention is not limited to the following embodiments. Hereinafter, the present invention will be described in more detail.
（ネフェリンサイヤナイト）
ネフェリンサイヤナイトは、霞石（ネフェリン）を含む準長石閃長岩であり、通常ｘＳｉＯ２・ｙＡｌ２Ｏ３・ｚＮａ２Ｏ・ａＫ２Ｏの組成式で表わされ、石英を含まない。本発明に用いるネフェリンサイヤナイトの平均粒子径（Ｄ５０）は、好ましくは０．０５〜５０μｍの範囲内であり、より好ましくは０．１〜３０μｍの範囲内であり、さらに好ましくは０．３〜２０μｍの範囲内である。
(Nepheline Saiyan Night)
Nepheline saiya Knight is a feldspar syenite containing nepheline (the nepheline), typically represented by a composition formula of xSiO 2 · yAl 2 O 3 · zNa 2 O · aK 2 O, does not contain silica. The average particle size (D 50 ) of nepheline saiyanite used in the present invention is preferably in the range of 0.05 to 50 μm, more preferably in the range of 0.1 to 30 μm, and further preferably in the range of 0.3. It is in the range of ~ 20 μm.
（ハイドロタルサイト）
ハイドロタルサイトは、通常、Ｍ２＋ １−ｘＭ３＋ ｘ（ＯＨ）２Ａｎ− ｘ／ｎ・ｍＨ２Ｏの組成式で表わされ、結晶構造が層状構造をしており、２価（Ｍ２＋）及び３価（Ｍ３＋）の金属の複合水酸化物からなる基本層と、その基本層間にアニオン（Ａｎ−）と水を有する中間層からなる。基本層は２価の金属イオンの一部の代わりに３価の金属イオンが配位することで正に帯電しており、基本層の層間にアニオンがインターカレートすることで、トータルの電荷が中和している。本発明に用いるハイドロタルサイトの平均粒子径（Ｄ５０）は、好ましくは０．０５〜１０μｍの範囲内であり、より好ましくは０．１〜５μｍの範囲内である。
(Hydrotalcite)
Hydrotalcite is usually represented by a composition formula of M 2+ 1-x M 3+ x (OH) 2 An - x / n · mH 2 O, and has a layered crystal structure and is divalent (divalent). It consists of a basic layer composed of a composite hydroxide of M 2+ ) and trivalent (M 3+ ) metals, and an intermediate layer having anions (An−) and water between the basic layers. The basic layer is positively charged by the coordination of trivalent metal ions instead of a part of the divalent metal ions, and the anion intercalates between the layers of the basic layer to increase the total charge. It is neutralizing. The average particle size (D 50 ) of the hydrotalcite used in the present invention is preferably in the range of 0.05 to 10 μm, more preferably in the range of 0.1 to 5 μm.
（樹脂）
本発明において用いる樹脂は、ネフェリンサイヤナイト及びハイドロタルサイトを含有させて透明樹脂フィルムとすることができる樹脂であれば特に限定されない。樹脂としては、例えば、塩化ビニル系樹脂、ポリオレフィン系樹脂、エチレン−酢酸ビニル共重合樹脂、生分解性樹脂などが挙げられる。また、これらの樹脂からなるフィルムを、２枚以上重ねた多層フィルムであってもよい。これらの中でも、塩化ビニル系樹脂、ポリオレフィン系樹脂、及びエチレン−酢酸ビニル共重合樹脂が特に好ましい。ポリオレフィン系樹脂としては、低密度ポリエチレン樹脂（ＬＤＰＥ）または直鎖状低密度ポリエチレン樹脂（ＬＬＤＰＥ）が特に好ましい。
(resin)
The resin used in the present invention is not particularly limited as long as it is a resin that can contain nepheline syanite and hydrotalcite to form a transparent resin film. Examples of the resin include vinyl chloride resin, polyolefin resin, ethylene-vinyl acetate copolymer resin, biodegradable resin and the like. Further, a multilayer film in which two or more films made of these resins are laminated may be used. Among these, vinyl chloride-based resins, polyolefin-based resins, and ethylene-vinyl acetate copolymer resins are particularly preferable. As the polyolefin resin, a low density polyethylene resin (LDPE) or a linear low density polyethylene resin (LLDPE) is particularly preferable.
（樹脂組成物の調製方法）
本発明の透明樹脂フィルムを製造するための樹脂組成物は、ネフェリンサイヤナイト及びハイドロタルサイトと樹脂とを、ニーダー、バンバリーミキサー、１軸押出機、２軸押出機などで溶融混練することにより製造することができる。
(Method for preparing resin composition)
The resin composition for producing the transparent resin film of the present invention is produced by melt-kneading neferin saiyanite, hydrotalcite, and a resin with a kneader, a Banbury mixer, a single-screw extruder, a twin-screw extruder, or the like. can do.
（樹脂組成物中の含有量）
樹脂組成物中のネフェリンサイヤナイトとハイドロタルサイトの質量比（ネフェリンサイヤナイト：ハイドロタルサイト）は、１０：９０〜９０：１０の範囲内である。このような範囲内にすることにより、ネフェリンサイヤナイトとハイドロタルサイトを併用することによる相乗効果として、高い赤外線吸収性能を得ることができ、高い保温効果を得ることができる。質量比（ネフェリンサイヤナイト：ハイドロタルサイト）は、１５：８５〜８５：１５の範囲内であることが好ましく、２０：８０〜８０：２０の範囲内であることがより好ましい。
(Content in resin composition)
The mass ratio of nepheline saiyanite to hydrotalcite (nepheline saiyanite: hydrotalcite) in the resin composition is in the range of 10:90 to 90:10. Within such a range, high infrared absorption performance can be obtained and a high heat retention effect can be obtained as a synergistic effect by using nepheline saiyanite and hydrotalcite in combination. The mass ratio (nepheline saiyanite: hydrotalcite) is preferably in the range of 15:85 to 85:15, more preferably in the range of 20:80 to 80:20.
樹脂組成物中のネフェリンサイヤナイトとハイドロタルサイトの合計の含有量は、０．５〜１０質量％の範囲内である。このような範囲内にすることにより、高い赤外線吸収性能を得ることができ、高い保温効果を得ることができる。ネフェリンサイヤナイトとハイドロタルサイトの合計の含有量は、１〜８質量％の範囲内であることが好ましく、２〜６質量％の範囲内であることがより好ましい。 The total content of nepheline saiyanite and hydrotalcite in the resin composition is in the range of 0.5 to 10% by mass. Within such a range, high infrared absorption performance can be obtained, and a high heat retention effect can be obtained. The total content of nepheline saiyanite and hydrotalcite is preferably in the range of 1 to 8% by mass, more preferably in the range of 2 to 6% by mass.
（樹脂フィルムの調製方法）
樹脂組成物を、プレス成形、インフレーション成形、押出成形、１軸延伸成形、２軸延伸成形などの方法で成形することにより、樹脂フィルムを調製することができる。
(Preparation method of resin film)
A resin film can be prepared by molding the resin composition by a method such as press molding, inflation molding, extrusion molding, uniaxial stretching molding, or biaxial stretching molding.
以下、本発明について、具体的な実施例に基づいて、さらに詳細に説明する。本発明は、以下の実施例に何ら限定されるものではない。本発明の要旨を変更しない範囲において適宜変更して実施することが可能である。 Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is not limited to the following examples. It is possible to carry out the present invention with appropriate modifications without changing the gist of the present invention.
（実施例１〜３及び比較例１〜２）
ネフェリンサイヤナイト、ハイドロタルサイト、及び低密度ポリエチレンとして、以下のものを用い、表１に示す配合割合（質量％）で、以下のようにして樹脂組成物を調製し、樹脂フィルムを作製した。
(Examples 1 to 3 and Comparative Examples 1 to 2)
Using the following as nepheline syanite, hydrotalcite, and low-density polyethylene, the resin composition was prepared as follows at the blending ratio (mass%) shown in Table 1 to prepare a resin film.
・ネフェリンサイヤナイト：ユニミン社製、商品名ＨＣ−２００，平均粒子径（Ｄ５０）２０μｍ
・ハイドロタルサイト：協和化学工業社製、商品名ＤＨＴ−４Ａ，平均粒子径（Ｄ５０）０．５μｍ
・低密度ポリエチレン：日本ポリエチレン社製、商品名ノバテックＬＤ（ＬＦ６４０ＭＡ）
-Nepheline saiyanite: manufactured by Unimin, trade name HC-200, average particle size (D 50 ) 20 μm
-Hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd., trade name DHT-4A, average particle size (D 50 ) 0.5 μm
-Low density polyethylene: Made by Japan Polyethylene Corporation, trade name Novatec LD (LF640MA)
低密度ポリエチレンとネフェリンサイヤナイト及びハイドロタルサイトを、２軸押出機（テクノベル社製；スクリュ径２０ｍｍφ、Ｌ／Ｄ＝４５）を用いて、温度１８０℃、押出量６ｋｇ／ｈの条件にて溶融混練し、樹脂組成物を得た。
Low-density polyethylene, nepheline syanite, and hydrotalcite are melted using a twin-screw extruder (Technobel Co., Ltd .;
２軸押出機によって得られた樹脂組成物を、圧縮成形機(東洋精機製作所社製)にて、温度１８０℃、時間３分、圧力２ＭＰａの条件でプレスし、厚さ０．１ｍｍの透明樹脂フィルムを作製した。 The resin composition obtained by the twin-screw extruder is pressed by a compression molding machine (manufactured by Toyo Seiki Seisakusho Co., Ltd.) under the conditions of a temperature of 180 ° C., a time of 3 minutes, and a pressure of 2 MPa, and a transparent resin having a thickness of 0.1 mm. A film was made.
（比較例３）
ネフェリンサイヤナイト及びハイドロタルサイトを含有しない低密度ポリエチレンを用いて、上記と同様にして樹脂フィルムを作製し、比較例３とした。
(Comparative Example 3)
A resin film was prepared in the same manner as above using low-density polyethylene containing no nepheline saiyanite and hydrotalcite, and used as Comparative Example 3.
＜全光線透過率の測定＞
ヘーズメータ（日本電色工業株式会社製、ＮＤＨ７０００）を用いて、ＪＩＳＫ７１０５に準拠して、フィルムの全光線透過率を測定した。
<Measurement of total light transmittance>
The total light transmittance of the film was measured using a haze meter (NDH7000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7105.
表１に測定結果を示した。 The measurement results are shown in Table 1.
＜ヘイズの測定＞
ヘーズメータ（日本電色工業株式会社製、ＮＤＨ７０００）を用いて、ＪＩＳＫ７１３６に準拠して、フィルムのヘイズを測定した。
<Measurement of haze>
The haze of the film was measured according to JIS K7136 using a haze meter (NDH7000, manufactured by Nippon Denshoku Industries Co., Ltd.).
表１に測定結果を示した。 The measurement results are shown in Table 1.
＜赤外線吸収率の測定＞
上記各実施例及び各比較例の樹脂フィルムについて、波長域（１５００〜５００ｃｍ−１）及び波長域（１４００〜７００ｃｍ−１）における赤外線吸収率を測定した。
<Measurement of infrared absorption rate>
The infrared absorptivity in the wavelength range (1500 to 500 cm -1 ) and the wavelength range (1400 to 700 cm -1 ) was measured for the resin films of each of the above Examples and Comparative Examples.
図１は、波長域（１４００〜７００ｃｍ−１）における赤外線吸収スペクトルを示す図である。図１において、縦軸は透過率であり、透過率が低くなるほど赤外線吸収率は高くなる。 FIG. 1 is a diagram showing an infrared absorption spectrum in the wavelength range (1400 to 700 cm -1). In FIG. 1, the vertical axis is the transmittance, and the lower the transmittance, the higher the infrared absorption rate.
各実施例及び各比較例の樹脂フィルムの波長域（１５００〜５００ｃｍ−１）及び波長域（１４００〜７００ｃｍ−１）における赤外線透過率を、表１に示した。 Table 1 shows the infrared transmittances of the resin films of each example and each comparative example in the wavelength range (1500 to 500 cm -1 ) and the wavelength range (1400 to 700 cm -1).
表１に示すように、ネフェリンサイヤナイト及びハイドロタルサイトを本発明の範囲内となるように併用した実施例１〜３は、ネフェリンサイヤナイトまたはハイドロタルサイトを単独で用いた比較例１及び２に比べ、高い赤外線吸収率を示しており、優れた保温効果が得られることがわかる。 As shown in Table 1, Examples 1 to 3 in which nepheline saiyanite and hydrotalcite are used in combination so as to be within the scope of the present invention are Comparative Examples 1 and 2 in which nepheline saiyanite or hydrotalcite is used alone. Compared with, it shows a high infrared absorption rate, and it can be seen that an excellent heat retention effect can be obtained.
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| JPS6049047A (en) * | 1983-08-30 | 1985-03-18 | Mitsubishi Chem Ind Ltd | Manufacture of antifogging polyolefin film |
| JPS63254164A (en) * | 1987-04-11 | 1988-10-20 | Sakai Chem Ind Co Ltd | Resin composition |
| US5961943A (en) * | 1996-08-01 | 1999-10-05 | Mizusawa Industrial Chemicals, Ltd. | Regularly-shaped aluminosilicate and its use |
| JP2004034604A (en) * | 2002-07-05 | 2004-02-05 | Du Pont Mitsui Polychem Co Ltd | Agricultural film |
| JP2005047601A (en) * | 2003-07-31 | 2005-02-24 | Sumitomo Bakelite Co Ltd | Polypropylene sheet for push through package |
| JP2007314648A (en) * | 2006-05-25 | 2007-12-06 | Du Pont Mitsui Polychem Co Ltd | Agricultural film |
| JP5275345B2 (en) * | 2007-07-09 | 2013-08-28 | ユニミン コーポレーション | Meteorite syenite powder with controlled particle size and its new production method |
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