JP3126079B2 - Resin coated paper - Google Patents
Resin coated paperInfo
- Publication number
- JP3126079B2 JP3126079B2 JP04358006A JP35800692A JP3126079B2 JP 3126079 B2 JP3126079 B2 JP 3126079B2 JP 04358006 A JP04358006 A JP 04358006A JP 35800692 A JP35800692 A JP 35800692A JP 3126079 B2 JP3126079 B2 JP 3126079B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- weight
- paper
- resin layer
- coated paper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は、紙基体の片面をポリエ
チレン系樹脂組成物からなる樹脂層で被覆した樹脂被覆
紙に関するものである。詳しくは、樹脂層の成形加工が
良好で、樹脂層と紙基体との接着性に優れ、さらに樹脂
層にゲルの少ないポリエチレン系樹脂被覆紙に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin-coated paper in which one side of a paper substrate is coated with a resin layer made of a polyethylene resin composition. More specifically, the present invention relates to a polyethylene-based resin-coated paper in which the molding process of the resin layer is good, the adhesiveness between the resin layer and the paper substrate is excellent, and the resin layer has little gel.
【０００２】[0002]
【従来の技術】紙、板紙、セロハン等の紙基体(以下、
基紙という)上にフィルム形成能のある樹脂を溶融して
押出し、被覆することは広く行なわれており、これを用
いた食品用容器、包装材料、剥離紙、印刷用紙、写真用
支持体等の樹脂被覆紙はよく知られている。2. Description of the Related Art Paper substrates such as paper, paperboard, cellophane, etc.
It is widely used to melt, extrude and coat a resin capable of forming a film on a base paper), and use it for food containers, packaging materials, release paper, printing paper, photographic supports, etc. Are well known.
【０００３】基紙に溶融したポリエチレン系樹脂を押出
して被覆する場合は、ポリエチレン系樹脂の融点よりも
かなり高い温度で行なわれている。例えば、低密度ポリ
エチレンの融点は１０５〜１１０℃付近であり、高密度
ポリエチレンの融点は１２０〜１３０℃付近であるのに
対し、Ｔダイ法による溶融押出し温度は、薄膜塗布を行
なうために３００℃付近で行なう必要がある。[0003] When extruding and coating a molten polyethylene resin onto a base paper, the temperature is considerably higher than the melting point of the polyethylene resin. For example, the melting point of low-density polyethylene is around 105 to 110 ° C. and the melting point of high-density polyethylene is around 120 to 130 ° C., whereas the melt extrusion temperature by the T-die method is 300 ° C. to perform thin film coating. It needs to be done nearby.
【０００４】一般にポリエチレン分子中には、エチレン
モノマ−の重合体としての直鎖状炭素鎖の他に、炭素-
炭素二重結合のような不飽和結合や、メチル基あるいは
それ以上の炭素骨格を結合した側鎖状の炭素鎖を含むこ
とが知られている。ポリエチレンに対し、３００℃付近
での温度は加工適正面からは適度な温度であるが、分子
レベルでは活性化を促進させる範囲であり、実際の長時
間操業では、溶融ポリエチレン系樹脂の流動変化等の要
因により、分子中の不飽和結合や側鎖状の炭素付近でラ
ジカルが発生し易い状態になり、ラジカルが連鎖反応し
て橋かけ反応を起し、フィルムとなって押出されたとき
にゲル状の欠陥となって現れることがしばしばある。こ
のゲルは樹脂被覆紙表面の突起となって外観を損ない、
機能的にも種々の障害となる。In general, a polyethylene molecule contains not only a linear carbon chain as a polymer of ethylene monomer but also a carbon
It is known to include an unsaturated bond such as a carbon double bond, or a side chain carbon chain having a methyl group or a higher carbon skeleton. For polyethylene, the temperature around 300 ° C is an appropriate temperature from the viewpoint of proper processing, but it is within the range that promotes activation at the molecular level. Due to the above factors, radicals are likely to be generated near unsaturated bonds and side-chain carbon in the molecule, and the radicals undergo a chain reaction to cause a crosslinking reaction, and when extruded into a film, a gel is formed. Often it manifests itself as a shape defect. This gel becomes a projection on the surface of the resin-coated paper and impairs the appearance,
There are various obstacles in function.
【０００５】食品用容器、印刷用紙等では樹脂層にゲル
が存在すると、その部分の印刷不良や基紙との接着不良
による剥離等を生じる。また、剥離紙ではゲルの存在が
樹脂層上へのシリコ−ン等の離型剤塗布工程で品質不良
を招く場合が多い。さらに写真用支持体の場合には、ゲ
ルの存在そのものが写真画像としての質を低下させた
り、正常な写真画像を形成できない場合は、写真印画紙
としての商品価値を喪失することが多い。このため、充
分なゲル防止対策を講ずることが必要である。[0005] In a food container, printing paper, or the like, if a gel is present in the resin layer, peeling due to poor printing at that portion or poor adhesion to the base paper occurs. In the case of release paper, the presence of the gel often causes poor quality in the step of applying a release agent such as silicone on the resin layer. Further, in the case of a photographic support, the presence of the gel itself deteriorates the quality of the photographic image, or when the normal photographic image cannot be formed, the commercial value of the photographic printing paper is often lost. For this reason, it is necessary to take sufficient measures to prevent gel.
【０００６】このようなゲルの生成を防止する方法とし
て、押出し加工温度を下げて操業する方法があるが、そ
の場合、ポリエチレン系樹脂と紙との接着性が低下する
ため、所要の接着性を維持するためには加工速度が制限
され生産性が低下する。また、短い周期で押出機の分解
掃除を行なえば効果はあるものの生産性の低下は避けら
れない。As a method for preventing the formation of such a gel, there is a method of operating at a lower extrusion temperature, but in this case, the adhesion between the polyethylene resin and the paper is reduced. In order to maintain it, the processing speed is limited and productivity is reduced. Further, if the disassembly and cleaning of the extruder is performed in a short cycle, although the effect is obtained, a decrease in productivity is inevitable.
【０００７】一方、ポリエチレン系樹脂のフィルム製造
において、このゲルの生成を防止するために酸化防止剤
を添加することにより効果を挙げている場合がある。し
かし、基紙上にポリエチレン系樹脂を押出し被覆する場
合に、ゲルを防止するため酸化防止剤を添加することは
基紙とポリエチレン系樹脂の接着を悪化させるため一般
的にはあまり行なわれていない。On the other hand, in the production of a polyethylene resin film, an effect may be obtained by adding an antioxidant in order to prevent the formation of the gel. However, in the case of extruding and coating a polyethylene resin on a base paper, addition of an antioxidant to prevent gelation is generally not often performed because the adhesion between the base paper and the polyethylene resin is deteriorated.
【０００８】また、樹脂層の平滑性、耐熱性、耐摩擦性
等が要求される剥離紙等では、樹脂層に融点の高い高密
度ポリエチレンを用いているが、該樹脂被覆紙を製造す
る際、サ−ジングあるいはドロ−レゾナンスの程度によ
る流動の不安定性、ネックイン、ドロ−ダウン性による
膜切れ等の成形加工性がなお不充分である。特に、基紙
の走行速度１５０ｍ／分以上である高速条件で生産した
場合には、上記の問題に加え、樹脂層と基紙との接着性
が悪化して樹脂層が剥離し易くなるという問題があっ
た。上述のように、従来、樹脂層の成形加工が良好で樹
脂層と基紙との接着性に優れ、かつ樹脂層中のゲル発生
を極力防止したポリエチレン系樹脂被覆紙を得ることは
実際上困難であった。In a release paper or the like in which the resin layer is required to have smoothness, heat resistance, friction resistance, etc., a high-density polyethylene having a high melting point is used for the resin layer. Insufficiency in molding processability such as instability of flow due to the degree of surge or draw resonance, and breakage of the film due to neck-in and draw-down properties. In particular, in the case of production under high-speed conditions in which the running speed of the base paper is 150 m / min or more, in addition to the above-mentioned problems, the problem that the adhesiveness between the resin layer and the base paper is deteriorated and the resin layer is easily peeled off. was there. As described above, conventionally, it is practically difficult to obtain a polyethylene-based resin-coated paper in which the molding process of the resin layer is good, the adhesiveness between the resin layer and the base paper is excellent, and the generation of gel in the resin layer is minimized. Met.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、ポリエチレ
ン系樹脂被覆紙における叙上の問題を解決し、樹脂層の
成形加工が良好で、樹脂層と基紙との接着性に優れ、樹
脂層のゲル生成を極力防止して樹脂被覆紙としての性能
を損なうことのないポリエチレン系樹脂被覆紙を生産性
を低下させることなく得ることを目的とするものであ
る。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems in polyethylene-based resin-coated paper, provides good molding of the resin layer, has excellent adhesion between the resin layer and the base paper, It is an object of the present invention to obtain a polyethylene-based resin-coated paper that prevents the formation of a gel as much as possible and does not impair the performance as a resin-coated paper without lowering the productivity.
【００１０】[0010]
【課題を解決するための手段】本発明者等はこの目的を
達成するため検討を重ねた結果、基紙の片面にポリエチ
レン系樹脂を主成分とする樹脂層を有する樹脂被覆紙に
おいて、樹脂として特定の高密度ポリエチレン樹脂と低
密度ポリエチレン樹脂もしくは中密度ポリエチレン樹脂
との溶融混合組成物からなり、かつその臨界剪断速度を
特定のものとすることにより所期の樹脂被覆紙が得られ
ることを見い出し本発明に到達した。Means for Solving the Problems The inventors of the present invention have repeatedly studied to achieve this object, and as a result, as a resin-coated paper having a resin layer mainly composed of polyethylene resin on one side of a base paper, It has been found that the intended resin-coated paper can be obtained by using a melt-mixed composition of a specific high-density polyethylene resin and a low-density polyethylene resin or a medium-density polyethylene resin, and by setting the critical shear rate to a specific value. The present invention has been reached.
【００１１】即ち、本発明の要旨は、紙基体の片面にポ
リエチレン系樹脂を主成分とする樹脂組成物からなる樹
脂層を有する樹脂被覆紙において、樹脂層がメルトフロ
−レ−トが１０．０ｇ／１０分〜４０．０ｇ／１０分、
密度が０．９６０ｇ／ｃｍ3以上である高密度ポリエチ
レン樹脂９０重量部〜６５重量部と、メルトフロ−レ−
トが０．２ｇ／１０分〜２ｇ／１０分、密度が０．９３
５ｇ／ｃｍ3以下、分子量５０万以上の割合が１０重量
％以上、臨界剪断速度が０．５(１／秒)以下である低密
度ポリエチレン樹脂もしくは中密度ポリエチレン樹脂１
０重量部〜３５重量部とを溶融混合したポリエチレン系
樹脂組成物からなり、かつ該溶融混合した樹脂組成物の
臨界剪断速度が１０(１／秒)以下であることを特徴とす
る樹脂被覆紙に存する。ここで、臨界剪断速度とは、コ
−ン・プレ−ト型回転式粘度計を用い、後述する方法に
より２４０℃において測定した剪断応力と第一法線応力
差が等しくなる点における剪断速度のことをいう。That is, the gist of the present invention is to provide a resin-coated paper having a resin layer composed of a resin composition mainly composed of a polyethylene resin on one side of a paper substrate, wherein the resin layer has a melt flow rate of 10.0 g. / 10 minutes to 40.0 g / 10 minutes,
90 parts by weight to 65 parts by weight of a high-density polyethylene resin having a density of 0.960 g / cm 3 or more;
0.2 g / 10 min to 2 g / 10 min, density 0.93
Low-density polyethylene resin or medium-density polyethylene resin 1 having a ratio of 5 g / cm 3 or less, a molecular weight of 500,000 or more, 10% by weight or more, and a critical shear rate of 0.5 (1 / second) or less
A resin-coated paper comprising a polyethylene resin composition obtained by melt-mixing 0 to 35 parts by weight, wherein the melt-mixed resin composition has a critical shear rate of 10 (1 / sec) or less. Exists. Here, the critical shear rate is defined as the shear rate at the point where the first normal stress difference is equal to the shear stress measured at 240 ° C. by a method described later using a cone-plate rotary viscometer. That means.
【００１２】以下、本発明を詳細に説明する。本発明の
樹脂被覆紙における樹脂層に用いられる高密度ポリエチ
レン樹脂は、そのメルトフロ−レ−ト(以下、ＭＦＲと
いう)が１０．０ｇ／１０分〜４０．０ｇ／１０分、好
ましくは１０．０ｇ／１０分〜３０．０ｇ／１０分の範
囲であり、密度が０．９６０ｇ／ｃｍ3以上、好ましく
は０．９６２ｇ／ｃｍ3以上のものである。上記の物性
を有する高密度ポリエチレン樹脂(以下、ＨＤＰＥとい
う)としては、ＨＤＰＥ単独の外、エチレンを主成分と
し、これとプロピレン、ブテン等の低級α−オレフィン
との共重合体あるいはこれらの混合物等が擧げられる。Hereinafter, the present invention will be described in detail. The high-density polyethylene resin used for the resin layer in the resin-coated paper of the present invention has a melt flow rate (hereinafter, referred to as MFR) of 10.0 g / 10 min to 40.0 g / 10 min, preferably 10.0 g. / 10 min in the range of ～30.0G / 10 min, density of 0.960 g / cm 3 or more, preferably 0.962 g / cm 3 or more. As the high-density polyethylene resin having the above physical properties (hereinafter, referred to as HDPE), in addition to HDPE alone, a copolymer containing ethylene as a main component and propylene, a lower α-olefin such as butene, or a mixture thereof, or the like Is raised.
【００１３】ＨＤＰＥのＭＦＲが１０．０ｇ／１０分よ
り低い場合は、基紙と樹脂層との接着性、成形加工性等
が劣化し、４０．０ｇ／１０分より高いと樹脂の混合
性、成形加工性等が悪くなる。また、密度が０．９６０
ｇ／ｃｍ3より低い場合は、裁断性等の二次加工性が悪
化し好ましい結果が得られない。樹脂のＭＦＲ及び密度
が上記の範囲であれば、各種のＭＦＲ、密度、分子量、
分子量分布のものを単独で又は混合して使用することが
できる。When the MFR of HDPE is lower than 10.0 g / 10 min, the adhesiveness between the base paper and the resin layer, the moldability and the like are deteriorated. Molding processability etc. deteriorate. The density is 0.960
If it is lower than g / cm 3, the secondary workability such as cutability will be deteriorated, and a favorable result cannot be obtained. If the MFR and density of the resin are in the above ranges, various MFRs, densities, molecular weights,
Those having a molecular weight distribution can be used alone or in combination.
【００１４】一方、樹脂層に用いられる低密度ポリエチ
レン樹脂もしくは中密度ポリエチレン樹脂(以下、ＬＤ
ＰＥという)は、そのＭＦＲが０．２ｇ／１０分〜２ｇ
／１０分、好ましくは０．２ｇ／１０分以上１．０ｇ／
１０分未満の範囲であり、密度が０．９３５ｇ／ｃｍ3
以下、好ましくは０．９３０ｇ／ｃｍ3以下であり、分
子量５０万以上の割合が１０重量％以上、好ましくは１
２重量％以上であり、臨界剪断速度が０．５(１／秒)以
下、好ましくは０．４(１／秒)以下のものである。On the other hand, a low-density polyethylene resin or a medium-density polyethylene resin (hereinafter referred to as LD) used for the resin layer.
PE) has an MFR of 0.2 g / 10 min to 2 g
/ 10 min, preferably 0.2 g / 10 min or more and 1.0 g /
Less than 10 minutes, with a density of 0.935 g / cm 3
Or less, preferably 0.930 g / cm 3 or less, and the proportion of a molecular weight of 500,000 or more is 10% by weight or more, preferably 1% by weight or more.
It is 2% by weight or more, and has a critical shear rate of 0.5 (1 / sec) or less, preferably 0.4 (1 / sec) or less.
【００１５】ＬＤＰＥのＭＦＲが０．２ｇ／１０分より
も低いと、樹脂の混合性、基紙と樹脂層との接着性、成
形加工性等が悪化し、２ｇ／１０分より高いと成形加工
性が悪くなる。また、密度が０．９３５ｇ／ｃｍ3より
高いと基紙と樹脂層との接着性、成形加工性等が悪くな
り好ましい結果が得られない。また、樹脂の分子量５０
万以上の割合が１０重量％より少ないと成形加工性、特
にネックインが大きくなり好ましくない。ここで、分子
量の測定は、ウォ−タ−ズ社製１５０−Ｃ(カラム：東
ソ−社製ＧＭＨ−ＸＬ ＨＴ ８ｍｍφ×３０ｃｍ×３
本、溶媒：1,2,4-トリクロロベンゼン、温度：１３５
℃、流量：１ｍｌ／分)を用いるＧＰＣ法により行なっ
た。If the MFR of the LDPE is lower than 0.2 g / 10 minutes, the mixing properties of the resin, the adhesion between the base paper and the resin layer, the moldability, etc. are deteriorated. Worse. On the other hand, if the density is higher than 0.935 g / cm 3 , the adhesiveness between the base paper and the resin layer, the moldability and the like are deteriorated, so that favorable results cannot be obtained. The resin has a molecular weight of 50.
If the ratio is more than 10% by weight, molding processability, especially neck-in, is undesirably large. Here, the measurement of the molecular weight was carried out using Waters 150-C (column: GMH-XL HT 8 mmφ × 30 cm × 3 made by Tosoh Corporation).
Book, solvent: 1,2,4-trichlorobenzene, temperature: 135
(C, flow rate: 1 ml / min).
【００１６】また、ＬＤＰＥの臨界剪断速度は０．５
(１／秒)以下であることが必要であり、これより大きい
と成形加工性、樹脂層のゲル発生等の問題が生じる。図
１は、剪断応力及び第一法線応力差と、剪断速度との関
係を表わす図表であり、図１における縦軸は剪断応力及
び第一法線応力差を示し、横軸は剪断速度を示す。ま
た、図１中の線ａは剪断応力を示し、線ｂは第一法線応
力差を示す。The critical shear rate of LDPE is 0.5
(1 / second) or less, and if it is larger than this, problems such as moldability and gelation of the resin layer occur. FIG. 1 is a chart showing the relationship between the shear stress and the first normal stress difference, and the shear rate. In FIG. 1, the vertical axis indicates the shear stress and the first normal stress difference, and the horizontal axis indicates the shear rate. Show. In addition, a line a in FIG. 1 indicates a shear stress, and a line b indicates a first normal stress difference.
【００１７】本発明における臨界剪断速度の測定は、コ
−ン・プレ−ト型回転式粘度計(レオメトリック社製 レ
オメトリックメカニカルスペクトロメ−タ−、コ−ン・
プレ−ト直径：２５ｍｍ、角度：０．１ｒａｄ、温度２
４０℃)を用いて行ない、図１において、剪断応力と第
一法線応力差が等しくなる点(線ａと線ｂとの交差点)に
おける剪断速度である。剪断応力及び第一法線応力差は
次式で表わされる。 剪断応力＝(粘度)×(剪断速度) 第一法線応力差＝(第一法線応力差係数)×(剪断速度)2 In the present invention, the critical shear rate is measured by using a cone-plate type rotary viscometer (Rheometric Mechanical Spectrometer, manufactured by Rheometrics Co., Ltd.).
Plate diameter: 25 mm, angle: 0.1 rad, temperature 2
40 ° C.), and the shear rate at the point where the shear stress equals the first normal stress difference in FIG. 1 (the intersection of line a and line b). The shear stress and the first normal stress difference are represented by the following equations. Shear stress = (viscosity) x (shear rate) First normal stress difference = (first normal stress difference coefficient) x (shear rate) 2
【００１８】本発明の樹脂被覆紙における樹脂層として
は、９０重量部〜６５重量部の前記物性を有するＨＤＰ
Ｅと、１０重量部〜３５重量部の前記物性を有するＬＤ
ＰＥとを、予め溶融混合して調製したポリエチレン系樹
脂組成物からなるコンパウンド樹脂が用いられる。そし
て、その臨界剪断速度が１０(１／秒)以下であることが
必要であり、特に８(１／秒)以下のものが好適である。
臨界剪断速度が１０(１／秒)より大きいとゲルが生成し
易く好ましくない。The resin layer of the resin-coated paper according to the present invention may comprise 90 to 65 parts by weight of HDP having the above-mentioned properties.
E and 10 to 35 parts by weight of the LD having the above physical properties
A compound resin composed of a polyethylene-based resin composition prepared by previously melt-mixing PE with PE is used. It is necessary that the critical shear rate is 10 (1 / sec) or less, and particularly preferably 8 (1 / sec) or less.
If the critical shear rate is higher than 10 (1 / second), a gel is easily formed, which is not preferable.
【００１９】本発明によるゲル生成の抑制は、溶融押出
被覆時の高い樹脂温度下における樹脂の粘弾性的性質に
起因するものと考えられ、臨界剪断速度で樹脂の性質が
粘性的から弾性的になることによって、ゲル化の機会減
少、ゲルの粉砕及び混練等によりゲルの抑制が発現され
るものと思われる。It is considered that the suppression of gel formation according to the present invention is caused by the viscoelastic properties of the resin at a high resin temperature during melt extrusion coating. At a critical shear rate, the properties of the resin change from viscous to elastic. It is thought that the suppression of gel is exhibited by reducing the chance of gelation and crushing and kneading the gel.
【００２０】上記割合のＨＤＰＥとＬＤＰＥを溶融混合
する方法としては、単純溶融混合法、多段溶融混合法等
を用いることができる。例えば、バンバリ−ミキサ−、
加圧ニ−ダ−、加熱ロ−ル練り機、押出機、二軸押出機
等が使用される。なお、ＨＤＰＥとＬＤＰＥを予め溶融
混合することなく、乾燥混合のままの状態で溶融被覆用
押出機を用いて押出被覆した場合には、基紙と樹脂層と
の接着性、樹脂の混合性、成形加工性等が悪くなる。As a method of melt-mixing the above ratios of HDPE and LDPE, a simple melt-mixing method, a multi-stage melt-mixing method, or the like can be used. For example, Banbury mixer,
A pressure kneader, a heating roll kneader, an extruder, a twin screw extruder and the like are used. In addition, when the HDPE and LDPE are not melt-mixed in advance and are extrusion-coated using a melt-coating extruder in a dry-mixed state, the adhesiveness between the base paper and the resin layer, the mixing property of the resin, Molding processability etc. deteriorate.
【００２１】樹脂層に用いるポリエチレン系樹脂組成物
には、本発明の効果を損なわない範囲で、紫外線防止
剤、熱安定剤、帯電防止剤、酸化防止剤、光安定剤、滑
剤、核剤、着色剤等の各種添加剤を適宜加えることがで
きる。これらの添加剤は、使用するＨＤＰＥ又はＬＬＤ
ＰＥに予め加えるか、溶融混合時に加えるか、あるいは
これらの樹脂に高濃度に添加した所謂マスタ−バッチを
予め調製し、このマスタ−バッチを溶融押出被覆時に該
樹脂に添加してもよい。The polyethylene resin composition used in the resin layer may contain, as long as the effects of the present invention are not impaired, an ultraviolet ray inhibitor, a heat stabilizer, an antistatic agent, an antioxidant, a light stabilizer, a lubricant, a nucleating agent, Various additives such as a coloring agent can be appropriately added. These additives are used in HDPE or LLD
A so-called masterbatch may be added in advance to PE, added during melt mixing, or added to these resins at a high concentration, and the masterbatch may be added to the resin during melt extrusion coating.
【００２２】本発明に使用される基紙としては、通常の
天然パルプを主成分とする天然パルプ紙、天然パルプと
合成繊維とからなる混抄紙、合成パルプ、合成繊維、あ
るいは合成樹脂フィルムからなる合成紙の何れでもよ
い。また、基紙には、サイズ剤、紙力増強剤、填料、定
着剤，ｐＨ調整剤、着色剤、蛍光増白剤等の各種の添加
剤を含有させることができる。The base paper used in the present invention is a natural pulp paper mainly composed of ordinary natural pulp, a mixed paper made of natural pulp and synthetic fibers, a synthetic pulp, a synthetic fiber or a synthetic resin film. Any of synthetic paper may be used. Further, the base paper may contain various additives such as a sizing agent, a paper strength enhancer, a filler, a fixing agent, a pH adjuster, a colorant, and a fluorescent whitening agent.
【００２３】本発明の樹脂被覆紙を製造するには、走行
する基紙上に上記ポリエチレン系樹脂組成物を溶融押出
機を用い、そのスリットダイからフィルム状に流延して
被覆する、いわゆる溶融押出し被覆法が採用される。溶
融押出温度は、通常２８０℃ないし３４０℃であるのが
好ましく、また、ポリエチレン系樹脂組成物を基紙に被
覆する前に、基紙にコロナ放電処理、火炎処理等の活性
化処理を施すことが好ましい。樹脂層の厚みとして特に
制限はないが、５ミクロンないし５０ミクロン程度の厚
さに塗布したものが一般的である。In order to produce the resin-coated paper of the present invention, the above-mentioned polyethylene resin composition is cast on a running base paper from a slit die into a film by using a melt extruder. A coating method is employed. The melt extrusion temperature is usually preferably 280 ° C. to 340 ° C., and the base paper is subjected to an activation treatment such as corona discharge treatment or flame treatment before coating the polyethylene resin composition on the base paper. Is preferred. The thickness of the resin layer is not particularly limited, but is generally applied to a thickness of about 5 to 50 microns.
【００２４】[0024]
【実施例】以下、本発明を実施例について更に具体的に
説明するが、本発明はその要旨を超えない限りこれ等の
実施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist of the present invention.
【００２５】実施例１ ＭＦＲ１５．０ｇ／１０分、密度０．９６７ｇ／ｃｍ3
のＨＤＰＥ(後記する表１のＡ)７０重量部と、ＭＦＲ
０．６ｇ／１０分、密度０．９２４ｇ／ｃｍ3、分子量
５０万の割合が１５重量％以上、臨界剪断速度が０．０
６(１／秒)のＬＤＰＥ(表１のｅ)３０重量部とを予め溶
融混合し、これを樹脂温度３２０℃で押出機より坪量１
７０ｇ／ｍ2の平滑性の高い紙に厚さ２５μｍとなるよ
う押出塗工して作製した。Example 1 MFR 15.0 g / 10 min, density 0.967 g / cm 3
70 parts by weight of HDPE (A in Table 1 described below) and MFR
0.6 g / 10 min, density 0.924 g / cm 3 , molecular weight of 500,000, 15% by weight or more, critical shear rate of 0.0
30 parts by weight of 6 (1 / sec) LDPE (e in Table 1) were melt-mixed in advance, and the mixture was extruded at a resin temperature of 320 ° C. from an extruder to a basis weight of 1
It was prepared by extrusion coating a 70 g / m 2 highly smooth paper to a thickness of 25 μm.
【００２６】樹脂の溶融押出被覆時の成形加工性の評価
方法としては、樹脂被覆部分の横方向の長さを測定して
ネックインの程度を評価すると共に、溶融樹脂膜のスジ
の発生の程度、ドロ−ダウン性の程度による膜切れ発生
の有無、サ−ジング又はドロ−レゾナンスによる流動の
不安定性等の成形加工性について総合的に評価した。評
価基準としては、○：良好、△：やや悪いが実用上問題
がない程度、×：悪く実用上問題がある程度、を表わ
す。As a method of evaluating the moldability during melt extrusion coating of the resin, the length of the resin-coated portion in the lateral direction is measured to evaluate the degree of neck-in, and the degree of occurrence of streaks in the molten resin film. Molding processability such as the presence or absence of film breakage due to the degree of drawdown, and instability of flow due to surge or draw resonance were comprehensively evaluated. The evaluation criteria are as follows: ：: good, Δ: slightly bad but no practical problem, x: bad and practically problematic.
【００２７】樹脂被覆紙の基紙と樹脂層との接着性の評
価方法としては、試料を基紙層と樹脂層とに剥離し、剥
離した樹脂層に付着した基紙層の面積率を測定すること
により、基紙と樹脂層との接着性を評価した。評価基準
としては、○：面積率が１００％で良好、△：面積率が
１００％未満で８０％以上であり、接着性がやや悪いが
実用上問題がない程度、×：面積率が８０％未満であ
り、接着性が悪く実用上問題がある程度、を表わす。As a method for evaluating the adhesiveness between the base paper and the resin layer of the resin-coated paper, a sample is separated into the base paper layer and the resin layer, and the area ratio of the base paper layer adhered to the separated resin layer is measured. Then, the adhesiveness between the base paper and the resin layer was evaluated. The evaluation criteria were as follows: ：: good at 100% area ratio, Δ: 80% or more with less than 100% area ratio, a little poor adhesion but practically no problem, x: 80% area ratio , Which indicates that the adhesion is poor and there is some practical problem.
【００２８】樹脂の溶融押出時のゲルの評価方法として
は、設定温度３２０℃、１時間あたり２．５ｋｇとなる
条件下で８時間フィルム状に押出した後の０．０１ｍ2
のフィルム中における０．１ｍｍ以上のゲルの個数を測
定し、初期の値と比較することによりゲルを評価した。
評価基準としては、○：８時間後のゲルの個数が初期値
と変わらない、×：８時間後のゲルの個数が初期値より
増加した程度、を表わす。As a method for evaluating the gel at the time of melt extrusion of the resin, 0.01 m 2 after extruding into a film for 8 hours at a set temperature of 320 ° C. and 2.5 kg per hour.
The gel was evaluated by measuring the number of gels having a size of 0.1 mm or more in the film and comparing with the initial value.
As evaluation criteria, ○: the number of gels after 8 hours does not change from the initial value, x: the degree to which the number of gels after 8 hours increased from the initial value.
【００２９】樹脂被覆紙の二次加工性の評価方法として
は、試料を市販のギロチンカッタ−で裁断した切り口の
状態の毛羽立ちの程度による裁断性の評価、樹脂被覆紙
の樹脂層面を相互に重ね擦り合わせた場合の樹脂層表面
の傷の程度による耐摩擦性、樹脂被覆紙の腰等の二次加
工性について総合的に評価した。評価基準としては、
○：良好、△：やや悪いが実用上問題がない程度、×：
悪く実用上問題がある程度、を表わす。本実施例に用い
たＨＤＰＥ及びＬＤＰＥの物性を表１に示し、また、得
られた樹脂被覆紙につき上記評価方法により得られた評
価結果を表２に示す。The secondary workability of the resin-coated paper was evaluated by evaluating the cuttability of the sample cut with a commercially available guillotine cutter based on the degree of fluffing of the cut edge, and overlapping the resin layer surfaces of the resin-coated paper with each other. Comprehensive evaluation was performed on the friction resistance according to the degree of scratches on the resin layer surface when rubbing, and the secondary workability such as the stiffness of the resin-coated paper. As evaluation criteria,
：: good, △: slightly bad, but no practical problem, ×:
It is bad and has some practical problems. Table 1 shows the physical properties of HDPE and LDPE used in this example, and Table 2 shows the evaluation results obtained by the above-described evaluation method for the obtained resin-coated paper.
【００３０】実施例２〜９ 実施例１で使用したＨＤＰＥとＬＤＰＥの組合せの代り
に、夫々表１に示すＨＤＰＥとＬＤＰＥを組合せた種々
の樹脂組成物を用い、実施例１と同様にして樹脂被覆紙
を得た。それらにつき上記評価方法による評価結果を表
２に示す。Examples 2 to 9 In place of the combination of HDPE and LDPE used in Example 1, various resin compositions each combining HDPE and LDPE shown in Table 1 were used. A coated paper was obtained. Table 2 shows the results of the evaluation by the above evaluation method.
【００３１】比較例１〜９ 比較例１〜８では、実施例１で使用したＨＤＰＥとＬＤ
ＰＥの組合せの代りに、夫々表１に示すＨＤＰＥとＬＤ
ＰＥを組合せた種々の樹脂組成物を用いた以外は、実施
例１と同様にして樹脂被覆紙を得た。それらにつき上記
評価方法による評価結果を表３に示す。また、比較例９
では、実施例１と同一の種類及び組成のＨＤＰＥ及びＬ
ＤＰＥの樹脂組成物を使用し、これを溶融混合すること
なく、そのまま乾燥混合したもの用いた以外は、実施例
１と同様にして樹脂被覆紙を得た。その上記評価方法に
よる評価結果を表３に示す。Comparative Examples 1 to 9 In Comparative Examples 1 to 8, the HDPE and LD used in Example 1 were used.
Instead of the combination of PE, HDPE and LD shown in Table 1 respectively
A resin-coated paper was obtained in the same manner as in Example 1, except that various resin compositions in which PE was combined were used. Table 3 shows the results of the evaluation by the above evaluation method. Comparative Example 9
Then, the same kind and composition of HDPE and L
A resin-coated paper was obtained in the same manner as in Example 1, except that a resin composition of DPE was used, and the mixture was dried and mixed without being melt-mixed. Table 3 shows the evaluation results obtained by the above evaluation method.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【表２】 [Table 2]
【００３４】[0034]
【表３】 [Table 3]
【００３５】表２の結果から、本発明に規定する物性の
ＨＤＰＥ９０重量部〜６５重量部と、ＬＤＰＥ１０重量
部〜３５重量部を配合した樹脂組成物で、かつその臨界
剪断速度が１０(１／秒)以下の樹脂層を有する樹脂被覆
紙(実施例１〜９)は、成形加工性及び接着性が良好であ
り、かつゲルが少なく優れた品質のものであることが理
解される。From the results shown in Table 2, it is found that a resin composition containing 90 to 65 parts by weight of HDPE and 10 to 35 parts by weight of LDPE having the physical properties defined in the present invention and having a critical shear rate of 10 (1/1). Seconds) It is understood that the resin-coated paper having a resin layer of (less than or equal to) (Examples 1 to 9) has good moldability and adhesiveness, and has excellent quality with little gel.
【００３６】一方、表３の結果から、本発明の要件を具
備しない場合、例えば、ＨＤＰＥの含有量が９０重量部
より多い場合(比較例１〜２)には、成形加工性、接着性
が悪くゲルも多い。ＨＤＰＥの含有量が６５重量部より
少ない場合(比較例３)には二次成形加工性が劣り、ま
た、ＬＤＰＥの臨界剪断速度が０．５(１／秒)より大き
い場合(比較例４〜７)にはゲルが多く、ＬＤＰＥ中の分
子量５０万以上の割合が１０重量％より少ない場合(比
較例５〜８)には成形加工性が不良である。On the other hand, from the results in Table 3, when the requirements of the present invention are not satisfied, for example, when the content of HDPE is more than 90 parts by weight (Comparative Examples 1 and 2), the moldability and adhesiveness are poor. Bad gel. When the content of HDPE is less than 65 parts by weight (Comparative Example 3), the secondary molding processability is poor, and when the critical shear rate of LDPE is more than 0.5 (1 / sec) (Comparative Examples 4 to 5). In 7), the gel is large, and when the ratio of the molecular weight of 500,000 or more in LDPE is less than 10% by weight (Comparative Examples 5 to 8), the moldability is poor.
【００３７】更に、ＨＤＰＥとＬＤＰＥとの樹脂組成物
の臨界剪断速度が１０．０(１／秒)より大きい場合(比
較例１、２及び４〜７)にはゲルが多い。また、ＨＤＰ
ＥとＬＤＰＥの組成物を溶融混合せずに、そのまま乾燥
混合した場合(比較例９)には成形加工性が悪く好ましい
結果が得られない。Further, when the critical shear rate of the resin composition of HDPE and LDPE is larger than 10.0 (1 / sec) (Comparative Examples 1, 2 and 4 to 7), the gel content is large. Also, HDP
When the composition of E and LDPE is dry-mixed as it is without being melt-mixed (Comparative Example 9), the moldability is poor and a favorable result cannot be obtained.
【００３８】[0038]
【発明の効果】本発明によれば、樹脂層の成形加工性が
良好で、樹脂層と基紙との接着性に優れ、ゲルの少ない
ポリエチレン系樹脂被覆紙が提供される。According to the present invention, there is provided a polyethylene resin-coated paper having good moldability in the resin layer, excellent adhesion between the resin layer and the base paper, and low gel.
【図１】剪断応力及び第一法線応力差と剪断速度との関
係を表わす図表であり、縦軸は剪断応力及び第一法線応
力差を示し、横軸は剪断速度を示す。FIG. 1 is a chart showing a relationship between a shear stress and a first normal stress difference and a shear rate, wherein the vertical axis represents the shear stress and the first normal stress difference, and the horizontal axis represents the shear rate.
ａ 剪断応力 ｂ 第一法線応力差 a Shear stress b First normal stress difference
───────────────────────────────────────────────────── フロントページの続き (72)発明者 池谷 暢重 岡山県倉敷市潮通３丁目10番地 三菱化 成株式会社水島工場内 (72)発明者 世利 卓也 岡山県倉敷市潮通３丁目10番地 三菱化 成株式会社水島工場内 (72)発明者 新田 晃平 岡山県倉敷市潮通３丁目10番地 三菱化 成株式会社水島工場内 (56)参考文献 特開 昭60−150049（ＪＰ，Ａ) 特開 昭60−35728（ＪＰ，Ａ) 特開 昭58−95732（ＪＰ，Ａ) 特開 平５−107688（ＪＰ，Ａ) 特開 平５−40327（ＪＰ，Ａ) 特開 平５−307228（ＪＰ，Ａ) 実開 昭59−149944（ＪＰ，Ｕ) (58)調査した分野(Int.Cl.7，ＤＢ名) B32B 1/00 - 35/00 D21H 11/00 - 27/42 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Nobushige Iketani 3-10-10 Shiodori, Kurashiki-shi, Okayama Prefecture Inside Mizushima Plant, Mitsubishi Kasei Co., Ltd. (72) Inventor Takuya Seri 3-chome, Kuroshiki-shi, Okayama Address: Mizushima Plant, Mitsubishi Chemical Co., Ltd. (72) Kohei Nitta 3-10, Ushidori, Kurashiki-shi, Okayama Prefecture, Mizushima Plant, Mitsubishi Chemical Co., Ltd. (56) References JP-A-60-150049 (JP, A) JP-A-60-35728 (JP, A) JP-A-58-95732 (JP, A) JP-A-5-107688 (JP, A) JP-A-5-40327 (JP, A) 307228 (JP, A) Fully open sho 59-149944 (JP, U) (58) Fields investigated (Int. Cl. 7 , DB name) B32B 1/00-35/00 D21H 11/00-27/42
Claims (1)
成分とする樹脂組成物からなる樹脂層を有する樹脂被覆
紙において、樹脂層が、メルトフロ−レ−トが１０．０
ｇ／１０分〜４０．０ｇ／１０分、密度が０．９６０ｇ
／ｃｍ3以上である高密度ポリエチレン樹脂９０重量部
〜６５重量部と、メルトフロ−レ−トが０．２ｇ／１０
分〜２ｇ／１０分、密度が０．９３５ｇ／ｃｍ3以下、
分子量５０万以上の割合が１０重量％以上、臨界剪断速
度が０．５（１／秒）以下である低密度ポリエチレン樹
脂もしくは中密度ポリエチレン樹脂１０重量部〜３５重
量部とを溶融混合したポリエチレン系樹脂組成物からな
り、かつ該溶融混合した樹脂組成物の臨界剪断速度が１
０（１／秒）以下であることを特徴とする樹脂被覆紙。1. A resin-coated paper having a resin layer comprising a resin composition containing a polyethylene resin as a main component on one surface of a paper substrate, wherein the resin layer has a melt flow rate of 10.0.
g / 10 min to 40.0 g / 10 min, density 0.960 g
A high density polyethylene resin 90 parts by weight to 65 parts by weight is / cm 3 or more, melt flow - Le - DOO is 0.2 g / 10
Min to 2 g / 10 min, the density is 0.935 g / cm 3 or less,
A polyethylene-based mixture obtained by melt-mixing 10 parts by weight to 35 parts by weight of a low-density polyethylene resin or a medium-density polyethylene resin having a molecular weight of 500,000 or more at a rate of 10% by weight or more and a critical shear rate of 0.5 (1 / sec) or less. The melt-mixed resin composition has a critical shear rate of 1
Resin-coated paper characterized by being at most 0 (1 / second).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04358006A JP3126079B2 (en) | 1992-12-25 | 1992-12-25 | Resin coated paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04358006A JP3126079B2 (en) | 1992-12-25 | 1992-12-25 | Resin coated paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06190983A JPH06190983A (en) | 1994-07-12 |
| JP3126079B2 true JP3126079B2 (en) | 2001-01-22 |
Family
ID=18457062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04358006A Expired - Fee Related JP3126079B2 (en) | 1992-12-25 | 1992-12-25 | Resin coated paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3126079B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010215892A (en) * | 2009-01-28 | 2010-09-30 | Adeka Corp | Polyolefin resin composition |
| JP6827892B2 (en) * | 2017-07-24 | 2021-02-10 | 大日本印刷株式会社 | Polyolefin resin film |
| JP6450486B1 (en) * | 2018-04-13 | 2019-01-09 | 株式会社旭パック | Polyethylene sheet, composite sheet and method for producing polyethylene sheet |
| SE542945C2 (en) * | 2018-10-03 | 2020-09-22 | Stora Enso Oyj | Polymer coated paper and paperboard |
-
1992
- 1992-12-25 JP JP04358006A patent/JP3126079B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06190983A (en) | 1994-07-12 |
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