JPH0435163Y2 - - Google Patents

Description

[Detailed explanation of the idea]

[Industrial Application Field] The present invention relates to printed laminated paper that is made by laminating a polyolefin film on the printing surface of printed paper and has excellent adhesiveness, gloss, antistatic properties, flatness, and anti-blocking properties. It is. [Prior Art] Conventionally, print laminated paper has been known that is made by thermo-compression bonding a polypropylene film laminated with a thermal adhesive layer and printing paper without using an organic solvent (for example, JP-A-59-1999). Publication No. 24661,
(Japanese Patent Application Laid-Open No. 56-42652, etc.). [Problems that the invention aims to solve] However, although this printed laminated paper does have good thermal adhesion between the printed paper and polypropylene,
The antistatic properties and gloss were poor, and the laminated paper had a serious drawback of curling. The present invention provides a printed laminated paper that does not have these drawbacks, that is, has strong adhesion to printing paper, and has excellent antistatic properties, gloss, and flatness (i.e., does not curl). The purpose is to [Means for Solving the Problems] The present invention consists of a polyolefin layer containing an antistatic agent and a polypropylene layer containing 10 to 50% by weight of at least one of petroleum resin and terpene resin. In printed laminated paper in which printed paper ( ) is laminated on the layer ( ) of a composite film, the polypropylene layer ( ) is 100 mm from the surface of the side in contact with the paper ( ).
1 or more imino-type or/and amino-type nitrogen atoms per 100 carbon atoms in the surface layer up to Å,
and printed laminated paper having 10 or more carbonyl oxygen atoms. The polyolefin of the polyolefin layer () containing the antistatic agent of the present invention is a known polyolefin, and specifically, polypropylene, polystyrene, methylpentene polymer, polyparaxylylene, and copolymers thereof can be mentioned. Propylene homopolymer is particularly preferred. Furthermore, the antistatic agent contained in the layer () may be any known antistatic agent such as cationic, anionic, nonionic, or amphoteric antistatic agents, but in particular quaternary ammonium salts may be used. A betaine type antistatic agent is preferred. The amount of antistatic agent added is preferably 0.1 to 2% by weight, more preferably
It is in the range of 0.2 to 1% by weight. Those within this range are suitable for achieving both antistatic properties and thermal adhesion to the layer (). The polypropylene of the polypropylene layer containing at least one of a petroleum resin and a terpene resin may be any known polypropylene, and is not particularly limited, but is crystalline polypropylene with an intrinsic viscosity measured in boiling n-heptane [ η] is 1.4
~3.2dl/g, more preferably 1.8~2.3dl/g, isotactic index 90% or more,
More preferably, it is 95% or more. In addition, it is better to copolymerize a block of 2 to 13 mol%, more preferably 6 to 10 mol%, of ethylene, butene, etc. as an α-olefin component, rather than a homopolymer, as this produces minute irregularities on the film surface. It is preferable because it can be tightened and prevent blocking, and it is also preferable because it can be laminated with printing paper at a relatively low temperature. However, if the propylene component is less than 87 mol%, the resulting laminated paper will tend to curl and will have poor gloss, which is not preferred for the present invention. The petroleum resin contained in the layer () is a resin made directly from petroleum-based unsaturated hydrocarbons, and there are some whose main raw material is cyclopetadiene and others whose main raw material is higher olefinic hydrocarbons. , in the case of the present invention, the former is preferable. A typical resin name is hydrogenated dicyclopentadiene (such as "Escoretsu" manufactured by Exxon). In addition, the terpene resin contained in the layer () is a hydrocarbon having a molecular formula of (C ₅ , H ₈ ) _o (where n is a natural number from 3 to 50), and their oxygen derivatives and unsaturated derivatives. In the case of the present invention, saturated hydrocarbons consisting only of carbon and hydrogen are preferred. In the case of the present invention, the above-mentioned resins can have both low-temperature adhesion and antistatic properties by using hydrocarbons that do not substantially contain double bonds and do not contain atoms such as nitrogen, oxygen, and sulfur. The layer () contains 10 to 50% by weight, preferably at least one of the above petroleum resins and terpene resins.
It contains 15 to 35% by weight. If this content is less than 10% by weight, preferably less than 15% by weight,
Adhesion is poor, the laminated paper curls and has poor flatness, and the resulting laminated paper has poor gloss. On the other hand, if it exceeds 50% by weight, preferably 35% by weight, the film will not only whiten during heating and result in a laminated paper with poor gloss, but also the antistatic ability will decrease, and the productivity of the film will deteriorate, resulting in high costs. . In addition, the layer () has nitrogen atoms of imino or amino type per 100 carbon atoms in the surface layer up to 100 Å from the surface on which the paper () is laminated.
1 or more, and 10 carbonyl oxygen atoms O
Must have at least one. The ratio N/C of N and C is less than 0.01 and the ratio O/C of O and C is less than 0.01.
If it is less than 0.1, the adhesion to printing paper is poor and practical adhesive strength cannot be obtained. For this reason, when bonding is performed at a higher thermal bonding temperature, the adhesive strength appears to improve somewhat, but not only is the adhesive strength still insufficient, but the resulting laminate may be damaged due to heat shrinkage of the polyolefin composite film. The paper curls and becomes unusable. That is, if N/C is less than 0.01 and O/C is less than 0.1, it is impossible to obtain a laminated paper with good gloss and strong adhesion to printing paper without curling the laminated paper. The upper limits of the number of nitrogen atoms and the number of oxygen atoms per 100 carbon atoms are not particularly limited, but the number of nitrogen atoms N is preferably 8 or less, more preferably 5 or less. Further, in the case of oxygen atoms O, the number is preferably 50 or less, preferably 35 or less. The printed paper may be natural paper, synthetic paper, or mixed paper, but kraft paper is preferable, and paper with a basis weight of 50 to 400 g/m ² is preferable. Further, the printing may be any known printing. Note that the present invention has the above configuration, that is,
Polyolefin layer (), polypropylene layer (), printed paper () are ()/()/
It is a laminated paper laminated in the order of (). Representative examples of this laminated paper will be explained based on the drawings. The figure is a cross-sectional view of printed laminated paper, where 1 is a layer containing an antistatic agent (), 2 is a petroleum resin,
Layer containing terpene resin (), 3 is layer ()
4 is the imino (amino) nitrogen atom and carbonyl of a composite film in which layer 1 and layer 2 are laminated on the printed surface of printed paper 4. The surface layer portion 3 having oxygen atoms of 200 to 3000 is thermally bonded. Note that the present invention naturally also includes the following configuration. (a) Layer () contains a specific petroleum resin or terpene resin in an amount smaller than that contained in layer (), preferably less than 10% by weight. (b) The amount of antistatic agent contained in the () layer is less than that contained in the () layer, preferably 0.1% by weight.
Contains less than (c) Between the () layer and the () layer, there is another layer, specifically the antistatic agent used in the () layer, and the ()
A polyolefin layer containing a specific petroleum resin or terpene resin used in the layer. Although the present invention describes a method for manufacturing printed laminated paper, it is not necessarily limited thereto. Polyolefin mixed with an antistatic agent and polypropylene mixed with petroleum resin are fed to separate extruders, and the molten polymers are laminated in the die and placed on a casting drum maintained at 40 to 95°C. Nip cast and cool to solidify. The cast sheet was preheated in a hot air oven kept at 120-145°C, stretched 4-7 times in the longitudinal direction, and then stretched 7 times in the width direction in a tenter kept at 140-158°C.
It was stretched ~12 times and heat-treated at 150-165°C while being relaxed by a few percent. Next, after cutting and removing the edges, the layer () where the antistatic agent is mixed is subjected to corona discharge treatment, and the layer () where the petroleum resin is mixed is treated with an oxygen concentration of 0.1 Vol% or less, and nitrogen gas is applied to the layer () where the petroleum resin is mixed. (50~99.5Vol%) and carbon gas (0.5~50Vol%)
%) in a mixed gas atmosphere,
A film having a thickness of 5 to 100 μm was wound onto a roll to obtain a composite film. Of course, this film contains antioxidants, ultraviolet absorbers, flame retardants, etc. as necessary.
Various additives such as inorganic lubricants, anti-blocking agents, and clarifying agents may be added. Next, the printed surface of the printed paper and the () layer of the composite film are stacked so that they face each other, and
Metal roll kept at ~120℃ (surface roughness 0.2μm,
(mirror finish) and then bonded together with a linear pressure of 10 to 300 kg/cm and cooled. The laminated paper thus obtained does not curl, has strong adhesive strength between the paper and the polyolefin composite film, and has excellent antistatic properties and gloss. The thickness composition ratio of the polyolefin composite film is the polyolefin layer containing an antistatic agent ()
less than 50% of the total composite film thickness, preferably
A content of about 25 to 40% is preferable from the viewpoint of adhesive properties between the antistatic agent and the printing paper. [Effects of the invention] As described above, the present invention laminates a polypropylene layer () containing a specific petroleum resin (terpene resin) on a polyolefin layer () containing an antistatic agent, and By introducing specific nitrogen and oxygen atoms on the outer surface,
The obtained laminated paper did not curl and had excellent adhesion, gloss, and antistatic properties. Note that the method for measuring physical property values related to the present invention is as follows. (1) Imino or amino type nitrogen atoms,
The oxygen atoms of carbonyl and carbonyl are directly bonded to the carbon of the polypropylene polymer chain, and the amount thereof is measured using the ESCA method. The ESCA method used in this invention is an abbreviation for soft X-ray excitation photoelectron spectroscopy, which uses the spectra of photoelectrons ejected from atoms in a sample compound by soft X-ray irradiation to identify elements near the surface of the sample. This is a method to analyze the type and chemical bonding state of
In the ESCA method, the photoelectron transmission ability is small for hydrocarbon polymer materials, and ESCA measurements of the polymer materials have the characteristic that relatively strong information can be obtained from the surface, especially within 100 Å of the polar layer. Amino type and/or imino type nitrogen in the present invention refers to bonded nitrogen identified by the ESCA method, and is represented by amino groups and imino groups.
IS orbital of bonded nitrogen (N _IS ) measured by ESCA
Spectral binding energy is 397.0~402.5eV
(However, the main peak of C _IS in polypropylene is assumed to be 285.0 eV) (hereinafter simply referred to as amino-type nitrogen and/or imino-type nitrogen). Furthermore, the carbonyl oxygen atom is a bonded oxygen identified by the ESCA method.
The binding energy of the IS orbital (O _IS ) spectrum is
It has a peak in the range of 286.0 to 289.5 eV (hereinafter simply referred to as carbonyl oxygen). Specifically, an ESCA spectrometer ES-200 model manufactured by Kokusai Electric Co., Ltd. was used to measure the N _IS spectrum and C _IS spectrum of the treated surface of the treated film, and the amino type or I IS spectrum of the N _IS spectrum was measured.
and the ratio of the integrated intensity of the peak corresponding to the binding energy of imino nitrogen and the integrated intensity of the C _IS spectrum was calculated. The O _IS spectrum and the C _IS spectrum were similarly measured, and the ratio of the integrated intensity of the peak corresponding to the bond energy of carbonyl type oxygen in the O _IS spectrum to the integrated intensity of the C _IS spectrum was calculated. In the present invention, the number ratio N/C of amino type or imino type nitrogen and carbon atoms and the number ratio O/C of carbonyl type oxygen and carbon atoms are calculated based on the above-mentioned integrated intensity ratio. (2) Glossiness: Measured according to ASTM D-2457. The angle of incidence is 60°C. (3) Intrinsic viscosity: According to ASTM D-1601. (4) Antistatic properties were judged by the surface specific resistance value of the film, and those with a value of 10 ¹³ ohm cm or less were considered good. For surface resistivity, measure the film at 25°C.
After being left at 65RH% for 2 days and nights, measurements were taken using a Kiger ohmmeter manufactured by Kawaguchi Electric. (5) Adhesion is the interlayer adhesion force with the film paper (interlayer adhesion force is the force of peeling the film 180 degrees at a speed of 100 mm/min using Toyo Seiki Tensilon in a measurement atmosphere of 25°C) ) Comparison was made based on the surface temperature of the metal roll obtained at 100 g/cm. The lower the temperature, the better the adhesion. [Examples] The present invention will be described below based on Examples. As polypropylene, intrinsic viscosity [η] = 1.6,
Isotactic Index II = 98% homopolymer, 0.5% by weight of TPA-5028 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) as an antistatic agent, and EC-1 (manufactured by EC Chemical Co., Ltd.) as a crystal nucleating agent. The polymer () containing 0.2% by weight of was fed to a 30 mm extruder. On the other hand, ethylene propylene copolymer ([η] = 2.2), which is made by copolymerizing ethylene into a 7% block,
As a specific petroleum resin, dicyclopentadiene resin (“Escoretsu” 5320: Exxon Chemical Co., Ltd.) is used.
Polymer (20% by weight) was fed into a 65 mm extruder. In both extruders, the polymer heated to 220℃ is melted, the polymers () and () are laminated in two layers in the nozzle, and then extruded from the nozzle.
The polymer () is cooled and solidified on a casting drum maintained at a temperature of 0.degree. C. so that the polymer () is in contact with the casting drum to obtain a cast film. The cast film was preheated on a Teflon-coated heating roll, stretched 5 times in the longitudinal direction at 135°C, and then cooled. Subsequently, the film was stretched 9 times in the width direction in a tenter heated to 150°C, and then heat treated at 155°C while allowing 8% relaxation in the width direction. The obtained film had a total thickness of 15 μm, with the () layer being 5 μm and the () layer being 10 μm. Subsequently, the polymer () layer was subjected to corona discharge treatment in air, and the polymer () layer was subjected to corona discharge in a mixed atmosphere of 90% nitrogen and 10% carbon gas.
The () layer had a high N/C value of 0.02 and an O/C value of 0.25. Next, layer () of the above film was superimposed on the printed surface of the book cover, and a linear pressure of 100 kg/cm was applied using a heated mirror roll (100 mm).
They were bonded together at a speed of 5 m/min and then rapidly cooled. The properties of the laminated paper thus obtained are shown in Table 1. As is clear from these results, the laminated paper of the present invention is found to be excellent in appearance, ease of handling, adhesion, etc. Comparative Examples 1 to 3 () of the biaxially stretched film prepared in Example 1
We compared the properties of printed laminated paper by changing the method of corona discharge treatment applied to the layers (none, atmosphere in air, atmosphere in nitrogen). Results first
Shown in the table. From this result, the value of N/C is 1/
It can be seen that curl, gloss, low-temperature thermal adhesion, etc. cannot be obtained unless there are 100 carbon atoms or more and the O/C value is 10/100 carbon atoms or more. Comparative Example 4 A printed laminated paper was prepared in the same manner as in Example 1 except that only the ethylene propylene copolymer was used instead of the petroleum resin used in layer ( ) in Example 1. Table 1 shows the properties of the obtained laminated paper. It can be seen that if petroleum resin is not added, even if the N/C value and O/C value are high, not only can the laminated paper not be bonded at a low temperature without curling, but also excellent gloss cannot be obtained. Comparative Example 5 A print laminate was produced in the same manner as in Example 1, except that ethylene vinyl acetate EV _AC (vinyl acetate 12% by weight) polymer was used instead of the ethylene propylene copolymer used in the () layer of Example 1. Created a paper. Table 1 shows the properties of the obtained laminated paper. As can be seen from these results, changing the polymer used in the () layer to EV _AC not only has the fatal disadvantages of curling the laminated paper, poor antistatic properties, and reduced gloss. This has the disadvantage that the composite films tend to block each other. Comparative Example 6 “Quinton” D-100 was used instead of “Escolets” 5320, which is the specific petroleum resin used in Example 1.
Example 1 except that (manufactured by Nippon Zeon Co., Ltd.) was used.
Printed laminated paper was created in the same manner.
Table 1 shows the properties of the obtained laminated paper. It can be seen that excellent adhesiveness, antistatic properties, and gloss cannot be obtained unless the resin is a specific petroleum resin that does not substantially contain polar groups or double bonds. Example 2 Laminated paper was prepared in the same manner as in Example 1, except that the raw materials used in Example 1 were changed as follows in consideration of the recovery process, and the obtained quality is shown in Table 1. . As an additive, 7% by weight of a specific petroleum resin added to the polymer () layer is added to the polymer (). Furthermore, 0.08% by weight of the antistatic agent used in Polymer () is added as an additive to Polymer (). As is clear from the table, the present invention exhibits excellent properties as a laminated paper even when the additives are mixed with each other.

【table】

【table】 [Brief explanation of the drawing]

The figure is a cross-sectional view of a typical printed laminated paper of the present invention. 1... Layer containing an antistatic agent (), 2...
Layer containing petroleum resin and terpene resin (), 3
. . . Surface layer portion having imino (amino) nitrogen atoms of layer (), 4 . . . Printed paper.

Claims (1)

[Scope of utility model registration request] Polyolefin layer containing antistatic agent ()
and at least one of petroleum resin and terpene resin.
In a printed laminated paper in which printed paper ( ) is laminated on the layer ( ) side of a composite film laminated with a polypropylene layer ( ) containing 10 to 50% by weight, the polypropylene layer ( ) is
Characterized by having one or more imino-type and/or amino-type nitrogen atoms and ten or more carbonyl oxygen atoms per 100 carbon atoms in the surface layer up to 100 Å from the surface in contact with the paper (). Printed on laminated paper.