JPS5876269A - Easily adhesive film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polypropylene-based composite film, in particular, a polypropylene-based polymer is used as the film base film, and the film has properties such as printing ink refillability, adhesion to thin metals, and adhesion to aluminum alloys. is in good condition.

The present invention also relates to an easily [F-resistant film] with improved processability.

Food packaging and textile packaging #! For plastic films used in (V, -) (as well as under two layers), adaptability to high-speed printing, reduction of residual solvent.

Characteristics of low-cost inks and water-based inks, such as mW performance and suitability for direct coating processing, are also becoming desirable. For example, water-based inks are expected to be used more and more widely because they do not pose the problem of environmental pollution due to excessive bathing. One such ink is known, for example, one that uses a cellulose derivative as a binder (trade name: 6Cello8 ink). However, printing on currently commercially available polypropylene films requires special organic solvents. Each type of ink is used, and each ink is stored and stored in a tube, and the corresponding anchor coat (anchor coat agent for laminating low melting point films such as jib/liethylene) is also stored in the same way.

In the bag making process, many kinds of inks and adhesives had to be prepared.

In order to provide printability, there has also been an attempt to improve the I# adhesion of the film by coating the film surface with a resin liquid. However, it is a process that is complicated, expensive, and wasteful.In addition, polypropylene thread film has poor metal deposition properties and poor adhesion to metal foil.

Ply i-processing has been applied to cover this, but the primer tends to cause deterioration of the deposited metal (it inhibits printability and adhesion workability on the deposited surface, and it also requires primer treatment). Only 4 is uneconomical.

Polypropylene film KFi has various drawbacks as described above, but it has poor adaptability to water-based inks that have been developed in recent years and to the dye reflex of various polymers, and it is difficult to improve this. If possible, it would be extremely advantageous to prevent environmental pollution caused by solvents, omit pretreatment steps, save materials, and reduce residual solvents.

The present invention was made with attention to these circumstances, and includes improvements in the adhesiveness of seal ink and the conductivity of metal #film grade.

The object of the present invention is to provide a polypropylene thread composite film having good adhesion properties and easy adhesion.

Achieving the above objectives [A successful composite film is
For the base film containing polypropylene yarn polymer, at least one side thereof (acrylic acid-based amide derivative)
-(a-olefin) coelectrolyte (content ratio of acrylic acid-based amide derivative: 1 to 50 moles): 1 to 604 parts.

Polyolefin spinning wheel combination consisting of 100 to 60 tf of polyα-olefin and 0 to 40 tf of polybutadiene = 99 to 40 tf @ part of polyolefin &-f: The gist is based on the point where the layer is formed. It is.

The present invention will be explained below with reference to specific examples and application examples.

First, the polypropylene yarn polymer constituting the base film C and below AW and (Q) is (1) an α-olefin of 2fli or more selected from polypropylene, an α-olefin of +21u or more, preferably 10 or less; (However, a copolymer with a small fx (one gutter is propylene),
(3) The above-mentioned ill, +21 polymers and polymers with good affinity with these - for example, polyethylene, ethylene/propylene copolymer, polybutene-1, ethylene/two-tene copolymer, poly-4-methylpentene-1 Examples include polyolefin yarns alone or a mixture with a copolymer of polyolefin fibers, such as the following: *A polyolefin copolymer or a copolymer containing 111ff fluorine of propylene is used. In this case, the content ratio of propylene component a4i1t50 electric j1
It is desired that the polypropylene type 1 is
One is poor in the above-mentioned characteristics (printing ink resistance), and the effect of the present invention is extremely effective.

Next, the structure of the layer to be laminated (hereinafter referred to as B-) to be laminated on at least one side of 1c AP#IIJ will be explained in 4 minutes.

The 8 layers are (1) (acrylic acid-based amide conductor) - (α-
copolymer (content ratio of acrylic acid amide fiber conductor: 1 to 50 moles, hereinafter referred to as acrylamide copolymer): 1 to 80 parts, 100 to 60 parts of 121 polyα-olefin Polybutadiene 0-4
Poly α-olefin polymer consisting of 0 blind spears: 99~
40 parts by weight, but below 2 parts by weight will be discussed below. First of all, it includes all acrylic acid-based amide derivatives, acrylamide, methacrylamide, and those in which the hydrogen in the amide group is replaced with a legated hydrogen residue, but if we list the typical ones in 41j, Acrylamide, N-methylacrylamide, N.

N-dimethylacrylamide, N-ethylacrylamide, N,N-diethylacrylamide, N-n-propylacrylamide, N-isopropylacrylamide,
N-isobutylacrylamide, N,N-di-n-butylacrylamide, N-hexVylacrylamide, N-
Octylacrylamide, N-lauryl acrylamide, N-octade V-lylacrylamide, N-1' chlorohexylacrylamide, N-benzylacrylamide.

N-phenylacrylamide-N-methyl-N-phenylacrylamide, N-tolylacrylamide, methacrylamide, N-methacrylamide, N
-ethyl methacrylamide, N, N-diena V methacrylamide, N-lowpropyl methacrylamide a N,
Examples include N-di+1-butylmethacrylamide, N-octylmethacrylamide, N-V chlorohexaVA/methacrylamide, N-benzylmethacrylamide, and N-phenylmethacrylamide.

On the other hand, α-olefins include ethylene, propylene,
Examples include butene-1, pentene-1, methylpentene-1, and the like.

The acrylic/L' acid-based amide preventive conductor and α
- In copolymers with olefins, Acrylic J4-/
The content of the amide conductor must have a specific force of 51 to 5 mol A/%, of which the preferred range is 1 to 20 moA/%. At this time, this copolymer was placed in a xylene solution at 120°C &12. The value of intrinsic viscosity is 0.1 to 4.6 dll from the viewpoint of mixing stability with other components (specifically, the polyolefin yarn polymer described below) and extrusion stability.
H is preferred. If the content ratio of the acrylic acid-based amide derivative is less than 1 mole, printing ink, metal vapor deposited film or foil, 1! For plastic products, especially chlorine-containing resins and resins, W! However, if the adhesion property is not sufficiently exhibited, but if it is mixed with 50% resistance, the blocking property, lubricity, scratch resistance, transparency, and extrusion stability will decrease, especially the adhesion property.
! The heat treatment after F causes the adhesive strength to decrease and high-speed extrusion to be rapid (this exposes the disadvantages of the sieve).

As the polyα-olefin in the polyolefin polymer, Fi is a homopolymer or copolymer formed from an a-olefin having an r prime number of 2 to 10 (for example, polypropylene-polypten-1.poly-4-methyl). Penten-1
, ethylene/propylene coelectrolyte, ethylene/butene-
1 copolymer, propylene/butene-1 copolymer, propylene/4-methylpentene-1 copolymer, etc.), or mixtures thereof, but the melt index x
(2110℃) is 0.5 to 80 g/10si, especially #
Those with IC1jlI~IMg/10m will be awarded. The other component, polybutadiene, makes the adhesion improvement effect of the polymeric olefin even more pronounced on the I/C# scale, but when the molecular weight is 500, the migration is severe, resulting in a decrease in adhesion and the occurrence of blockade. P and scratch resistance are significantly reduced. On the other hand, the molecular weight is 20,000
When the molecular weight exceeds 600, the transparency decreases.
It is recommended to select from the range of 20.006. But I! The preferred range is goo to io, ooo. The blending ratio of N1a-olefin and polybutadiene is 100 to 60 parts by weight of the former and 0 to 40 parts by weight of the latter.
It should be part by weight, and polybutadiene should be added to 1! k
(Although there is no problem in achieving the objective of the present invention, if it exceeds 40 parts by weight, the transparency when laminated with AJilK will be poor.) This is not a desirable thing because it reduces the

And acrylamide copolymer and d? As for the blending ratio of the 9m-chandyne polymer, it is recommended that the former be 1 to 60 parts carbonate to the latter 99 to 40 parts carbonate. The reason for this is that if the amount of the six components is less than 1 part, the adhesion of printing ink as B#, the adhesion of thin metal 11, and the adhesion to organic polymers (especially chlorine-containing resins) will be insufficient. On the other hand, the former is 60'
This is because if the amount exceeds M parts, the transparency will be lowered, the extrusion stability will be lowered, and the adhesive force will be lowered due to heat history after bonding, and in any case, commercial productivity and commercial value will be significantly deteriorated.

4 The chemical composition of the composite film according to the present invention is as clarified by the above explanation, and the A layer.

Although there are no restrictions on the method of forming layer B and the method of laminating it, the method described below is most preferred. That is, the composite film #A1 consisting of the A layer and the B layer of the present invention can be bonded by coextrusion, melt extrusion lamination VM, heat stretching by ay grinding and adhesion at the same time, or one of them can be bonded in the longitudinal direction. A method of compositely adhering the other side after stretching, and a method such as method 1 of gluing after longitudinal stretching and subsequently stretching in a direction perpendicular to the above method can be adopted. Of course, these combinations may be used as appropriate, or applied means other than those described above may be used.

In the case of two-wheel stretching, there is no particular restriction, and two-wheel stretching is carried out in stages.Usually, an unstretched film is first stretched longitudinally in the longitudinal direction of the film using a gold roll stretching machine, and then stretched vertically in the longitudinal direction of the film using a tensile machine. A method of horizontal stretching in the direction of
In the case of simultaneous two-wheel stretching, use the tenter method.

Any of the inflation VWIV methods can be used.

In either method, the unstretched film of the present invention can be stretched using the stretching ratio, stretching temperature, and grinding speed y1t that are possible for ordinary polypropylene films.

It should be noted that the A layer and B layer used in the present invention, or the composite film formed by laminating them, may be unstretched or stretched, but from the viewpoint of glossiness or mechanical suitability, it is necessary to stretch the film in at least one direction. It is hoped that this will be done. Therefore, the composite film of the present invention includes one in which the A layer and the B layer are entirely uniaxially stretched, one in which the B layer is uniaxially stretched and the A layer is biaxially stretched, and one in which the A layer is uniaxially stretched and the B layer is biaxially stretched. Stretched, layer A is two-wheel stretched and layer B is unstretched, B
Examples include those in which the layer is biaxially stretched and the A layer is unstretched. Now, to describe this more specifically, biaxially stretched t-BO1
- When abbreviated as axially stretched υ0, unstretched t-NO, No.
-A layer/No-B layer, UO-A layer/No-BJIl, U
OA layer/UO-B layer.

No-A layer/UO-B layer, BO-A layer/N0-B layer, B
O-A layer/UO-B layer, Bo-A layer/BO-B layer, N
Various design combinations such as o-A layer/BO-B layer, UO-A layer/BO-B layer, etc. can be performed.

The above design examples are all two-layer composite films, but if necessary, composite films with eight or more layers can also be designed and manufactured.
A layer or eight layers is sufficient.

A layer and 89g) There is no need to set any special restrictions on the thickness of each layer, and there is almost no limit for the special KA layer, but for the B layer, the final thickness is 0.1#80μm, preferably 0.4 #15P It is desirable to design it so that it is ugly, and it is also possible to design it to be thicker depending on the use. That is, if the B layer is less than 0.1 .mu.m, the adhesion stability will be poor, and if it exceeds 807111 .mu.m, the transparency will be impaired, which will limit the application. The most preferable value is oHioμm or less.

The composite film of the present invention constructed as described above has (1) adhesion to an adhesive containing a cellulose derivative or a printing ink using this as a binder (Reacry V type, Hikari Vinyl I type).
! Adhesiveness to various polymer-based copolymer-based adhesives such as %/type and expanded vinyl-day type, or printing inks using these as binders (3) Excellent adhesion to metal vapor deposited layers and metal foils, etc. Therefore, by utilizing these characteristics, it is possible to provide the following complex composite products. - As an example, the adhesion with printing ink using cellulose derivatives as a binder is as follows. As cellulose thread derivatives, nitrified cotton and trocellulose are preferred, but other examples include methyl cellulose, ethyl cellulose, human Cellulose ethers such as ethyl cellulose, cellulose esters such as cellulose propionate, etc. are used. In addition to these cellulose derivatives, polyamide-based W fats made of condensates of polymerized fatty acids and polyamines, cyclized rubbers, rubber derivatives such as cyclized rubbers, ester rubbers such as glycerin esters, urea, and amines such as mefmin resins. For example, when nitrified cotton is added as a binder, the degree of nitrification is usually 9-1.
At 15 liters, the degree of polymerization was 20 seconds to 1 second, as determined by the Vercules method. Inorganic or organic pigments and dyes are further used in the mixture containing the above cellulose derivatives, such as titanium white,
Yellow lead, copper powder, phthalo V anine blue, etc. are used as appropriate depending on the color. Koremineya Konshamono t alcohol,
Esters, ketone ll01 agents, ethylbenzene acetate,
It is used after diluting with various organic solvents such as toluene and dichloromethane to adjust the viscosity. Furthermore, volatile linis or the like may also be used as a color vehicle. Part or all of the printing ink iB layer is overprinted once or several times. These printing ink layers adhere extremely well to the film, and are well resistant to rubbing, scratching, and peeling with adhesive tape, etc., so that even if other polymers or films are laminated, the ink and film interface will remain intact. For example, for packaging materials, practical strength varies depending on weight, shape, properties, etc.4! Sf/15w
II width or more, preferably t-jloOf/1511 or more.The film used in the present invention exhibits extremely good adhesion to printing inks containing cellulose derivatives when subjected to copier discharge treatment, compared to conventional polypropylene films. This is unacceptable.

Another characteristic effect of the present invention is that the power required for conventional corona discharge (for polypropylene film) and the same root KO
[By using force, a more advanced processing effect can be obtained, and conventional polypropylene film has the disadvantage that even if the power consumption of corona discharge is increased, it reaches a ceiling at a certain level. On the other hand,
The B layer in the composite film of the present invention also has the advantage that a processing effect substantially proportional to power consumption can be obtained.

The composition of the composite film according to the present invention is as described above, but an antistatic agent, a lubricant, an anti-blocking agent, a dye, a pigment, a weathering agent, an ultraviolet inhibitor, and various stabilizers are added to the A layer and the B layer. You are free to do what you want.

For example, when synthetic zeophyte is incorporated into either or both of the A layer and the B layer (generally the B layer), antistatic properties and slip properties are improved.

That is, synthetic zeophyte is a highly hygroscopic component (9) and is thought to increase the moisture content of the film by adsorbing moisture in the atmosphere, thereby reducing electrical resistance and exhibiting antistatic properties. In order for this effect to be exhibited, it is desirable that the synthetic zeolite has an average grain size of 0.2 to 20 pm, and that it is contained in the B layer, for example, in a proportion of O, OS to @wt. In addition, the average particle size of synthetic zeolite) is O
If it is less than Jμ■, there will be little effect on antistatic properties, anti-blocking properties, etc., and if it exceeds 20 pmt,
Transparency tends to decline. If the amount is less than 0.05 weight, the above effects will not be exhibited, while if it exceeds 6 weight, the transparency will tend to decrease.

The composite film constructed as described above is mainly used as a packaging material, but in this case, a printing ink layer, an adhesive layer, or a resin (especially chlorine-containing resin) layer is formed in three layers. It is preferable to further layer a polymer having a lower melting point than layer A before bag making. Other uses include films or tapes for covering metal products and plastic products.

Next, Examples and Comparative Examples of the films of the present invention will be described, and the characteristics of the films produced were in accordance with the following method of determination.

(1) Transparency (haze) According to JIB K6714.

(2) Adhesiveness of printing ink A commercially available cellophane tape was brought into close contact with the printed surface and then peeled off at high speed, and the size of the remaining area of the printing ink was determined.

Cellophane ink CL-C (manufactured by Dainippon Ink Co., Ltd.) was used as the printing ink, and the evaluation was based on the following criteria.

Evaluation points Peeling rate 5 0 4 - 10% 8 - 20 2 - 50 g & 1 50% or more (3) Adhesiveness of vapor-deposited AN Commercially available cellophane tape kA# Adhered to vapor-deposited surface and tested and evaluated in the same manner as (2) did. In addition, the peeling direction is the orientation direction of fi-fi resin (vertical) and the direction perpendicular to this (straight). In Table 1, "immediately" means "directly vkJ of Ag evaporation," and "immediately after the treatment""After" means "after aging for 48 hours at r40" 0.90% RH.

(4) Lamination strength Regarding the printing ink, printing was carried out on eight layers, and then low density polyethylene was melt-extruded and the lamination strength of the printed area was measured. The test results were obtained by peeling the laminate layer at 90 degrees! 00111/ff1I
Regarding Ag evaporation, the results are shown in the strength flatness value (fi-6) when peeled off at a reasonable speed.After forming a 600 μm hgys adhesion layer, the results were similarly tested for a product that was inserted and fuminated in the same way.・PVDC 8f/m for courts
A similar laminate was applied to the PVDC coated surface of the sample, and the results were then similarly tested.

(5) Bag durability (in the case of printing ink) After printing on 8 layers and melt-extrusion laminating low-density polyethylene on top of the 8 layers, using an automatic filling and packaging machine, 180℃, 200℃
Bags were made under the condition of 2 pieces/win. Then, place a steel plate on the top flat part of the bag, and place each plate on top of the steel plate. While applying pressure, we measured the critical pressure at which air begins to leak from the base material, and determined the influence of the adhesive force between the base material and the ink.

(6) Adhesion of flour to bags When bread crumbs were automatically filled and packaged, the adhesion of crumbs to the heat-sealed part of the bag was investigated. The evaluation is in 4 stages,
A mark of 0 indicates that there is no adhesion at all, a mark of O indicates that the adhesion is so thick that it becomes a practical problem, a mark of Δ indicates that some adhesion is observed, and a mark of Δ indicates that there is adhesion to the extent that it causes damage to the sealing part. is indicated by an x.

Example 1 Isotactic daliderovirene (MI-1'1.O
g/10 minutes), synthetic zeolite powder (particle size: 2.5μ
Add 0.2 weight of m) with alkyl V amine ethylene oxide @, 1 i, o weight,
It was set as A layer.

On the other hand, a composition (I) prepared by mixing 280 parts by weight of N,N-diethylacrylamide/propylene copolymer (84.4 parts by weight/65.1 parts by weight) and 70 parts by weight of polypropylene.
was prepared. Composition (2) was prepared using a mixture of polypropylene and polybutadiene (weight ratio 4/1) in place of the brewed polypropylene. and these compositions (I), ■
0.8 weight of 2# silicone and 0.8 weight of industrial acid amide, respectively.
Add 06 weight.

These are used as layer B and one side of layer A (laminated using the co-zen method,
An unstretched composite film with layer H: 7 g O 11 m and layer B: 40 jl 1 m was obtained. Next [After stretching 4.6 times in the longitudinal direction at 186°C and further stretching 9.0 times in the transverse direction at 150°C to make a biaxially stretched film, one surface of the film is subjected to corona discharge treatment on the B layer side. A composite film with a wetting strength of 45 dynes/d was obtained. BMK printing, A/distillation, PVDC coating, and low-density polyethylene lamination were applied, followed by bag making. The results of each test are collectively shown in Table 1 VC mentioned in @.

Example 2 In the combination of A- of Example 1 and composition (I), A
The same treatment and evaluation were performed for the case where no synthetic zeolite was added to the layer.

'jlFm Example 8 In Example 2, synthetic zeolite with a particle size of 4 μm was mixed in the B layer at a ratio of 0.2 times 1/kq&, and the same treatment and evaluation were performed. However, as the printing ink, an aqueous acrylic ink diluted with water-iso61 panol yarn was used.

Example 4 In Example 1, the ink was changed to a water-based ink, and exactly the same treatment and evaluation were performed.

Comparative Example 1 Similar evaluations were conducted on a film of Example 1, in which the A layer alone was stretched in the same way and the corona discharge was increased by 51°.

Comparative Example 2 Layer A was formed with the same composition as the base material of Example 1 and biaxially stretched. Next, a melt-extrusion laminate of ethylene/vinyl acetate M# polymer (L) and BJ+Il with a thickness of 15 μm was formed on one side thereof. The B layer was subjected to corona discharge treatment.

Wet tension was set at 48 dynes/unit. Example 1 for layer B
The same treatment was applied and the same evaluation was performed.

! ：、、＜代IJl

Claims (1)

[Claims] 11) At least one side of a base film containing a polypropylene polymer. (AcryA/#-based amide derivative)-(α-olefin)
Copolymer (content ratio of acrylic acid-based amide rust conductor: 1~
50 mol If): 1 to 60 parts by weight. An easily adhesive film characterized by laminating a coating layer consisting of 99 to 40 parts by weight of a polyα-olefin polymer consisting of 100 to 60 parts by weight of -9α-olefin and 0 to 40 parts by weight of polybutadiene. . 2. The easily carbonable film according to claim 1, wherein each coating layer contains 0.05 to 6 weight of synthetic zeolite having an average particle size of 0.2 to 204 m.