JPS5876270A - 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 which a Ka polypropylene-based polymer is used as a base film, and has excellent printing ink adhesion and metal HWIWJ adhesion.

Good adhesion to organic polymers and improved processability*
This is a story about a highly adhesive film.

Plastic eye V used for food packaging and textile packaging
(V-): below between @)K, adaptability to high-speed printing,! Reduction of 4-distillate solvents.

Characteristics such as low-cost inks and water-based inks, compatibility with direct coating processing, etc., have also become desirable. For example, water-based inks are expected to be used more widely in the future because they do not have the problem of environmental pollution caused by organic solvents. As such an ink, for example, an ink using a ``SeV loose;l Kasumi conductor'' as a binder (trade name: ``Ink for 1 Cello8'') is known.However, currently commercially available /l propylene-based film V There is a dedicated service for printing
I # Ink point is used, each ink is stored and managed, and each KJ1 is combined with a large anchor coating agent (ml
Anchor coating agent for laminating low melting point films such as EthiV is stored in the same way.

There was a problem in that multipolar ink and adhesive had to be prepared during the bag making process, such as the need to embed the tube.

In order to improve printing properties, attempts have been made to improve the adhesion of the film by coating one side of the film with a resin liquid. However, it is a process that is complicated, expensive, and wasteful.In addition, polypropylene films have excellent metal deposition properties and metal foil adhesion properties.

Primer processing has been used to cover this problem, but the primer tends to produce a vapor-deposited gold lll4VC texture, which impedes printability and adhesion processability on the vapor-deposited surface, and the primer treatment is necessary. It's also the economy.

Poly Y'CR pyrene thread film has various drawbacks as described above, but it has poor adaptability to water-based inks that have been developed in recent years and direct coating of various yuzu polymer electrolyte, and we are trying to improve this. If possible, it would be possible to prevent environmental pollution due to solvents, omit one culm pre-treatment, save materials, reduce residual solvent, etc.
This is extremely convenient.

The present invention was made with attention to such circumstances, and includes adhesiveness of seal ink and thin metal film.

The object of the present invention is to provide a polypropylene-based composite fiber A/A having good adhesion properties such as organic polymer adhesion properties.

A composite film that successfully achieves the above objectives is:
A base film containing a polypropylene yarn polymer is copolymerized with at least one selected from alkylene imines, vinyl lactams, N-vinyl carbazoles, vinyl pyridines, and vinyl amines and an α-olefin on at least one side thereof. Combined with: 1 to 50 parts by weight.

The gist is that a coating layer consisting of 99 to 40 parts by weight of a polyα-olefin thread polymer consisting of 100 to 60 parts by weight of polyα-ole 7-if and 0 to 40 parts by weight of polybutadiene is laminated. be.

Specific examples and application examples of the present invention will be explained below.

First of all, the polypropylene thread polymer constituting the base film (hereinafter referred to as A-) is (1) polypropylene +
A copolymer of two or more α-olefins (however, at least one is propylene) selected from α-olefins having an F21 disease prime number of 2 or more and a preference mechanism of 10 or less, 13) the above ill, f2+ polymer, Polymers with good affinity with these, such as polyolefin fibers or copolymers such as polyethylene, ethylene/propylene coelectrolyte, polybutene-1, ethylene/butene coelectrolyte, poly-4-methylpentene-1, etc. Examples include mixtures of propylene, but propylene is used alone or with propylene as an example.
t copolymer is used. In this case, it is desired that the content ratio of the propylene component is more than 150% by weight, and the above-mentioned properties (
Printing ink adhesion) is poor, and the several-fold effect of the present invention is extremely significant.

Next, a coating layer laminated on one side (hereinafter referred to as 8
The components of the layer (referred to as a layer) will be explained below.

B11a, f+j alkylene imines, vinyltuctams, N-vinyl carbacy/L/lf4. 1 to 60 parts by weight of a copolymer of α-olefin and at least one selected from vinylpyridines and vinylamines (hereinafter referred to as polyolefin coelectrolymer); (2)
It is composed of 99-60 parts by weight of a poly-α-olefin polymer consisting of 100-60 parts by weight of poly-α-olefin and 0-40 parts by weight of polybutadiene, and these will be explained below in order.

(Examples of alkylene imines constituting the polyolefin copolymer include ethyleneimine, propyleneimine, butyleneimine, 1,1-dimethylethyleneimine, 1.1-!/ethylA/-2-methylethyleneimine,
Examples include 1.1-1' methyl-2-propylethyleneimine, vinyl lactams include vinylpyridines, vinyl cabrotams, and N-vinylcarbazoles include N-vinyl carbacyv+N. Examples include vinylpyridine-1,2,8,4-tetrahydrocarbazole, and examples of vinylpyridine include 2-vinylpyridine, 8-vinylpyridine, 4-vinylpyridine, 2-vinylpyridine,
Methyl-5-vinylpyridine, 2-methyl-6-vinylpyridine, 5-ethyl-2-vinylpyridine, 2.4-
Dimethyl-6-vinylpyridine.

Examples include 2-isopropenylvinylpyridine and 3-isopropenylvinylpyridine, and examples of the vinyl M amine include N,N-divinylamine. However, these examples are merely representative ones, and compounds that are analogous to or chemically derived from these exemplified compounds are included in the present invention.

Ethylene, propylene, butene-1,2-methyMbutykari, pentene-1,4-methylpentene-1, etc. are used as α-olefins that coelectrogate with such vinyl group-containing basic nitrogen-based compounds. Made by.

Of these, ethylene is the most versatile for economic reasons. And from these, what are the polyolefin copolymers that are neglected by coelectrolysis, 6U, random copolymerization, and block copolymerization? Regardless, a coelectric polymer of eight or more elements obtained by adding a polymerizable heptamer component other than those mentioned above can also meet the purpose of the present invention. Although the component composition of the copolymer #IC is not particularly limited, if the composition ratio of the above-mentioned vinyl group-containing basic nitrogen compound is less than 6 mo, various adhesion improving effects in the B layer will be weak (or vice versa). If the weight exceeds 60% by weight, the blocking resistance decreases to zero and discoloration due to heat is likely to occur. Therefore, it is desirable to adjust the coulage to a range of 6 to 60%.

The polyα-olefin in the α-olefin polymer is a homopolymer or copolymer formed from α-olefins having 2 to 10 carbon atoms (e.g. polypropylene, polybutene-1, poly-4-methylpentene). -1, ethylene/propylene copolymer, ethylene/butene-1 copolymer, propylene/butene-1 copolymer, propylene/4-methyV-pentene-1 copolymer, etc.), or a mixture of these However, the melt index (2
80°C) is 0.5 to 80 g/10i, especially 1.0 to If
)g/10i will be awarded. The other component, polybutadiene, pushes the adhesion-improving effect of polyα-olefin to -HIIJwa#, but if the molecular layer is less than 500, migration is likely to occur, resulting in a decrease in Km adhesion and the occurrence of blocking. It will not wear well and the scratch resistance will decrease. On the other hand, when the molecular weight exceeds 20,000 t-, the transparency decreases, so the molecular jiifi00~20,0
It is recommended to select from the range 00. However, the preferred range for - is 800 to 10. It's ooo. Also poly α-
The blending ratio of olefin and polybutadiene should be 100 to 60 parts by weight for the former to 40 parts by weight for the latter, and although there is no problem in achieving the objective of the present invention without blending polybutadiene, 40 m1 If the thickness exceeds 100 mm, the transparency when laminated on the A layer will be poor, and the aesthetic appearance of letters and figures printed from the 8th layer side will deteriorate, which is not preferable.

As for the blending ratio of the polyolefin copolymer and the poly(a-V74) polymer, it is recommended that the former be 1 to 50 parts by weight and the latter be 99 to RQIlli parts. The reason for this is that when the former is partially untreated, the B layer has insufficient ink-grade adhesion, metal thin film adhesion, and organic polymer (H contains chlorine fruit tree) adhesion. On the other hand, if the former exceeds 50 volts, it will lead to a decrease in transparency, a decrease in insertion and insertion stability, and a decrease in adhesive strength due to a thermal history after welding. This is because the value of goods suddenly increases.

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

Although there are no restrictions on the method of forming layer B and the method of laminating it, the most preferred method is the method described below. That is, in order to obtain a composite film consisting of layer A and layer B of the present invention, a method of bonding at the same time as extrusion, melt extrusion, and heating stretching using roll sanding, or a method of adhesion at the same time as stretching using a roll sander, or a method of bonding at the same time as stretching using a roll grinder, or a method of bonding at the same time as stretching using a roll grinder, or a method of bonding at the same time as stretching using a roll grinder, or a method of bonding at the same time as drawing with a roll grinder, or a method of adhering at the same time as stretching using a roll grinder, or a method of bonding at the same time as drawing with a roll grinder. How to bond other parts together, l! For this purpose, a method of longitudinally stretching, adhering, and subsequently stretching in a direction perpendicular to the above-mentioned direction, or a thickening method can be adopted. Of course, combinations such as ξ may be used as appropriate, or applied means other than those described above may be used.

When performing two-wheel stretching, there are no particular restrictions.To carry out sequential knee stretching, the unstretched film is first stretched vertically in the longitudinal direction of the film using a roll stretching machine, and then stretched in a direction perpendicular to the longitudinal direction of the film using a tenter. A method of horizontal stretching is used, but
Longitudinal stretching with a transverse stretching machine may be carried out in the reverse order.In the case of simultaneous biaxial stretching, either the tenter method or the inflation VH method can be used. In either method, the stretching ratio, stretching temperature, and stretching speed F that are possible with ordinary lripropylene film
! It is possible to stretch the unstretched film of the present invention using ILt''.

It should be noted that the A layer and B layer used in the present invention, or the composite film formed by laminating them, regardless of whether it is unstretched or stretched, has at least one of them in terms of glossiness and Fi machine suitability. It can be seen that it is stretched in the direction 1a. 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 knee stretched, and one in which the A layer is uniaxially stretched and the BM is biaxially stretched. Examples include those in which the A layer is biaxially stretched and the B layer is unstretched, and those in which the B layer is biaxially stretched and the A layer is unstretched. Now, to describe this more specifically, biaxial stretching tB
O1-axial stretching t-UO1 wood grain stretching [-N.

and abbreviated rdLl case 1. NO-A layer/No-B layer, UO
-A layer/No-B layer, UO-A layer/UO-B layer.

No-A layer/UO-Bjll, BO-A layer/No-B layer, BO-A layer/UO-8 layer, BO-A layer/BO-B layer,
No-A layer/BO-B layer, UO-A layer/BO-B layer, etc.
Seven designs can be carried out.

The above design examples are all 2R composite examples, but if necessary, composite films with eight or more layers can also be designed. However, if it is used for manufacturing purposes, 2
A layer or 8 layers is sufficient.

There is no need to set any special requirements for the thickness of the AM and B layers, and there is no limit to the thickness of the A layer in particular.
As for the layers, finally o, tg.

It is desirable to design it so that it has a thickness of μm, preferably 0.4 to 16 μm, and depending on the application, it may be designed to be as thick as 4.
When R[, that is, the B layer is less than 0.1 Rm, the adhesion stability becomes rapid, and on the other hand, when the value exceeds Oμmt, transparency is impaired, which is a problem that limits the application. The most preferable thickness is 10 μm or less.

The composite film of the present invention constructed as described above has (1) adhesion to an adhesive containing a cellulome derivative or printing ink using this as a binder; and (2) adhesiveness to an adhesive containing a cellulome derivative or a printing ink using this as a binder. (3) Adhesiveness with various polymer and copolymer-based adhesives or printing inks using these as binders. By using the characteristics,
It can be provided as a composite composition product as described below. - As an example, the adhesion of cellulose-based derivatives with printing ink is as follows.

For cellulose yarn induction stop, use nitrified cotton and trocellulose)
is preferred, but other examples include cellulose ethers such as methtv*pv Leeds, ethyl Vcellose, hydroxyethyl cellulose, and cellulose esters such as cellulose diapionate. In addition to this cellulose thread I conductor, polyamide-based 11 resin consisting of a condensate of polymerized fatty acids and polyamines, cyclized rubber, rubber derivatives such as clay rubber, and mouth V
ester rubber such as glycerin ester, urea, amine resin such as mehumine resin, etc. are added, but are not limited to these, of course. For example, nitrified cotton is added as a binder. 1 If the appropriate degree of nitrification is 9-116- has a degree of polymerization and a viscosity of 20 seconds to ij seconds as measured by the Vercules method. Inorganic or organic pigments and mulberry pigments are further used in the mixture containing the above-mentioned cellulose pigment, such as titanium white, titanium white,
Yellow lead, copper powder, and phthalo V-animp are used as appropriate depending on the color. This mixture is similar to alcohol,
Diluted with M agent of esters and ketones, ethyl acetate, toluene, and 411 solvent,
Use after adjusting the viscosity. Further, volatilized varnish or the like may also be used as a coloring agent. Part or all of the printing ink t-B 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, the strength of packaging materials varies depending on the weight, shape, and properties, but the strength is 461/1!
1. The film used in the present invention exhibits extremely good adhesion to printing inks containing cellulose thread conductors by corona discharge treatment, compared to conventional polypropylene. This is not allowed in film.

Another characteristic effect of the present invention is that a higher processing effect can be obtained by using the same electric power as the conventional corona radiation ViFlr (for polypropylene film), and Whereas the film had the drawback of showing a plateauing phenomenon at a certain level even if the corona discharge power consumption was increased, the B layer of the composite film of the present invention achieved a treatment effect that was almost proportional to the power consumption. There is also the advantage of being able to

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 weathering agent, an ultraviolet ray inhibitor, and each stabilizer are added to the A layer and the B layer. Free to refrigerate.

For example, if it is incorporated into either the t-A layer (for example, synthetic zeolite) or the B layer (generally the B layer), the antistatic properties and slippage VT4 will be improved.

In other words, synthetic zeophyte is a highly hygroscopic component, and by adsorbing moisture in the atmosphere, the moisture content of the film increases, which reduces electrical resistance and prevents static electricity. It is considered that the In order for this effect to be exhibited, the synthetic zeolite must have a diameter of 0.2 to 205 m.
, and for example, it is desirable to contain it in the B layer at a ratio of 0.06 to 6 kg by weight. If the average grain size of the synthetic zeolite is 0.2 μm, it will not be able to exhibit antistatic properties, anti-blocking properties, etc., and if it exceeds 20 μm, transparency will tend to decrease. In addition, if the blending amount is less than 0.06% by weight, the above effect will not be exhibited;
&t-, transparency tends 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 gold resin) layer is formed on the B layer, Furthermore, a polymer having a lower melting point than layer A is laminated and then the bag is made. Other uses include films or tapes for covering industrial products and plastic products.

Next, Examples and Comparative Examples of Films of the Present Invention - The properties of the film produced by the production of sea breams were determined according to the following method of definition.

tU transparent If (haze) ls　According to K6714.

(Adhesiveness of No. 27 Printing Ink) When a commercially available cellophane tape was attached to the printed surface and then peeled off at high speed, the size of the remaining area of the printing ink was determined.

The printing ink used was cellophane ink CL-C (manufactured by Dai-Nippon Ink Co., Ltd.), and the evaluation was based on the following criteria.

Evaluation points Peeling pm ratio 5 0% 4 ~ 10 g 8 ~ 20% 2 ~ 50 g & 1 60% or more (3) Adhesion of vapor deposited AI Commercially available cellophane tape Cura A # Adhered to vapor deposit 1 sum and tested in the same manner as (2) and evaluated. The peeling direction was the orientation direction of the film resin (vertical) and the direction perpendicular to this (horizontal).
In Table 1, "[after"] means "immediately after A4 deposition", and "after treatment" Ur40℃, 90% R
It means "after Ht'48 1tlz -s)".

(4) Fuminate strength Regarding the printing ink, printing was performed on layer B, and then low density polyethylene was melt-extruded to determine the fuminate strength of the printed area. The test results were obtained by peeling the fuminate layer at 90 degrees.
Strength flattening value when peeled at a speed of 0 m/mm (
1 to 5005 m for Ae deposition, denoted by fi = 5)
After the formation of the A7i deposited layer of PVDC:I-
) K fl 8 f/m Q) The same lamination was applied to the PVDC coated surface, and then the results were tested in the same way.
illt-performed, low-density polyethylene t-melt extrusion fuminate thereon, and then using automatic filling packaging mt-
go”c, 2oo pieces/mia o condition Xu Az from copper plate top
While I was in charge, the limit pressure t- where the air started to flutter
Measurements: The influence of the adhesion between the substrate and the ink tl was measured.

(6) Adhesion of flour to the twill The state of adhesion of the bread crumbs to the bottom of the bag when the bread crumbs were automatically filled and packaged was examined. The evaluation is in 4 stages,
There is no adhesion at all (t"0 mark), there is no adhesion to the extent that it poses a practical problem (t-0 mark), and there is some adhesion (t").
The seals were marked with Δ, and those in which adhesion was observed to the extent that they caused disturbing noises were marked with X.

Example 1 Tactical polypropylene (MI=8.0g/
10 minutes) K1 synthetic zeolite powder C particle size: 2.5 μm)
was added in an amount of 0.2 carbonate and 1.0 weight of an alkyl M amine ethylene oxide adduct to form layer A.

On the other hand, propylene/N-vinyl carbacyv copolymer (7
A mixed composition of 0118 parts/jlOJirit parts) and llipropylene (the former 20 parts by weight: the latter Sonori (I) was prepared.Also, instead of 80 parts by weight of polypropylene, a polypropylene/polybutadiene mixture (80 parts by weight 11&l!/l) was prepared.
#J
Made by I4. And these compositions (I), (II
) and silicon dioxide*0. s blind ridge and 0.05 parts by weight of erucic acid amide were added, and these were co-extruded onto one side of the AW as layer B, MWL, Am: 760 μm.

B layer: A 4-fold μm unstretched composite film was obtained. Next, the BM
By subjecting 911 to corona discharge treatment, a composite film with a surface wetting tension of 45 dynes/(Ah) was obtained.B
Printed on layer, A/deposited, PVDC coated, low v! Laminated with polyethylene.

I gave m bags to history. The results of each test are summarized in Table 1 below.

Example 12 In the combination of layer A of Example 1 and composition (I).

Exactly the same treatment and evaluation were performed for the case where no synthetic zeolite was added to the A layer.

Example 8 In Example 2, 0.2 m of synthetic zeolite with a particle size of 4 μm was mixed in layer B, and the same treatment and evaluation were performed. However, as the printing ink, the water-based ink for acrylic thread was -Isolinol thread solvent VC diluted 1- was used.

Example 4 In Example ivc, the ink was changed to a water-based ink, and the same treatment and evaluation were carried out.

Dicing example 5 Propylene/ethylene/methyl methacrylate (1 part carbonate/a part by weight/25 parts by weight) copolymer 85 Denshu part &C, propylene/ethylene (96 parts part by weight/4 parts part by Densha) copolymer 85 The B layer composition was completed by adding an electric violet part, and the same treatment and iI+ value were carried out in accordance with Example 1.

Comparison example 1 In Example 1, the film of A-serious crime was similarly subjected to &C4 elongation and corona discharge treatment, and the same evaluation was conducted.

Comparative Example 2 A layer A having the same composition as the base material of Example 1 was shaped and biaxially stretched. Next, a B layer of 1.15 μm thick was formed on one side of the film by bath-extrusion lamination of ethylene/vinyl acetate V# polymer. Bm was subjected to corona discharge treatment to give a wetting force of 48 dynes/a. Layer B was subjected to the same treatment as in Example 1 and evaluated in the same manner.

Claims (1)

[Claims] Il+polypropylene thread heavy threads are combined on at least one side of a pace film V. alkyleneimines, vinyltuctams, N-bi=pv
iJv selected from bazoles, vinylpyridines and vinylamines and a co-electrolytic combination of 4-al and a-olefin = 1 to 50 parts. 100 to 6 o 111 parts of polyolefin and 0 to 40 parts of polybutadiene. An easily adhesive film characterized by laminating a coating layer consisting of 99 to 50 parts by weight of a polyα-olefin polymer. (2) The coating layer has an average particle size of 0.2 The easily adhesive film according to claim 1, which contains 0.05 to 1% of synthetic zeolite with a diameter of 20 μm.