JPS5876271A - 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 a Par-X film,
Printing ink adhesion, metal j [lK adhesion.

The present invention relates to an easily adhesive film that has good adhesion to an organic electrolyte and has improved processability.

For plastic films (V-) used for food packaging, textile packaging, etc. (as well as double line bottoms), adaptability to high-speed printing and low residual solvent levels.

Properties such as low-cost ink and water-based ink adhesion and compatibility with direct coating processing 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, Uchino (trade name "Nanakuchihen" ink) which uses a cellulose thread derivative as a binder is known. However, organic solvent-based inks exclusively for #i are used for printing on polypropylene thread films currently on the market, and each ink must be stored and expanded in number of tubes. Anchor coating agent for laminating a low melting point film) is stored in the same way.

There were problems such as the need to bury the tubes, and the need to prepare ink and adhesives for polyplants at the time of table preparation.

In order to provide printability, there has also been an attempt to improve the adhesion of the film by coating the film surface with persimmon fat liquid. However, the process is complicated, the price is expensive, and it is a wasteful method. In addition, polypropylene films have high metal deposition properties and gold M W +
The contact is poor.

Primer processing is also applied to cover this, or you can use primer 〇 to deposit gold! It is easy to cause 11ttC deterioration (this impairs the printability and adhesion processability on the vapor-deposited surface, and it is also uneconomical as it requires brimer treatment.

Borif °C pyrene thread Fil-5 has such shortcomings in terms of IQ, but its resistance to water-based inks and adaptability to Direct-F Coating VC, which is a combination of single-molecule blind combinations that have been developed in recent years, is amazing. If you can improve it, R
This is extremely advantageous because it is possible to prevent contamination of the castle grounds by one field, omit the pretreatment process, save materials, and (b) reduce the amount of residual l# agent.

The present invention has been made by focusing on the above-mentioned circumstances, namely, the adhesion of printing ink and the adhesion of gold to thin layers.

The object of the present invention is to provide a polypropylene composite film V having good adhesion properties such as organic polymer adhesion properties.

A composite film that has succeeded in achieving the above objectives,
A base film V containing a polypropylene polymer is coated with an (α-olefin)-(acrylic acid amide derivative)-(α-olefin unsaturated compound) terpolymer (molar ratio = t) on at least one side thereof. :o, ot~Q, Ofi
: 0.01 to OJ): 1 to 60 parts of carbon dioxide, a polyα-olefin polymer consisting of 100 to 60 parts of polyα-olefin and 0 to 40 parts of polybutadiene = 99 to 40 parts densified The gist of this work is that it has accumulated and advanced the 61 wisdoms that consist of the following.

A first specific example and application examples of the present invention will be described below.

First of all, the polypropylene-based polymer that makes the base film c (hereinafter referred to as AV) is 11) polypropylene,
(2) A copolymer of two or more a-olefins selected from α-olefins having a W cumulative number of 2 or more and preferably 10 or less (however, a small amount (in both cases, 1 yuzu is propylene)), (3) upper t
'llll, +21 polymers and their affinity 1
Raw good polymers such as polyethylene, ethylene/
Examples include propylene copolymers, polybutene'-1, ethylene/butene sulfate composites, and polyolefin-based monopolymers or wet products with copolymers such as poly-4-methylpentene-1. A homopolymer or a structure copolymer having IJm as an IJm component is used. In this case, it is desired that the content ratio of the propylene component is 50% or more, and such a polypropylene polymer has the above-mentioned characteristics.
- (Printing ink adhesion) is poor, and the improvement effect of the present invention is extremely significant.

Next, there is a small amount of A# (also a coating layer laminated on one side (hereinafter B)
The four parts of the structure (referred to as m) will be explained.

BMFi, mouth) (α-olefin) - (acrylic fiber amide bleached conductor) - (a-olefinic unsaturated compound) terpolymer C molar ratio = 1:0.01 to 0.5 to 0.01 ~
0.5. (hereinafter referred to as ternary symmetrical polymer): 1 to 60 irises; (2) poly α-olefin polymer consisting of 100 to 60 parts of polyalpha-olefin and 0 to 40 parts of polybutadiene; 99 to 40 parts of polybutadiene; ≠5. These will be explained in order below.

First, what is the α-olefin in the terpolymer?

Ethylene, propylene, butene-1,8-methyV-butene-1,4-methyV-pentene-to-g are used. Also, the acrylic acid-based amide derivatives in the same polymer include acrylamide and methacrylamide.

N-alkyl substituted acrylamide, N-alkyl rdt
Examples include acrylamide, N-methylacrylamide, N.

N-dimethylacrylamide, N-ethylacrylamide, N,N-diethylacrylamide, N-II-propylacrylamide, N-isopropylacrylamide, N-isobutylacrylamide, N-8th-butylacrylamide, N,N-di 1j-Butylacrylamide, N-hexyl acrylamide, N-octyl acrylamide, N-riuryl acrylamide, N-octade V14/acrylamide, N-ncrohexylacryl!
Ami F, N-Pen! /A/acrylamide, N-phenylacrylamide, N-methyl-N-phenylacrylamide, N-)rulylacrylamide, methacrylamide 2N-ethylmethacrylamide.

N,N-diethylmethacrylamide, N-n-propylmethacrylamide, N-8th-butylmethacrylamide, N,N-di-n-butyA/)lcrylamide, N-
Examples include octylmethacrylamide, N-Vchloromethacrylamide, N-benzylmethacrylamide, and N-phenylmethacrylamide. In addition, as the α-olefin thread unsaturated compounds, vinyl ferron group compounds such as styrene, vinyl acid, vinyl
Vinyl esters such as vinyl benzoate, vinyl benzoate, vinyl diethyl acetate, and pinyl chloride.

Vinylpalites such as vinyl bromide: Vinyl V ethers such as methyl vinyl ether, ethyl vinyl ether, and FeniV vinyl V ether A/Vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone Niacrylic acid, methacrylic acid, and methyl acrylate , ethyl acrylate, methyl methacrylate, ethyl methacrylate, N-71st-butylaminoethyl acrylate, N
-8th-butylaminoethyl methacrylate%N-methylaminoethyl acrylate), N,N-dimethylaminoethyl acrylate), N,N-dimethylaminoethyl acrylate), N,N-νx - Acrylic compounds such as 1-A/aminoethyl acrylate and N,N-diethylaminoethyl methacrylate; other examples include acrylonitrile, methacrylatrile, N-vinylpyridine, and N-vinylimides.

The 1I + Kida element co-ammonium, which is a member of the composition of the present invention, contains -4 or more than 0.01 mol or more of acrylic acid amide derivative units per 1 mol of a-olefin units, or 0.01 mol or more and 0.5 mol Contains the following and one or more α-olefinic unsaturated compound units from 001 mol to 6.6 mol, and has an intrinsic viscosity value of 01 to 4.5 when determined as tetrazine KM at 186°C cte/g books are preferred. The viscosity is a suitable index for ensuring mixing stability with the polyolefin mixture described below and volatilization stability. If the ratio of the acrylic acid-based amide derivative or the a-olefin thread unsaturated compound to 1 mole of α-olefin is less than 0.01 mole, even when blended with a polyolefin mixture, printing ink and metal vaporization 7F or foil.

Dark blue does not exhibit sufficient adhesion to plastic products, especially chlorine-containing resins. But 0. If the amount exceeds ft-t, blocking resistance, lubricity, scratch resistance, transparency, and extrusion stability will decrease.

In particular, heat treatment after adhesion exposes disadvantages such as a decrease in if# adhesion strength and poor high-speed extrusion.

The poly(a-olefin) in the poly(alpha)-onfin yarn polymer is a homopolymer or copolymer formed from a-olefins having 2 to 1 G carbon atoms (for example, polypropylene, polybutene-1, poly-4-methylpentene- 1,
Ethylene/propylene co-combination, ethylene/butene-1
Coelectric polymers, propylene/butene-1 copolymers, propylene/4-methylbentyl-1 copolymers, etc., or mixtures of these are used, but the melt index (2
80°C) 0.5-80 g/10m, especially <t.

~15 g/10 m will be awarded. On the other hand, polyptadiene improves the adhesion improvement effect of polyolefin even further, but if the molecular weight is less than 500, migration is severe, resulting in a noticeable decrease in adhesion and occurrence of blocking. Otherwise, the scratch resistance will decrease. On the other hand, when the molecular weight exceeds 20,000, the transparency decreases, so one molecular weight is 500 to 20.0.
It is recommended to select from the range 00. However, a more preferred range is 800 to 10,000. Also poly α-
The blending ratio of olefin and polybutadiene should be 100 to 60 parts of the former to 0 to 40 parts of the latter, and there is no problem in achieving the objective of the present invention even if 55 parts of polybutadiene is not provided. If it exceeds 40 parts of sodium bicarbonate, it will be A.
This is not preferable because the transparency when laminated in layers is poor (and the aesthetic appearance of letters and engravings printed from the 8th layer side when viewed from the All side is degraded), which is not desirable.

The blending ratio of the terpolymer and polyα-olefin polymer is 1 to 60 parts of the former to 99 parts of the latter.
~40 dens can be recommended.

The reason for this is that when the former is less than 1 df part, the printing ink adhesion, metal film adhesion, and organic 1 combination (especially containing 8! yarn resin) adhesion as the B layer are insufficient; (If it exceeds 60 parts, it will lead to a decrease in transparency, a decrease in extrusion stability, and a decrease in adhesive strength due to the thermal history after bonding, and in any case, the productivity of acrobatics and the value of the product will deteriorate significantly. Because it does.

The chemical composition of the composite film according to the present invention is clear from the above explanation, but AM.

There are no restrictions on the formation method and lamination method of layer B, but it is preferred that V>O be the method described below.

That is, in order to obtain a composite film consisting of layer A and layer B of the present invention, coextrusion and bath melt extrusion are performed. 1, row, 4/A method of adhering simultaneously with heating stretching with abrasive stretching, or a method of adhering one of the two by T-longitudinal stretching and then adhering the other by t-W bonding. Method 1, such as a method of stretching in a direction perpendicular to the above, can be adopted. Of course, for these combinations, applied flat membranes other than those described above may be used.

In the case of two-wheel stretching, there is no particular need for 5eFa, and in order to carry out sequential knee stretching, the unstretched film is usually longitudinally stretched in the longitudinal direction of the film using a final roll stretching machine, and then stretched in a direction perpendicular to the longitudinal direction of the film using a tenter. Although a method of transverse stretching is used, it is also possible to perform transverse stretching-wk longitudinal stretching in the reverse order.In the case of simultaneous biaxial stretching, either the tenter method or the inflation VM method can be used. In either method, the stretching rate, stretching temperature, and
The unstretched film of the present invention can be stretched using a stretching speed.

The A layer and B layer used in this article, or the composite film formed by laminating these layers, may be unstretched or stretched, but from the viewpoint of glossiness or #'i machine suitability, at least It can be seen that it is stretched in one direction. Therefore, the composite film of the present invention includes one in which the eight and B layers are entirely uniaxially stretched, and one in which the B layer is monoaxially stretched and the A layer is two-wheel stretched. , t, the A layer is uniaxially stretched and the B layer is knee stretched, the A layer is biaxially stretched and the B layer is unstretched, the B layer is two-wheel stretched and the A layer is unstretched, etc. It will be done. Now this is tlJ! If I were to describe it specifically.

When biaxial stretching is abbreviated as BOl-Hosotoshin II-Uo and Kiyoshishin is abbreviated as NO, No-A layer/No-BJII, UO-A
layer/N0-B layer, UO-A layer/UO-B layer.

No-AM/UO-B layer, BO-A layer/No-B layer, B
OA layer/Do-RM, BO-A layer/BO-B layer, No.
-A layer/BO-B layer, 00-A layer/BO-B layer, etc. This can be done depending on the design.

In addition, in all of the above design examples, the amount of 2 pieces is 0, and the number of pieces is 7.
We can design composite films of 8M or more as needed.
It can also be manufactured. However, when used for sea bream fiber, two or eight layers are sufficient.

Special details regarding AM and B#IO thickness.
There is no need to provide t, especially for AJIII/c.
′! 'Unlimited, but for B layer, final KO,
It is best to design it so that it has a diameter of 1 to 30 μm, preferably 04 to 16 #II! However, depending on the application, it is possible to design it to be extremely thick. That is, if the thickness of layer B becomes ◎lpm, the adhesion stability will be compromised.On the other hand, if the thickness exceeds 80 .mu.m, the transparency will be impaired, which will limit the application. Most preferably, the value of i is 10μ or less.

Composite film t of the present invention constructed as described above (13
Contains cellulose derivatives! Ii! Adhesiveness with adhesives or printing inks using this as a binder (2) Adhesives of various Hashiden polymers and copolymers such as acrylic A/thread, KM vinyl type, vinylidene chloride type, etc., or printing using these as a binder Adhesion with ink (3) It exhibits excellent properties in terms of adhesion with metal vapor deposited layers and metal foil, so if these properties are utilized, it can be provided as Kaeda's composite composition products as described below. Things dance. - As an example, the adhesion between the printing ink and the 7V rose type binder is as follows: i+tl.

Cellulose derivatives include nitrified cotton and trocellulose)
is preferred, but other examples include cellulose esters such as methyl v-/I/rose, ethyl cellulose, hydroxyl rose ethers such as hydroxyl v-/I/rose, and cellulose propionate. In addition to these cellulose derivatives, polyamide resins made of condensates of polymerized fat and polyamines, cyclized rubbers, rubber conductors such as Gonhwa Rubber, Esul rubbers such as Kuchi Vun and Glycerine Esthe V, urea, melamine resins, etc. Although amine resins and the like may be added, the present invention is of course not limited to these. For example, when nitrified cotton is contained as a binder, the degree of nitrification is 9-12.6 liters, and the degree of polymerization is 20 seconds to 0 seconds according to the Vercules method, which exhibits the characteristics of nitrocellulose. An inorganic or organic S material or dye is used in the mixture containing the cellulose rust conductor, such as titanium white, yellow lead, copper powder, phthalocyanine blue, etc., depending on the color. The mixture was diluted with alcohol, ester, ketone solvents, ethyl benzene acetate, toluene, chlorine, etc., and the viscosity was 441. Use as i1. Also, volatilized varnish is also used as a coloring agent. This printing ink kBH is layered 9.1 to several times over a part or the entire surface. These printing ink layers adhere extremely well to the film and resist rubbing, scratching, and peeling with adhesive tape, so that even when laminated with other electrolyte or adhesive materials, the ink and film remain intact. For example, @Igt on the east side is 461/115m wide or more, preferably 100F, although it differs depending on the packaging material, weight, shape, properties, etc.
/15 m or more The film used in the present invention is cellulose-based 11 by corona discharge treatment.
The V*t value of 14 points is extremely good compared to the marked ink, which is not observed in conventional polypropylene films.

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 discharge (for polypropylene film). Whereas the polypropylene film had the disadvantage that it rarely plateaued at a certain level as the corona discharge power was increased,
The B layer in the composite film of the present invention also has the advantage that a treatment effect that is approximately proportional to the dissipated power can be obtained.

The composition of the composite film according to Book@4 is as described above, but the A and B layers contain an antistatic agent, a lubricant, an anti-blocking agent, a dye, a pigment, a weathering agent, an ultraviolet inhibitor, and each stabilizer. You are free to participate.

For example, when it is added to either (synthetic zeolite) t-All, layer B, or both (generally layer B 1), the antistatic properties and excretion properties are improved.

That is, synthetic zeophyte is a highly hygroscopic component, and it is thought that by adsorbing moisture in the atmosphere, the moisture content of the film increases, reducing electrical resistance and exhibiting antistatic properties. And in order for this effect to be achieved,
It is preferred that the synthetic zeophyte has an average grain size of 0.2 to 20 μm and is contained in the B layer, for example, with a specific gravity of 0.06 to 6 weight s. If the average grain size of the synthetic zeolite is less than 0.2/II m, the effect of antistatic properties, blocking resistance, etc. will be poor, and 'fl
If it exceeds Osm, transparency tends to decrease. If the amount is less than 0.06% by weight, the above effects will not be exhibited, while if it exceeds 6:att*, the transparency will tend to decrease.

The composite film constructed as described above is mainly used as a packaging material. ) layer and further laminate an electric composite having a lower melting point than layer A before making a bag. Other uses include films or tapes for covering metal products and plastic products. Ru.

Next, *Example and Comparative Example t of the film of the present invention - Explained - The characteristics of the film that were missed were determined according to the following fixed method.

(1) Transparent YTT Heime) According to JIB K6714.

(Adhesive properties of printing ink No. 21) Commercially available Shichikuchi Hentade was completely applied to the printing surface, and then another layer was applied at high speed, and the extent of the remaining area of the printing ink was determined.

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

tF value point Peeling rate 5 01 4 ~ 101 8 ~ 20 approx. 2 ~ 60111 1 60% or more (3; Evaporation jllA # OI #! Adhesiveness Ichiei cellophane tape 'the vapor deposition surface (!) and tIJ14 + 1 K test The peeling direction was the film-fat orientation direction (vertical) and the direction perpendicular to the grain (vertical).
"Direct invasion" in Table 1 refers to "A# non-deposited [
``After'' means mean, and ``after'' means r40℃m9
This means ``after 48wI relationship x -@l at 0*RH.

(4) Lamination Strength Regarding the printing ink, the laminate strength of 11 parts of the mark Jl was measured when the printing ink was printed on the B layer and then laminated with low WI degree polyethylene by melt interpolation. The test results are the strength flatness value (Q W
M ), A of 500 pla for ^-no vapor deposition
After the formation of the adhesion layer, the PVDC coat was extrusion laminated in 8 ways and the following was tested in 11341.
)tc)-11/ImI PVDC--A similar laminate was applied to the PVDC surface, and the results were then similarly tested.

(Durability (for printing ink)) Print on layer B, then apply low-density polyethylene 1 on top of it.
After 1 melt extrusion fuminate, 1
Bags were made at 80°C #2001N/5nlaO conditions.

Then, a steel plate was placed on the upward flat plate part of the bag, and while applying gradual pressure from above the steel plate, the critical pressure tm at which air begins to escape from the edge was determined, and the influence of the adhesive force between the base material and the ink t
(・) Heat of bag when automatically filling and packaging breadcrumbs with flour adhesion V-14/
Adherence of breadcrumbs to @1! I looked into I. The evaluation is in 4 stages: 10 marks if there is no adhesion at all, O if the adhesion is black enough to be a practical problem, tΔ mark if there is some adhesion, and tΔ mark if it is enough to cause trouble in the F-A layer. Those in which adhesion of
10 minutes), synthetic zeolite powder (particle size: 2.5 μm)
A layer A layer was obtained by adding 0.2 mol of ethylene oxide and 1.0 carbon chloride of the acylamine ethylene oxide adduct.

On the other hand, ethyl acrylamide/vinyl acetate terpolymer C/V ratio = 1:0.2:0.1)
Composition (I) was prepared by mixing 26 parts by weight of Sergeant and 76 parts by weight of polypropylene. Also, in place of the polypropylene, a mixture of polypropylene and polybutadiene (weight ratio 4/1)
Composition (2) was prepared using the following. and these compositions (
I), (Silicon dioxide (18wt) and erucic acid amide (0.05fi) were added to ID, and these were laminated as B layer on one side of A layer by coextrusion method, AN11 near 60
μrn, B-240. um.

An unstretched composite film was obtained. Next, 4 in the vertical direction at 186℃
．． After stretching 5 times and further stretching 9.0 times in the machine direction at 150°C to make a biaxially stretched film, the 8th layer side was subjected to corona discharge treatment, resulting in a surface folding tension of 45 dynes/c.
A composite film of M was obtained. Printed on BPij, A/Non-deposition PVDC coat, low percentage! It was laminated with F degree polyethylene and then made into a bag. The results of each test are shown in Table 1 below.

Example 2 In the combination of Calendar A of Example 1 and Composition (I).

The same treatment and evaluation were performed for the case where synthetic zeotite was not added to the A layer.

Example 8 In Example 2, synthetic zeolite with a B-layer pressure particle size of 4 μm was added in an amount of 0.2 J1, 4/J! The same treatment and evaluation were performed. However, as the printing ink, an allocrylic aqueous ink diluted in a water-iso Y<nol yarn solvent was used.

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

Comparative Example 1 The film of the A-layer car was subjected to the same stretching and corona discharge treatment in Example 1, and was evaluated in the same manner.

Comparative Example 2 Layer A was formed with the same composition as the base material of Example 10 and was biaxially stretched. Then melt extrusion lamination with ethylene/vinyl acetate copolymer on one side) 1. ．． A layer B having a thickness of 15 μm was formed. The B layer was subjected to corona discharge treatment.

Wet tension was 48 dynes/cs. Layer B was subjected to the same treatment as in Example 1 and evaluated in the same manner.

Claims (1)

[Claims] (1) On at least one side of the base film containing the polypropylene polymer, (α-olefin)-(acrylic acid-based amide derivative 1-
(a-olefin thread unsaturated compound) terpolymer (molar ratio = 1:0.(11~OJ:0.01~0.5):1~
60 commercial parts. Easy adhesion characterized by laminating a coating layer consisting of 299-40 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. film. 121. The easily adhesive film according to claim 1, wherein the coating layer contains 0.05 to 6% by weight of synthetic zeolite having an average particle size of 0.2 to 20 μm.