JPS5876272A - 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 base film, and has printing ink adhesion and metal thin film adhesion.

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

#-1 for K (including plastic films (V-) used for food packaging, textile packaging, etc.; the same applies hereinafter). Adaptability to high-speed ropes, reduction of residual solvent.

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 and more widely in the future since they do not have the problem of environmental pollution due to wasteful ink. One known example of such ink is one that uses a 7V loin derivative as a binder (product name: 1 Cellophane Ink).However, currently commercially available printing VC for polypropylene thread film uses a special organic solvent. #
X fruit ink is used, and each ink is stored and managed separately, and the appropriate anchor coating agent (anchor coating agent for laminating low melting point films such as polyethylene) is stored and managed in the same way. When necessary, there was a misunderstanding that many types of inks and adhesives had to be prepared during the bag making process.

In order to provide printability, an attempt has also been made to improve the adhesion of the film by coating the film surface with a resin liquid. However, the process is complicated and the price is also high9. This is a wasteful method. In addition, polypropylene films have poor metal deposition properties and poor adhesion to metal foils.

Primer processing is also applied to cover this, but the primer alters the quality of the deposited metal and causes JI (,t
Printability and adhesion processability for the electrodeposited surface of A are hindered, and it is also uneconomical since primer treatment is required.

The pyrene-based 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 polymers, so it is important to try to improve this. If this could be done, it would be possible to prevent environmental pollution due to solvents, omit pretreatment steps, save materials, and reduce the amount of PAgiI solvent, which would be extremely advantageous.

The present invention has been made with attention to such circumstances, and includes the adhesion of printing ink to WI and the adhesion of thin metal strips.

The object of the present invention is to provide an easily adhesive polypropylene composite film with good organic polymer adhesive properties.

A composite film that successfully achieves the above objectives is:
A base film containing a polypropylene polymer vA< is coated with an (acrylic A'# ester derivative)-(a-olefin) copolymer on at least one side thereof, using the general formula % formula %) where R1 and R2 are the same. - or different hydrogen or leg water 1! In the residue, hydrogen in the hydrocarbon residue may be converted to amino Mi or Al*A', and may be replaced with an amino group to form V4. Also treated with amino alcohols represented by Rii (representing a divalent hydrocarbon residue), 9 = 1 to 6
0″I regret the amount.

The gist lies in the fact that a coating layer is laminated with a poly-alpha-olefin polymer of 99-4031 weight and composed of 100-60 weight of poly-a-olefin and 0-40 weight of polybutadiene.

Specific examples of the present invention, VC application examples, etc. will be described below.

First, the polypropylene polymers constituting the base film (hereinafter referred to as layer A) include (1) polypropylene;
(Copolymer of 2 or more a-olefins selected from a-olefins having 2 or more carbon atoms, preferably 10 or less (however, a little (both 1m is propylene), (a) above) * Polymer of f21 and polymers with good affinity with these, such as polyolefin-based homopolymers or copolymers such as polyethylene, ethylene/propylene copolymer, polybutene-1, ethylene/butene copolymer, poly-4-methylpentene-1, etc. Examples include mixtures with
*: Propylene tin is used alone or in a co-electrical combination. In this case, it is desired that the content ratio of the propylene component is at least aoz-31. Such polypropylene polymers have poor properties (printing ink adhesion), and the improvement effect of the present invention is extremely significant.

Next, at least 4 layers are laminated on one side of layer A & layers c and below B
Let's take a closer look at each of the 5irlt layers (referred to as layers).

BM is 1sl (acrylic acid ester V derivative) - (α
- olefin) co-electrolytic polymers of amino alcohols (
(hereinafter sometimes referred to as a modified copolymer): A polyolefin-based polymer consisting of 1 to 60 parts, (2) 100 to 40 parts of polyα-olefin, and 0 to 40 parts of polybutadiene. It consists of weight parts,
These will be explained in order below.

First of all, acrylic acid beauty salon A/@conductor is Acrylic 7L/
It includes all Wm esters, methacrylic A/acid esters, etc., but particularly representative ones include alkyl esters A/ of acrylic acid and methacrylic acid, such as methyl acrylate, ethyl arylate, propy V acrylate, Butyl acrylate-F.

Pentyl acrylate 1. Methyl methacrylate.

Examples include methyl methacrylate and butydimethacrylate. However, in the above, the selection of the acyl group is not particularly important.

Therefore, from an economic point of view, relatively inexpensive materials such as methyl acrylate, ethyl acrylate or methyl methacrylate are most advantageously used.

Examples of a-olefins include ethylene, propylene, butene-1, pentene-1, and methylpentene-1 fathom. be. The composition ratio of the copolymer of acrylic acid ester and a-olefin selected in this way does not limit the present invention, but according to various studies, the acrylic acid ester unit is 1 to 50 mopvt4. Preferably, those containing 1 to 80 moles and having an intrinsic viscosity of 0.06 to 44 dt/g determined as a xylene Pa solution at 120° C. are preferable as raw materials for producing the composition of the present invention.

A copolymer having an acrylic acid ester unit content of less than 1 mole is prepared by treating with aminoalco-V (1),
Even if mixed with a poly-α-olefin polymer, if the proportion of the copolymer added to the polyolefin polymer is in an appropriate amount as described below, it will not substantially contribute to improving the adhesion properties. If more than the appropriate amount is added and mixed, printability can be improved, but the good #jJA@It properties inherent to 4 polyolefins will no longer be retained in the mixed composition. Improved printability & CFi cannot be used. Award Akuri A'M
A modified copolymer prepared by treating a copolymer containing more than 50 7 l of yarn compounds alone with amino alcohols has poor compatibility with polyα-olefin polymers ( P, l and α-olefin yarn polymers are unfavorable for improving printability in terms of die quality.

Also, this -〇 copolymer aminoalcohol-/L/type (1)
The viscosity of the treated copolymer is generally lower than that of polyα-olefin polymers, so if the copolymer has an intrinsic viscosity of 0.06 to 4.5 dl/g, You can use any of them without any problem.

Next, in 7 Minoan Calls (I) RL and RQ
The hydrocarbon residue represented by is alkyl.

Examples include V chloroalkyl V, aralkyl, aryl, etc.
The divalent hydrocarbon residue represented by R is exemplified by alkylene, cycloalkylene, and arene, but one representative amino alcohol Jm(I),! - for example aminoethanol, N-methylaminoethanol-A/,
N,N-dibutylaminoethanol, N-ethylaminoethanol, N,N-diethylaminoethanol, N,
N-dibutylaminoethanol, N,N-benzylaminoethanol, N,N-dibutylaminoethanol, N
-Ethylanilinoethano-JL/, N-phenylaminoethanol, N-(aminoethyl A/)aminoethanol, N-j/Yoshihexylaminoethanol.

Aminopropano-A/, N-methylaminopropano-A
/, N, N-digtylaminozolopanol, N-ethylaminopropano-A/, N, N-ethylaminoderovano/L/, N, N-digtylaminozolopanol, amino 1 Tanol, N,N-dimethylaminobutano-tV,N,N-s! ethylaminobutano-A/,
N,, N-dimethylaminohexanol.

Examples include aminopheni V ethanol.

When treating an acrylic #-based ester and an a-olefin copolymer with an amino alcohol (D).

1 copolymer and one or more aminoalks (
I) in the absence of a catalyst or in the presence of a catalyst, generally at a temperature of 100 to 850°C. When the process is carried out at a low temperature outside of this temperature range, the reaction rate is low, and when the process is carried out at a high temperature, undesirable side reactions occur. Since such obstacles are slightly opposite even within the 1M degree range, it is preferable to
Treatment with aminoalcohol Jvm (I) is carried out at a temperature of -800°C. This reaction is aminoalcohol-N @
Type (1).

-AE can be carried out under elevated pressure or normal pressure depending on the reaction solvent sui+ and the processing temperature. Furthermore, this reaction can be carried out without a catalyst.

In this case, generally only a treated product with a low transesterification rate is obtained, but in order to obtain a treated product with a high ester exchange rate, it is effective to use a suitable catalyst. Suitable catalysts include natural metal salts, metal oxides, organometallic compounds, Friedel-Crafts type catalysts, and the like. For example, zinc acetate, lead acetate.

Cadmium acetate, mercury acetate, manganese acetate, calcium acetate, nickel acetate A/, sodium acetate, iron acetate, cobalt #acid, zinc formate, lead formate, cadmium daate, zinc propionate, n-wIil zinc, n-valeric acid Zinc, n-
Zinc caprate, zinc lyurate, zinc stearate,
*Zinc acid, zinc chloride, aluminum chloride, tin chloride, titanium tetrachloride, bulk fluoride, p-) Luens A/Chinese Soviet Union,
Zinc glycoside, manganese oxide, sodium methoxide, sodium ethoxide, sodium phenoxide, a/nium inderoboxide, lead oxide.

Zinc oxide, cadmium oxide, etc. can be used.

In addition, the treatment with amino alcohol V alcohol (I) K is carried out without solvent, that is, the molten copolymer and amino alcohol I
This can be carried out by contacting j(I), but it can also be carried out in the presence of an organic solvent. Yes a
ii*g is mainly used for smooth reaction and control of 121 degrees, and suitable examples include decalin, tetralin, xylene, tovene, penyne, vchlorohexitone, tetrahydrofuran, vchloride, etc. A/, those that can dissolve the copolymer, such as tetrachlorinated legs, are preferred.

The modified copolymer obtained by the treatment with aminoacols (I) can be transformed into an ester of the copolymer or the copolymer component in the composition by appropriately selecting the treatment conditions. Up to about 98 molecules of A can be transesterified.In general, a product with a high transesterification rate can be obtained quickly if the treatment is carried out at a temperature of 100 to 200 m.As a component when producing the B layer composition of the present invention A suitable modified copolymer preferably has a transesterification rate of 2 mo or more, and the transesterified acrylic ester V units amount to about 1 to 49 molecules of the treated material.

The dlIJa-olefin in the polyα-olefin polymer is a homopolymer or copolymer formed from a-olefins having 2 to 10 leg primes (e.g. polypropylene, polybutene-1, poly-4-methylpentene-1).
, ethylene/propylene copolymer, ethylene/butene-
Melt index X
(280℃) mO4~80 g/10 m, especially Vcl
, 0 to 16g/10ai* will be awarded. The other component, polybutadiene, further enhances the adhesive property improvement effect of polyα-olefin.
When the molecular weight is less than 500, migration is severe, resulting in a significant decrease in adhesion and occurrence of blocking], and scratch resistance is also decreased. On the other hand, when the molecular weight exceeds 20,000, the transparency decreases (1 molecular weight at 20,000 ~ 20,000
It is recommended that you select from the following range. However, a more preferred range is 800-10.0 GO. In addition, the blending ratio of polyα-olefin and polybutadiene is 10 for the former.
The latter should be 0 to 40 parts by weight per 0 to 5 parts by weight, and it is not inconvenient to achieve the objective of the present invention even if polybutadiene is not added, but if it exceeds 40 parts by weight, A
1 when laminated in layers! The transparency of i has deteriorated, and the letters and figures printed from the 8th layer side are A! This is not a desirable thing, since it reduces envy when viewed from the side.

The blending ratio of the modified copolymer and the polyolefin polymer is 1 to 60 parts by weight of the former to 99 parts by weight of the latter.
~40 parts by weight of the tube can be used.

The reason for this is that when the former is less than 1 part by weight, the adhesion of the printing ink, metal thin film, and organic polymer (especially wood-based resin) as the B layer is insufficient69; so
This is because if the adhesive exceeds y-curve, there will be a decrease in transparency, a decrease in extrusion stability, a decrease in adhesive strength due to heat history after bonding, and in any case, commercial productivity and commercial value will be significantly deteriorated.

Chemical group w1 of composite film V according to the present invention. Although there is a general p″e clarified by the above explanation, it is the A layer.

B90 For each formation method and lamination method, i'c is limited.
However, it is most preferable to use the second ecjllpe method, i.e., to prepare the composite film consisting of the OA layer and the B layer of the present invention, the following methods are used: 1-VH-1, 4-L stretching, A method of gluing at the same time as heating stretching with a tower, or a method of combining 11,000 tons of longitudinal stretching and the other', or a method of gluing after longitudinal stretching, and subsequently stretching in a direction perpendicular to the above. Method 1 and other methods can be adopted. Of course, combinations of ξ, etc., tJI, Ichiku, and Ii may be applied using means other than the above.
For sequential knee stretching, unstretched film t* is used instead of @.
The first method is to stretch the film longitudinally in the longitudinal direction using a roll abrasive machine and then horizontally stretch the film in a direction perpendicular to the longitudinal direction using a tenter. In the case of simultaneous knee stretching, either the tenter method or the inflation V-tumor method 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 that are possible with ordinary polypropylene films.

In addition, the A layer and B layer used in the present invention, and the relative It is desirable that the film be stretched in at least one direction. Therefore, the composite film of the present invention includes one in which the A11l and B layers are entirely wheel-stretched, a film in which the B layer is wheel-stretched and A- is two-wheel stretched, and a film in which the A layer is uniaxially abraded and the B layer is knee-stretched. Examples include those in which the A layer is biaxially stretched and BP#I is unstretched, and the B layer is two-wheel stretched and the A layer is unstretched. Now, if I were to express this in t-t' terms.

When abbreviated as biaxially stretched IBO1-axially stretched iUo, Kinenobeki t-NO, No-A layer/No-B layer, UO-A layer/N
o-B layer, υO-A layer/υO-B layer.

NO-AM/DO-B layer, BO-A layer/No-11 layer,
BO-A layer/UO-871140-A layer/BO-B layer,
No-A layer/BO-B layer, Do-A layer/BO-B layer, etc.
This can be done by design.

The example of the 3o design on the granite is - the deviation is also the 2nd amount O example, and the female pi is,
We design composite films with eight or more layers as needed.
It is also possible to make one. Motomo II! When used for textiles, eight layers of two layers are sufficient.

There is no need to provide a special thickness for the A layer and B layer, and there is almost no limit on the A layer in particular, but the B layer
For the layer, the final Ko,t Ns.

μm, preferably 0.4 to 15 μm, depending on the application. It is also possible to design it to be thicker. When the BNI is less than 0.1 μm, the adhesion stability becomes poor, and when it exceeds 801 μm, the transparency becomes poor! I can't use it because of the drawback of vomiting.
I get 9. The most preferable value is 10 μm or less.

The composite film of the present invention constructed as described above has excellent adhesion to an adhesive containing a cellulome derivative or a printing ink using this as a binder (phantom acrylic, Naruka Vinyl I4).
Copolymer-in-polymer-based adhesives and printing inks and O-based binders.
IR adhesion (3) Gold XS adhesion layer exhibits excellent adhesion with metal foils, so if these characteristics are utilized, it can be used as a complex composite product as described below. I can do it. - As an example, the adhesion with printing ink using cell fours yarn derivative as a binder is as follows.

As the cellulose thread@conductor, nitrified cotton (=trocellulose) is preferred, but other examples include methyl cellulose, ethyl cellulose, hydroxy-V-ethyl cellulose cape 7-rose ether, and cellulose ester exclusively for propionate cellulose. In addition to this cellulose derivative, a polyamide resin consisting of a condensate of a polymerized fatty acid and a boria electron, a cyclized rubber, a rubber derivative of Gonka rubber,
Glycerin Esthe A/V rubber, raw material, amine resin such as Messin resin, etc. can be added, but are not limited to these. For example, when containing nitrified cotton as a binder, the The degree of polymerization is 9P-118-, and the viscosity is 20 seconds to 1 second according to the 8-cures method, which indicates the characteristics of a polymerization degree of 9P-118-. In a mixture containing the above cellulose-conductor 7, inorganic or organic 1 iu
For example, titanium white, yellow lead, copper powder, phthalocyanine blue, etc. are used depending on the color. These mixtures are diluted with alcohols, esters, ketones, and organic bath agents such as ethyl acetate, benzene, toluene, and dichloromethane to adjust the viscosity before use. Volatile 9 varnish cicada is also used as a coloring agent. Part or all of the eight layers of printing ink are overprinted once to several times. These printing ink layers adhere extremely well to the film and are well resistant to rubbing, stretching, and peeling with adhesive tape, etc., so that even when laminated with other polymers or films, the ink and the film remain intact. For example, the strength on the east side of the interface means a width of 46F/15111 or more, preferably 100F/115M or more, although it differs depending on the weight, shape, and properties of packaging materials.The film used in the present invention is The fact that it exhibits extremely good adhesion to printing ink containing cellulose fibers through corona discharge treatment, which is not observed in conventional polyester film, is another characteristic effect of Honkokiri. By using the conventional o:Ia discharge Flr power required (for polypropylene film) and the electric power of tq11j degrees, it has been found that a higher processing effect can be obtained, and with the conventional polypropylene film: However, in the B layer of the composite film of the present invention, the discharge power consumption is almost proportional to the power consumption. It also has the advantage of being effective.

The structure of the composite film according to the present invention is the above j! As for ID, it is free to add antistatic agents, beak agents, anti-blocking agents, dyes, potting agents, weathering agents, ultraviolet inhibitors, and various ellipsoidal stabilizers in the A and B layers.

For example, if synthetic zeophyte [^JIS e] is added to either or both of the B layers (generally the B layer), the antistatic properties and slip-on properties will be improved.

Synthetic Zeo Tsui) Ti is a component with 0* humidity and % water molecules in the atmosphere: By adhering to it, the water work of the film increases, reducing electrical resistance and exhibiting antistatic properties. it is conceivable that. In order for the young fruit to be exhibited after the zeolite is set, the synthetic zeolite must have a flat grain size of 0.2 to 205 m, and even if the ijB layer contains O, OS ~ 6 violet 1* on this shore. It is desirable that the If the average particle size of the synthetic zeolite is Q, gPflll, the effect of antistatic properties, anti-blocking properties, etc. is poor, and if it exceeds 20 μm, transparency tends to decrease. Also, the amount added is 0
．． If the weight is less than 0.6 kg, the above effect will not be exhibited, and on the other hand, if the weight is less than 6.
If the weight exceeds 1&t-, transparency tends to decrease.

The composite film constructed as described above is mainly used as a packaging material, but in the case of chicks, a printing ink layer, an adhesive layer, or a W resin (kin seed resin) layer is formed on the B leg axis. However, a polymer having a lower melting point than layer A is further laminated before bag making. Other uses include films or tapes for covering metal products and differential plastic products.

Next, 81! of the film of the present invention! Examples and Comparative Examples will be described. The properties of the forged films were determined according to the following Ofs standard method.

(1) Transparency (haze) Conforms to JIS K6714.

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

The printing ink was cellophane ink CL-C (manufactured by Dainippon Ink Co., Ltd.) tJ@M, and the evaluation was based on the following criteria.

Evaluation points Peeling ratio 6 0 4 ~10% 8 ~20% 2 ~50- 15 layers or more (3) Adhesiveness of vapor deposition A# Commercially available cellophane tape tA# Closely attached to the vapor deposition surface Same as (2) Tested and evaluated. The direction of the #11 can is the direction perpendicular to the orientation direction of the film resin (line) and the ξ angle (horizontal). In Table 1, "direct bite" means "immediately after arrival at the AI island". , and “after the treatment place” is r40@0190%RH
t-
Do family law.

(4) Laminate 5!1 For printing ink, there is no mark M11ktT on the 8th layer,
Next, the laminate strength of the printed area was measured when the low VB degree polyethylene t-melt insertion film was tossed. Tesshi results are obtained by peeling the laminate layer at 90 degrees! 0 0
The color intensity level value (f
It is shown as i-6). About AI deposition tyo500#1II
The results of the same test were shown for the AIIIA laminated layer of AIIIA, which was also extruded and laminated.* P V
DC:x-? K Tsun ”CF18 17W
* (2) Similar lamination was applied to the PVDC coated surface, and the results of the same test were shown. [
After melting and discharging and laminating, use automatic filling and packaging machine 7, 1
I at 80℃@200gj410aia O condition
Then, a steel plate was attached to the upper flat plate part of the leg, and while applying gradual pressure from the top of the steel plate, the critical force at which air begins to plow out from the edge was kept constant, and the influence of the adhesive force between the wiping material and the ink was measured.
-Related.

(・)Powder adhesion to the twill Automatic filling and packaging of bread crumbs and cooling bag O heat $/-A'
The adhesion of bread crumbs to lSK was investigated.Evaluation is in 4 stages: no adhesion at all (10 marks), no adhesion to the extent that it poses a practical problem ('to' marks), and those with significant adhesion [Δ Mark, Dan-A/ll 5K If adhesion is observed to the extent that it causes obstruction, it is indicated by a dot.
1 synthetic zeolite powder (particle size: 2.5 μm)
0.2] kJii alkylamine ethylene oxide adduct was added at 1.0 t% to form layer A.

On the other hand, methyl acrylate/propylene copolymer (methyl
Acrylate content: 18 moV%).

One composition (I) was prepared consisting of 80% by weight of a modified copolymer treated with N-dimethylaminoethanol and 70% by weight of a propylene/ethylene copolymer (ethylene content: 8.5jlrt). Also mentioned above! A composition (2) was prepared, which consisted of a polyolefin mixture consisting of a polypropylene (60% by weight)/polybutadiene (40% by weight) and a polypropylene (60% by weight)/polybutadiene (40% by weight). These compositions (I
), (Add 0.8 heavy J1 silicon dioxide and 0.0 fili Jl erucic acid amide to ID, and add these to B.
Laminated as M by co-extrusion method on one side of AP#I,
#11: An unstretched composite film of 760 μms 8 layers: 40/Jm was obtained. Next, 4. vertically at 186°C.
After stretching 5 times and stretching 9.0 times in the transverse direction at Vc1fiO°C to make a biaxially stretched film, the 8th layer side was subjected to corona discharge treatment to produce a composite film with a surface wetting tension of 46 dynes/side. I posted a V. Printing on B layer, AI vapor deposition, PVD
It was coated with C and laminated with low density polyethylene, and then made into a bag. The results of each test are summarized in Table 1 below.

Example 2 In the combination of layer A of Example 1 and composition (I).

The same treatment and evaluation were performed for the case where synthetic zeolite was not added to AJill.

Example 8 In the 2B layer, 0.2 weight of synthetic zeolite with a particle size of 4 μm was mixed, and the same treatment and evaluation as in Example 2 was carried out. However, as the printing ink, an acrylic water-based ink was used. was diluted in water-itbutanol solvent.

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

Comparative Example 1 Similar evaluations were performed on the A-layer heavy film of Example 1, which had been subjected to stretching and corona discharge treatment 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. Next, an ethylene/vinyl acetate v copolymer was melt-extruded laminated on one side to form a layer B having a thickness of 15 μm. BM is subjected to corona discharge treatment.

Wet tension was set at 48 dynes/(to). BM was subjected to the same treatment as in Example 1 and evaluated in the same manner.

Claims (1)

Claims: ill on at least one side of a base film comprising a polypropylene yarn polymer. (Acrylic ll#-based esthetics A/s conductor) -(--olefin) copolymer treated with aminoalco-V class 2 represented by the following formula: 1 to 60 parts by weight. In the formula c, Rl, a and Q are the same or different and are hydrogen or a hydrocarbon residue, and the hydrogen in the hydrocarbon residue may be substituted with an amino group or an alkyl-substituted amino group. . Also, R3 is a divalent hydrocarbon J! j group) Polyme olefin too (2) The easily adhesive film according to claim 1, wherein the coating layer contains 0.05 to B weight of synthetic zeolite with an average particle size of 0.2 to 20 μm.