JPS5953569A - Adhesive and laminated material manufactured using the same - Google Patents

Abstract

PURPOSE:To provide an adhesive containing chlorinated polypropylene and specific components such as paraffin wax, etc., and giving a laminated material useful as a press-through pack for the packaging of drug, etc. by firmly bonding a polypropylene base with an aluminum foil. CONSTITUTION:The objective adhesive is prepared by compounding (A) 15- 40wt% of a chlorinated polypropylene, (B) 2-8wt% of paraffin wax, (C) 50- 80wt% of an aromatic hydrocarbon (e.g. benzen) (D) 0-7wt% of an alcohol (e.g. methyl alcohol), (E) 0-7wt% of an ester (e.g. ethyl acetate) and (F) 0-7wt% of a ketone (e.g. acetone). The adhesive is applied to a polypropylene base or aluminum foil base, and both bases are bonded together to obtain a laminate. EFFECT:When the adhesive is applied to the polypropylene base or the aluminum foil base and dried and wound to a continuous roll, the obtained film has high slippery and is free from blocking tendency.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a chlorinated polypropylene adhesive containing paraffin wax and a laminate of a polypropylene ice phase and an aluminum foil ice phase using the same.

Polypropylene has excellent flexibility and transparency, high rigidity and hardness, and good workability, so it is molded into films, sheets, and other shapes.

Therefore, in the market, it is being bonded to aluminum foil, taking advantage of the properties of aluminum foil and the patents of polypropylene, and is being used to develop colors for food products, packaging materials for pharmaceuticals, etc.

However, polypropylene is non-polar and has poor adhesion to aluminum foil, making it completely impossible to directly adhere polypropylene film or tape to aluminum foil.

Therefore, in order to enable adhesion between polypropylene film and aluminum foil, polypropylene was partially modified with an unsaturated carbonic acid such as acrylic acid, maleic acid, or fumaric acid (=i/1). Modified polypropylene resin obtained by forming a film into polypropylene, interposing it between polypropylene and aluminum foil, and adhering it by heating and pressurizing it. Modified polypropylene is obtained by adding a polymeric treatment, a beating agent, and a major peroxide to polypropylene, and heating it. ]Proposals have been made to use pyrene as an adhesive.

However, in these methods, the adhesive layer of modified polypropylene must be interposed between the polypropylene and the aluminum foil, resulting in a thick adhesive layer and high production cost, and also because of the thin aluminum foil and polypropylene. Adhesion to films and sheets was strongly influenced by the adhesive interlayer, and the inherent durability of polyglopyrene was lost, resulting in products with poor marketability.

Therefore, aluminum foil is coated with chlorinated polypropylene and aromatic carbon.
A method has been proposed in which an adhesive dissolved in an arsenic solvent is applied, the solution is dried, and then the adhesive is bonded to a polypropylene film or sheet.

However, with these methods, the adhesive strength is weak, and when adhesive is applied to aluminum foil and rolled into a long length, a so-called blocking phenomenon occurs in which the adhesive and aluminum foil bond together.
It has not yet been possible to obtain aluminum foil coated with adhesive in a long form.

From this point of view, the inventors of the present invention have carried out intensive research, and have found that they have developed a method of strongly adhering polypropylene base materials and aluminum foil base materials, coating and drying them on aluminum foil and polypropylene base materials, and making them into long entertainment products. We have discovered an adhesive that exhibits excellent performance, with no blocking phenomenon caused by the adhesive, and with good slipperiness on rolled objects.

Moreover, this adhesive is used for bonding 1: A material,
We found that σ) is particularly suitable as a strong bonding material between a polypropylene base material and aluminum foil.

That is, P 'J' P is a packaging material, so a material that allows the contents of a single tablet, capsule, etc. to be clearly seen through is preferred, and P '
Since the I'P forming machine performs very high-speed thermoforming, the sheets used in it require good thermoforming T4+E and 1-ROHM.

First, most conventional products have used polyvinyl chloride. However, polyvinyl chloride has a high water vapor transmission rate,
When tablets and capsules are stored for a long period of time, they tend to absorb moisture, which is a drawback, and in some markets, pollution problems have been raised.

Therefore, in recent years, pollution-free and moisture-proof polypropylene has been studied. However, since polypropylene is non-polar, it has poor adhesion to aluminum foil.
l) It has been desired to develop an adhesive that can bond polypropylene and aluminum foil well in a molding machine.

As a result of extensive research, the present inventors have discovered an adhesive that can strongly bond polypropylene base materials and aluminum foil base materials using an FTP molding machine.

The present invention was completed based on the above findings, and includes 15 to 40% by weight of chlorinated polypropylene, 2 to 8% by weight of paraffin wax, 50 to 80% by weight of aromatic hydrocarbons, 0 to 7% by weight of alcohols, and esters. The present invention relates to an adhesive containing 0 to 7% by weight of ketones and 0 to 7% by weight of ketones, and a laminate formed by bonding a polypropylene profiteer and an aluminum foil base material through the adhesive, and according to the present invention, aluminum It is possible to provide an adhesive that can not only suitably bond a foil base material and a polypropylene base material, but also suitably bond other metal foils, polypropylene base materials, etc., and to demonstrate the excellent performance of such an adhesive. Using this method, a laminate consisting of an aluminum foil base material and a polypropylene base material can be easily made, and the laminate is made of polypropylene, which is also pollution-resistant and moisture-proof, and has strong adhesion to the aluminum foil. It is useful as FTP for pharmaceutical packaging, etc.

The present invention will be explained in more detail below.

The chlorinated polypropylene used in the present invention is MF
I 0.5-15 g/l 0 m1n polypropylene is 15-40% chlorinated; for example, this chlorinated polypropylene is dissolved in toluene and commercially available (trade name: Toren Toyo Kasei Kogyo Co., Ltd.) (Made by Kiki) can be used as is.

The blending amount of chlorinated propylene is 1% for the approved adhesive strength.
It is preferable that the content be 5 to 40% by weight; if it is more than 40% by weight, coating will be difficult, and if it is less than 15% by weight, the adhesiveness will be significantly reduced.

The paraffin wax used in the present invention has 40 carbon atoms.
-70 linear paraffin wax, and for example, a commercially available product (trade name: Micro Fine Wax, manufactured by Sasol, USA) can be used as is.

The appropriate amount of paraffin wax to be added is 2 to 8% by weight based on the total adhesive material. If the amount is less than 2%, the adhesion will drop significantly, and if it is less than 8%, the Adhesion is significantly reduced.

Specific examples of solvents (mixed solvents) used in the present invention include benzene, toluene, quinlev, ethylbenzene, flobylbenzene, cumene, subuurene, etc. for aromatic hydrocarbons, and methyl for alcohols. Alcohol, ethyl alcohol, isopropyl alcohol, methyl alcohol, isobutyl alcohol, etc., and esters include ethinoacetate, methyl acetate, butyl acetate, etc.
Ketones include acetone, methyl ethyl ketone, methyl propyl ketone, isopropyl methyl ketone, butyl methyl chtone, noethyl ketone, and the like.

The suitable blending amount of these solvents is 50 to 80% by weight of aromatic hydrocarbons, 0 to 7% by weight of alcohols, 0 to 7% by weight of esters, and 0 to 7% by weight of ketones based on the total amount of adhesive. Although changing the mixing ratio of mixed solvents within any of these ranges will not cause any problems, mixing even one type of solvent outside these ranges may cause uneven coating or uneven adhesive strength.
It becomes stiff, and its adhesive properties are significantly reduced without losing its function as an adhesive.

If necessary, phthalate esters, adipate esters, liquid capolybutene, polystyrene, ethylene-vinyl acetate copolymer, etc. may be added to the adhesive of the present invention as plasticizers and viscosity modifiers, and for the purpose of preventing discoloration. You may also add a small amount of antioxidant.

Examples of the polypropylene-based irrigation material used in the laminate of the present invention include polypropylene films or sheets.

Polypropylene is a crystalline propylene nonpolymer with an n-heptane extraction residue of at least 70%, random or blocked with ethylene or other prefines containing at least 75% by weight of dipropylene. There are copolymers, etc.

Films and sheets preferably have a thickness of 5/l to 5000μ. Films and notebooks can be produced using T-shaped molding, inflation molding, and other forming methods. This also includes products processed by slight stretching using roll rolling, and anything made of polypropylene that is made into a film or sheet is wrapped. The fine powder invention σ) polypropylene group 1g2 also includes molded products other than film and sheet shapes.

In addition, polypropylene may be blended with α-olefin polymers such as polyethylene, polybutene-1, poly-4-methylpentene-1, and copolymers thereof in an amount of up to 50% by weight based on the polypropylene. Alternatively, a clarifying agent such as a nucleating agent may be added.

Examples of methods for forming an adhesive layer on aluminum foil or polypropylene base materials include gravure coaters, roll coaters, Fushinote coaters, knife coaters, rod coaters, kiss coaters, impregnation coaters, air knife coaters, gui coaters, etc. and apply it on the substrate, ioo
It is sufficient to dry it in a drying oven at ~150°C, and it is sufficient to form it on at least one of the base materials, aluminum foil and polypropylene, and any conventionally known heat-pressing method can be used for adhesion. For example, if aluminum foil, polypropylene film, and a notebook with an adhesive layer formed on one side and one without an adhesive layer are heated to 110°C to 250°C using a hot plate or hot roll, and then pressed together. Adhesion is possible.

Similarly, a good polypropylene film P is obtained by bonding aluminum foil and a polypropylene base material using a molding machine.

The present invention will be explained in more detail below with reference to actual examples and comparative series, and the test methods used in the examples are as follows.

Peel Strength A test piece was prepared by making a sample of polypropylene resin and aluminum foil adhered to each other into a rectangular shape with a width of 15 mm and a length of 1001 TIITI. This test piece was pulled at a speed of 800 mm/, T11n
The 180° peel strength was measured.

Proking test: Overlap adhesive coated side, adhesive coated side, and adhesive coated side/aluminum foil side, 0.3 k in 40℃ atmosphere for 24 hours.
A load of "g/cm" was applied and the degree of the load was evaluated.

Examples 1-5 to 4F l a Og / 10ml1n chlorine content 30
% of chlorinated polypropylene and paraffin wax (trade name: Micro Fine Wax manufactured by Sasol, USA) were added to a mixed solvent consisting of wotoluene, ethyl acetate, Inglovil alcohol, and methyl ethyl ketone to dissolve the chlorinated polypropylene and paraffin wax as shown in Table 1. An adhesive consisting of the stated proportions was obtained.

b1) Apply the adhesive to a thickness of 20 μm using a gravure roll method.
Coat 4.0 g/mQ on one side of aluminum foil.

It was dried in a drying oven at 150°C.

Next, the adhesive-coated surface and MF of the adhesive-coated aluminum foil obtained
L 2. Og / 10ml Made by T-die method using 1n propylene homopolymer, 1 piece thickness 0.3 mn-+
polypropylene sheet at 180°C for 10 seconds
Adhesion was performed under a load of 1 kg/cm'', and the peel strength (180°C peel) between the aluminum foil and polypropylene was measured.

As shown in Table 1, the adhesive strength was extremely strong.

In addition, one-sided adhesive-coated aluminum foil was overlaid on the adhesive-coated surface/adhesive-coated surface and the adhesive-coated surface/aluminum foil surface, and shadow blocking was performed under a load of 0.8 kg/cm' in an atmosphere of 40°C for 24 hours. I did a test.

As shown in Table 1, the results were non-blocking.

Comparative Example 1 The same procedure as in Example 1 was conducted except that paraffin wax was not added.

As shown in Table 1, the results showed that the adhesive strength was weak and the surface to which the adhesive was applied was extremely blocking.

Comparative Example 2.3 Addition meter for chlorinated polypropylene in Example 1]
The same procedure as in Example 1 was carried out except that the proportions shown in the table were added.

The results are shown in Table 1. When the amount was too low, the adhesive strength was very weak, and when the amount was too much, the adhesive was not evenly applied to the aluminum foil, resulting in large variations in the adhesive strength.

Comparative Examples 4 to 7 Comparative Examples 4 to 7 Comparative Examples 4 to 7 were carried out in exactly the same manner as in Example 1, except that the blended amount of the mixed solvent was added to the proportions shown in Table 1.

As shown in Table 1, the results show that if even one type of mixed solvent is outside the scope of the claims of the present invention, the adhesive strength will be weak, and the adhesive will not be evenly applied to the aluminum foil, resulting in large variations in adhesive strength. Ta.

Example 6 The same procedure as in Example 1 was carried out except that instead of the chlorinated polypropylene used in Example 1, chlorine containing 20% chlorine (hypolypropylene) was used.

As shown in Table 1, the results showed that the adhesive strength was strong and there was no blocking.

Example 7 The same procedure as in Example 1 was carried out except that chlorinated polypropylene having a chlorine content of 40% was used instead of the chlorinated polypropylene used in Example 1.

As shown in Table 1, the adhesive strength was strong and there was no blocking.

Examples 8 to 14 The same procedure as in Example 1 was conducted except that the polypropylene films and sheets shown in Table 2 were used instead of the monopropylene monomer sheet used in Example 1.

As shown in Table 2, the results showed that the adhesive strength was strong.

Driving Examples 15-19 MJ” I & Og710 min Chlorine content 30%
Chlorinated polypropylene and paraffin wax (trade name: Micro Fine Wax, manufactured by Zazol, USA)'f,t
l-toluene, ethyl acetate, isopropyl alcohol,
The mixture was added to a mixed solvent of methyl ethyl and ketone, and chlorinated polypropylene and paraffin wax were dissolved to prepare an adhesive having the ratio shown in Table 3.

4. Apply this adhesive to 20μ thick aluminum foil using a gravure roll method. ．． 0g7ml was applied and it was dried in a 150''C drying oven.

The resulting adhesive coating and aluminum foil were then applied to a TP molding machine (
A polypropylene-1-f molded product was bonded at a sealing temperature of 180° C. using a M-600 type flat plate method manufactured by Misonori Koki Co., Ltd. (PTI).

As shown in Table 3, the obtained T"L' T) has strong adhesive strength between the polypropylene molded product and the aluminum foil, and one
Each pocket was securely sealed.

Comparative Example 8 The procedure of Example 15 was repeated except that no paraffin wax was added in Example i5.

As shown in Table 3 C, the results showed that the adhesive strength was weak, and some bulges occurred between the polypropylene molded product and the aluminum foil.
It was not a struggle to ensure that each individual pocket was sealed.

Comparative Example 9, ], 0 The same procedure as in Example 15 was carried out except that chlorinated polypropylene was added in the proportions shown in Table 3.

The results are shown in Table 3. When the amount is small, the adhesive strength is weak compared to the non-stick, and when the amount is large, the adhesive strength varies widely.
When sealing the polypropylene molded product with aluminum foil in both small and large cases, a portion of the adhesive surface bulged, making it impossible to reliably seal each pocket.

Comparative Example 11-Example 15! The same procedure as in Example 15 was carried out except that the proportions shown in Table 1 were added to the mixed solvent Blend Q-.

As shown in Table 3, the results show that even if one type of mixed solvent is used as claimed in claim 7f of the present invention, the adhesive strength is weak and the adhesive surface (
Some of the pockets were bulged and each pocket was reliably sealed, resulting in no lumps.

Example 20 The adhesive-coated aluminum foil obtained in Example 15 was used as I)
T I) Acid formation (11M225 manufactured by Techno Jidoki Seisakusho)
Transparent polypropylene sheet 'a? Molded product and nur temperature +y 1
FTP'a was obtained by adhering at s o ℃.

As shown in Table 3, the obtained 1t P l"P has a strong adhesive strength between the polypropylene molded product and the aluminum foil, and
One pocket that is securely sealed.

Claims (1)

[Claims] 1. 15 to 40% by weight of chlorinated polypropylene. Paraffin wax 2-8% heavy equipment, aromatic hydrocarbons 50%
An adhesive containing ~80% by weight of alcohols, ~7% by weight of alcohols, ~7% by weight of esters, and 0~7% by weight of ketones. 2 Polypropylene base material and aluminum foil base material are chlorinated polypropylene 15 to 40% by weight, paraffin wax 2
-8% by weight, 50-80% by weight of aromatic hydrocarbon water, O-7% by weight of alcohols, O-7% by weight of esters, and 0-7% by weight of ketones. A laminate made up of