JPH06504497A - barrier resin coated laminate - 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] name of invention Barrier up sheathing laminate field of invention The present invention relates to materials with improved heat sealability. In particular, the present invention is a metallized polymer film with improved heat sealability for use in packaging. It is about film.

Background of the invention Materials like polymeric films and metal foils can oxidize and protect products like food materials. It is used to protect against the effects of water vapor transmission. The above polymer film The film is typically coated with a polymeric barrier layer composition.

The barrier layer composition typically includes coating additives such as aluminum silicate. , talc, wax, etc. to achieve desired film properties, such as jaw release properties. , imparts printability, film slipperiness, etc. Unfortunately, these additives are It tends to reduce the coating adhesion and heat sealability of the overlying polymeric film.

Metal foils, for example aluminum foils, are also used as packaging materials for products such as food materials. It is also used. Metal foil has low permeability to oxygen and water vapor However, metal foils are subject to significant cost fluctuations and are heat-sealable. It has poor bending and cracking resistance.

The art has made efforts to improve the heat sealability of polymer fills.

In U.S. Patents 3.896.066 and 3.985.065, the patentee A copolymer barrier coating of hnylidene chloride has been applied to a polymeric substrate.

Japanese Patent Publication No. 6223174 published on 12th IO, 1987 in 1 sun is paper or and manufacturing of metallized sheets of plastics. This method uses methacrylic Acrylic acid ester, acrylonitrile, polyvinyl chloride and methacrylic acid Nylidene copolymer is suitable for use on the No. 1 metal-treated surface of paper or plastic. and then oxidizing the above polyvinylidene chloride copolymer. be.

The technology uses a hnylidene chloride copolymer barrier layer with a polymer film. However, due to the effectiveness of the coating additives, heavy metal processing using these barrier compositions is Coalesced films tend to have defects as packaging materials. Therefore, the coating using barrier layer compositions that overcome the disadvantages of prior art materials. A need exists for improved metal processing packaging materials.

Summary of the invention The present invention provides one or more surface coatings that exhibit improved barrier layer coating adhesion and heat sealability. A metallized material with a metal coating on the top surface will be trialled. these The metallized material has a vinylidene copolymer coating on the metal coating. This port Vinylidene chloride copolymers contain at least 80% vinylidene chloride, less than 4% % ethylenically unsaturated acrylic monomer, and for improving film properties Contains coating additives.

In accordance with the present invention, a metal treated coating exhibits improved barrier layer coating adhesion and heat sealability. Additives for coating a substrate material with a safe surface on it (one side of the material) ``Produced by treatment with a blended solution with hynylidene chloride copolymer. the above The polyvinylidene chloride copolymer contains at least 80% by weight of polyvinylidene chloride. and at least 4% by weight of an ethylenically unsaturated acrylic ester. salt A solution of a copolymer of vinylidene chloride and a coating additive is applied to a polymer having a metal layer thereon. A barrier that provides surprisingly improved adhesion and heat sealability to materials such as polyesters. Form a wall layer.

The application according to the invention of the above solutions results in surprisingly improved adhesion and heat sealability. is obtained. These types of substrates include plastics, regenerated cellulose, paper, and metal-treated This includes recycled plastics, metal-treated recycled cellulose, metal-treated paper, etc. , but is not limited to this. Plastics suitable for use in the present invention is polyester, polyolefin, polyamide, vinyl chloride, and copolymers thereof. and mixtures thereof, but are not limited thereto. its adhesion Materials whose properties and heat sealability can be improved by the vinylidene chloride copolymer described in the present invention Additional examples include, but are not limited to, metal foils, such as aluminum foils. It's not something you can do.

A blended solution of vinylidene chloride copolymer and conventional additives can be prepared using conventional methods known in the art. It can be applied to the substrate material by any number of methods. This kind of method Includes solvent solution coating, emulsion coating, melt coating, etc. Preferably, the present vinyl chloride Nylidene copolymer is mixed with vinylidene chloride copolymer and base material in a normal coating tower. The compounded PVC is passed through a solvent solution with coating additives and then the solvent is evaporated. A layer of redene copolymer and coating additive is applied in such a way that it is obtained on the substrate.

Substrate material coated with a mixed solution of vinylidene chloride copolymer and coating additive, preferably or metallized polymeric films have particular utility in packaging for substances such as food. These coated substrate materials can be used as manufactured, which Alternatively, but without limitation, the coated metallized substrate material described above may be laminated. It can be used in the form of a laminated film structure. Manufactured according to the invention Coated substrate materials can also be used in applications such as, but not limited to, insulating materials for the construction industry. It can also be used for applications where

Having provided a brief overview of the invention, reference is made to the specification and non-limiting examples below. The invention will now be described in detail. All percentages unless specified otherwise. The ratio is 96 degrees to 1 weight, and all temperatures are in degrees Celsius.

detailed description of the invention According to the present invention, vinylidene chloride (VDC) copolymer and 10% by weight or more of the copolymer A mixed solution with coating additives in the metal-retaining substrate, preferably metal-treated polymerization Applicable to body films, most preferably metallized polyethylene terephthalate do. The VDC copolymer has at least 80%, but not more than 95% chlorination. Contains vinylidene. The remainder of this vinylidene chloride copolymer is ethylenically unsaturated. It consists of an acrylic acid ester, preferably methyl methacrylate (~IMA). this The ethylenically unsaturated acrylic ester contains at least four of the above VDC copolymers. %. Replacing Ike's ethylenically unsaturated polyacrylic acid ester with MMA , or in combination with MMA. Adequate ethylenic unsaturation Examples of Japanese acrylic esters include aliphatic C2-C, acrylic ester, aliphatic Q Includes, but is not limited to, 2-C6 methacrylic acid ester, etc. stomach. Examples of ethylenically unsaturated acrylic esters include butyl acrylate, acrylic Examples include, but are not limited to, methyl acrylate, ethyl acrylate, and the like.

Examples of aliphatic methacrylates include methyl methacrylate and ethyl methacrylate. etc. are included.

The copolymer contains at least 4% ethylenically unsaturated polyacrylic ester. If so, add acrylonitrile (AN) to the present vinylidene chloride copolymer. It can also be included. Preferably, the copolymer has between 80 and 95% vinylidene chloride and 4 to 20% ethylenically unsaturated acrylic ester, Most preferably 88 to 92% vinylidene chloride and 6 to 12% ethylene. and a polyunsaturated acrylic ester.

Metal holding material that can be coated with a mixed solution of vinylidene chloride copolymer and coating additive is preferably a metal-treated polymer. Examples of suitable polymers include polyester , polyolefins, polyamides, polyvinyl chloride, copolymers thereof, and It includes a mixture of Oxidizable metals such as Fe, CuSAt, Ti1 Any of these alloys, etc., are most preferably aluminum metallized heavy metals. The metal component of the combined film can be formed. Most preferably, the metal processing The polymer film is aluminized polyethylene terephthalate.

Metal-treated polymers of this type may be used, for example, if the disclosure is incorporated by reference. Encyclopedia of Chemica l　Technology)”.

Kirk Otsudo? - (Kirk-Othmer), 3rd edition, Volume 15, 2 Manufactured by methods known in the art, such as those described on pages 64-265. However, the metal holding material that can be coated is other than the Uta gold rR treated polymer. Good too. Examples of additional metal-retaining materials that may be used in the present invention include metallized recycled cells. lurose and polyolefins, e.g. metallized paper, metallized oriented paper. Contains lipropylene, etc.

The improved product according to the invention preferably contains more than 90% by weight, at least 4% Hynylidene chloride copolymer with percent ethylenically unsaturated acrylic ester A coating solution of coalescence and up to 10% by weight of coating additive is applied to the metal-retaining substrate at a low temperature. It is also manufactured by applying it to metal holding surfaces. Examples of coating additives include talc and wax. , aluminum silicate, etc. Instead of this, hnylidene chloride copolymer The formulated solution can also be applied to both metal-retaining and non-metal-retaining surfaces of the base material. can.

The blended solution of vinylidene chloride copolymer and coating additive is preferably metal-treated. Applicable to base materials. Then, the solvent of the vinylidene chloride copolymer solution was evaporated to form a salt. Coating with vinylidene chloride copolymer and coating additive is applied to at least the metal-treated base material. surface. The application of formulated polyvinylidene chloride copolymer solutions is well known in the art. can be conveniently carried out in a conventional coating column. Alternatively, however, limited A mixed solution of vinylidene chloride copolymer and coating additives is mixed without being chlorinated. It can also be applied by emulsion coating of the hnylidene copolymer solution onto the substrate.

According to the preferred method of application of a blended solution of vinylidene chloride copolymer, and an ethylenically unsaturated monomer, preferably MMA, in a solvent, e.g. Tetrahydrofuran (THE), toluene, methyl ethyl ketone, nonpolar solvent For example, 1.3-bromobrobane, bromobenzene, α-chloronaphthalene, 2-Methylnaphthalene, 0-dichlorohenzene, polar aprotic solvents such as te Tramethylene sulfoxide, N-methylvirolitone, tri(Asahi disulfide, Isoprobyl sulfoxide, N-acetylpyrrolitra, N,N-dimethylaceta or a mixture thereof. Preferably the solvent is at least 15% of THF, the balance being a mixture of toluene, most preferably 60-75% THF. F and 25-40% toluene. Next, this vinylidene chloride A formulated solution of the copolymer is air-dried in a laboratory-scale coating tower to coat at least the polymer substrate, Preferably polyester, most preferably polyethylene terephthalate metal carrier. Apply to the holding surface. The temperature at the inlet and outlet of the coating tower is 70°C to 1. A range of 30°C is possible. Preferably, the inlet temperature is 120°C and the outlet temperature is 120°C. The temperature is 80°C. Coated polyethylene terephthalate is less than 30 per minute and passes through the coating tower at a rate of 90 feet per minute, preferably 90 feet per minute.

The coated material obtained according to the invention is capable of changing itself through oxidation and changes in moisture content. Particularly suitable for use as food packaging material where defects arising from It has the property of In the following examples, the properties are described below. Measure by test.

Heat sealing strength is measured by the following method. 1 x 10 inch of coated metal treated substrate Cut out three samples of size H. These samples can be cut into granules or along the length of the sample. Cut along the machine direction of the film. These samples were coated metal treated substrates. Take from the east end, west end and central part of. Fold each sample in half in the machine direction. width Applying 0.75 inch sealing bars to carefully controlled temperature, pressure and Join both halves of the specimen with each end at right angles to the body under conditions of contact time. . Open the resulting three sets of strips with the free ends and tie them together. - (Suter) Place it in the tester and keep the bent end perpendicular to the pulling direction. Pull them apart. The maximum force required to pull apart the strips in Durham It is taken as a measure of heat sealing bond strength. Heat sealing strength is measured with the coated material as it is. I will The strength of the laminate bond is determined by bonding the laminate using an adhesive such as a two-layer adhesive system. The sample is laminated to a 2 mil thick polyethylene film and measured. Application The weight of the adhesive coating is typically 1-15 pounds dry solids per ream) ・It is. Heat pressure Nino Roll to 170-200'F, typically 215' Set the lamination temperature to F.

While manufacturing the laminate of the sample film to the polyethylene film, the bond strength 15 or more strips of release material to aid in initiation of laminate debonding during testing. Place the paper approximately 5 feet apart between the film sample and the polyethylene film. to give the laminate an unbonded area. Typically tests bond strength The laminate is previously cured at 25° C. for at least 7 days.

After the laminate has cured, reinforce both sides with polyimide adhesive tape from the outside. Prevent tearing of the test film. For each test, remove 5 I x 8 inch specimens. Cut with the direction parallel to the web direction. The specimens were blasted across the width of the web at various Collect from location. Laminate samples can be tested for bond strength “as is” or Alternatively, test after adjusting the moisture conditions.

Moisture condition adjustment can be performed in two ways. with an exposed non-binding starting region. The samples were conditioned for 1.3 or 7 days, respectively, at 40°C in a honey-sealed container. Arrange. Fill the bottom of each denocator with water.

The laminate bond strength is determined by the laminate (separated by release paper) ) were tested in a tensile tester to ensure constant shear peeling. Holding the tail of the material perpendicular to the direction of pull, pull it off to create a 1-inch width. The binding strength reported for one sample is It is typically the average of five film samples tested under two replicate conditions.

Without further elaboration, one skilled in the art can utilize the preceding description to fully understand the present invention. It is thought that it can be used within a certain range. Therefore, the following preferred specifics The specific examples are merely illustrative and may not be disclosed in any manner or manner. It should be considered that there is no limitation regarding the residual amount shown. In the example below Unless otherwise indicated, all temperatures refer to temperature and all parts and and percentages are parts and percentages by weight.

It has a weight percentage composition of 91.3 vinylidene chloride, 1 acrylonitrile, 8. Methyl methacrylate 6.9o copolymer 90.64%, talc 101%, wax A mixed solution of 8.12% of sugar and 0.23% of aromatic polyester resin was added to THF6. 5% and 35% toluene. Heat this mixture at 40°C to 45°C. Heat to °C until the polymer is dissolved. The solids content of the bath solution is 18%. Distribution The aromatic polyester resin used in the mixture solution was made of terephthalic acid his-(ethylene titanium glycol) ester, isophthalic acid, ambic acid and acelaic acid According to the method of U.S. Pat. No. 2,892,747 using a tetraisopropyl acid catalyst. Produced by transesterification 1/2 mil aluminized polyethylene that travels 90 feet per minute Both metallized and unmetallized surfaces of phthalate films Apply the formulated solution to. The mixed solution is placed in an immersion storage tank maintained at 40℃, and Doctor transferred to metal-treated polyethylene terephthalate using rolls The roll set point is 0003 inches.

The tower temperatures at the inlet and outlet of the coating tower are 120°C and 80°C, respectively. . The inlet and outlet tower air supplies are 250 and 300 cubic flf per minute, respectively. It's eat.

Coating weight is determined by the weight difference between coated and uncoated samples. The coated sample is heated Test the melt sealability and laminate bond strength both as is and after condition adjustment. . Conditioning can be done by applying tincator over a period of 24 hours, 72 hours or one week. Perform this on the sample inside. Fill the bottom of the desiccator with water. The results are shown in Table 1. It is.

Example 2 Performed except that the hnylidene chloride copolymer has the following weight percentage composition: Follow the procedure of Example 1: Heat melt 90.5 hnylidene chloride, 95 o methyl methacrylate The properties and laminate bond strengths are shown in Table 1.

Example 3 Performed except that the vinylidene chloride copolymer has the following weight percentage composition: Follow the procedure in Example 1 - Vinylidene chloride 909, methyl methacrylate 91° heat sealing The strength of the laminate bond is shown in Table 1.

Example 4 Performed except that the hnylidene chloride copolymer has the following weight percentage composition: Following the procedure of Example 1: hnylidene chloride 91.6, acrylonitrile 4.0, methacrylate The methyl lylate 44° heat sealability and lamination bond strength are shown in Table 1.

Comparative example 1 Performed except that the vinylidene chloride copolymer has the following weight percentage composition: Follow the procedure of Example 1 - Vinylidene chloride 921, acrylonitrile 5.5, methacrylate The 2.5° heat sealability and lamination bond strength of methyl phosphate are shown in Table 1.

Comparative example 2 Following the procedure of Comparative Example 1 except that the formulation solution did not contain coating additives. . The vinylidene chloride copolymer used has the following weight percentage composition: chloride Hinylidene 92.1, Acrylonitrile 5.5, Methyl methacrylate 2.5o heat The sealability and lamination bond strength are shown in Table 1.

Comparative example 3 The ratios are as follows, except that the vinylidene chloride copolymer has the following weight percentage composition: Follow the procedure of Comparative Example 2 Hynylidene chloride 905, methyl methacrylate 9.5° hot melt The sealing properties and laminate bond strength are shown in Table 1.

Month child Example 1 2.0 220 384 467' 31832 2.1 277 518 290' 63833 2.1 170 218 192' 37634 2 ．． 1 293 443 4+9' 4413 Comparative example A cured laminate sample was conditioned in a desiccator at 40°C for 24 hours. Desiqe Fill the bottom of the meter with water.

The cured laminate samples were conditioned for 72 hours at 40°C in a desiccator. den Fill the bottom of the caterer with water.

3. Cured laminate sample conditioned for 1 week at 40° C. in a desiccator.

Fill the bottom of the desiccator with water.

Table 1 shows the heat sealability and lamination bond strength and force (at least In vinyl chloride-1-nodene copolymer containing 4% or more of IMA, It is shown that there is a significant improvement according to the amount of methyl taacrylate. child The improvement occurs with the presence of coating additives.

From the foregoing description, one skilled in the art will be able to easily ascertain the essential features of the invention. and to adapt the invention to a variety of usage situations and conditions. Various modifications and improvements of the present invention may be made without departing from the spirit and scope of the invention. be able to.

Copy and translation of amendment) Submission (Article 184-8 of the Patent Law)

Claims (24)

[Claims] 1. providing a substrate material having at least one surface having metal thereon; At least the above surface is coated with at least 4% by weight of ethylenically unsaturated acrylic acid ester. coated with a compound solution of a vinylidene chloride copolymer with a polyester and a coating additive. Obtaining a product with improved barrier coating adhesion and hot seal strength A method of manufacturing a product having improved barrier coating adhesion and hot seal strength, comprising: Law. 2. Groups where the above base material is plastic, recycled cellulose, and paper A method according to claim 1, characterized in that the method is selected from: 3. The above plastics are polyester, polyolefin, polyamide, polysalt selected from the group consisting of vinyl esters, copolymers thereof and mixtures thereof. 3. The method according to claim 2, characterized in that: 4. Claim 3, characterized in that the above plastic is polyester. How to put it on. 5. The above polyester is characterized in that it is polyethylene terephthalate. The method according to claim 4. 6. A group in which the above metals are Fe, Cu, A1, Ti and alloys thereof The method according to claim 1, characterized in that the method is one selected from: 7. The method according to claim 6, characterized in that said metal is aluminum. . 8. The above vinylidene chloride copolymer has at least 80% vinylidene chloride. 8. The method according to claim 7, characterized in that: 9. The vinylidene chloride copolymer has at least 88% vinylidene chloride. 9. The method according to claim 8, characterized in that: 10. The above ethylenically unsaturated monomer is methyl methacrylate. The method according to claim 9. 11. The above coating solutions may be talc, aluminum silicate, wax or aromatic polyester. Coating additives selected from the group consisting of ester resins or mixtures thereof The method according to claim 9, characterized in that it contains. 12. The amount of the above-mentioned coating additive present is 10% of the above-mentioned polyvinylidene chloride copolymer. The method according to claim 1, characterized in that the amount is within % by weight. 13. a substrate material having at least one surface with metal thereon; and A blended solution of a vinylidene chloride copolymer and a coating additive on at least the above surface. Consisting of a coating of The above polyvinylidene chloride copolymer contains at least 4% by weight of ethylenically unsaturated atom. Metal retention with improved coating adhesion and heat sealability with acrylate ester material. 14. The above base materials are glues made of plastic, recycled cellulose, and paper. 14. A material according to claim 13, characterized in that it is selected from the group consisting of: 15. The above plastics are polyester, polyolefin, polyamide, polyester From the group consisting of vinylidene chloride, copolymers thereof and mixtures thereof 14. A material according to claim 13, characterized in that it is selected. 16. Claim 1 characterized in that the above plastic is polyester. Materials described in 5. 17. characterized in that the above polyester is polyethylene terephthalate 17. The material according to claim 16. 18. The above metals are Fe, Cu, Al, Ti and alloys thereof. 14. A material according to claim 13, characterized in that it is selected from the group consisting of: 19. Claim 18, wherein the metal is aluminum. material. 20. The above vinylidene chloride copolymer has at least 80% vinylidene chloride. The material according to claim 19, characterized in that: 21. The above vinylidene chloride copolymer has at least 88% vinylidene chloride. 21. The material according to claim 20. 22. The above ethylenically unsaturated monomer is methyl methacrylate. The material according to claim 21. 23. If the above coating solution is talc, wax, aromatic polyester resin or a coating additive selected from the group consisting of mixtures thereof; The material according to claim 13. 24. The above coating additive contains 10% by weight or more of the above polyvinylidene chloride copolymer. 14. A material according to claim 13, characterized in that it is present in a material.