JPH04197631A - Laminated matter of thermoplastic resin film - Google Patents

Abstract

PURPOSE:To obtain favorable adhesion to a hydrophillic and hydrophobic polymer and inorganic matter, by a method wherein radiation curing resin obtained by causing at least one kind of a chemical compound containing carboxyl group and/or sulfonic group to react is laminated on at least one surface of a thermoplastic resin film. CONSTITUTION:Radiation curing resin is of radiation curing resin containing COOM and/or SO3M group containing at least one piece of an acrylic double bond within a molecule. Polyurethane acrylate resin, polyester acrylate resin and various acrylate chemical compound are mentioned concretely. A chemical compound containing a specific carboxyl group and/or a sulfonic group can be caused to react through various processes. At the time of manufacturing of raw material resin, for example, polyester polyol, polyalkylene glycol and epoxy resin, the same can be used as its one component. With this construction, a film which has favorable adhesion to a hydrophillic polymer and hydrophobic polymer and is effective for packing and industry can be obtained.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a thermal ijJ plastic resin film with improved adhesion, the object of which is to provide good adhesion to hydrophilic and hydrophobic polymers and inorganic materials. An object of the present invention is to provide a thermoplastic resin film having the following properties.

(Prior art) As is well known, heat [+J plastic resin films, such as polyester, polyamide, polypropylene, polycarbonate polyetherimide, polyether sulfone, polyphenylene sulfide, polyether ether ketone, etc.]
In particular, polyester films, especially polyethylene terephthalate films, have excellent mechanical strength, heat resistance, chemical resistance,
Because of its excellent transparency and uniformity, it is used in a wide variety of applications, including base films for magnetic tapes, insulating tapes, photographic films, tracing film, and food packaging films. However, polyester film generally has low adhesion, so ink, electrophotographic toner, etc.
When laminating heat/heat property imparting compositions, magnetic substances, photosensitizers, matting agents, metals, metal oxides, inorganic polymers, etc., corona discharge treatment is applied to the film surface, and an anchor coating agent is applied to the film surface. It is common to have one. Furthermore, when used for packaging gold goods, the adhesiveness with the printed layer and the heat roll layer is weak, resulting in a disadvantage that the overall heat/roll strength is reduced. Corona discharge treatment is generally used as a method to improve the adhesion of thermoplastic resin film surfaces.In addition, physical treatments such as ultraviolet irradiation treatment, plasma discharge treatment, flame treatment, and corona discharge treatment in a nitrogen atmosphere are also used. Chemical treatment methods such as alkali treatment and brimer treatment, and a treatment method using a combination of these methods are known.

However, there are no PIIF plastic resin films, especially polyester films, which have good adhesion to hydrophilic and hydrophobic polymers and to minerals.

(Problems to be Solved by the Invention) The present inventors have solved the problems in the conventional techniques, namely, the difficulty in imparting good adhesion to both hydrophilic polymers, hydrophobic polymers, and inorganic materials. As a result of intensive research and efforts, we have completed the present invention.

(Means for Solving the Problems) At least one of the laminated resins is a radiation-curing type resin in which at least 11 sides of a thermoplastic resin film are reacted with one or more compounds containing a carboxyl group and/or a sulfone group. A thermal IIJ plastic resin film characterized by being laminated as components.

Polyester polyol (B) as C00M compound
Oxycarboxylic acids such as polycarboxylic acids, glycolic acid, glyceric acid, N,N-noethanolglycine, hydroquinoloxine benzoic acid, glycolic acid, glyceric acid, /ami/propionic acid, /ami7 Aminocarboxylic acids such as benzoic acid and their derivatives.

-803M compounds are polycarboxylic acids and derivatives such as 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium, sulfoisophthalic acid, sodium sulfosuccinic acid, sodium sulfohydroquinone and alkylene oxide adducts, sodium sulfobisphenol A and alkylene oxide. Addenda etc.

The radiation curable resin of the present invention has at least one acrylic double bond in the molecule, and has at least one acrylic double bond in the molecule, and
or S(1,M compound) is a C00M or/and SQ, M-based radiation-curable resin made by reacting at least one of the compounds shown in the compound and a compound containing a hydrophilic polar group other than an atom.

Specifically, resins that are bonded to the acrylic double bond-containing compound (A) through at least one bond among urethane bonds, ester bonds, ether bonds, and amide bonds, such as polyurethane acrylate resins and polyester acrylates. Examples include resins, epoxy acrylate resins, various acrylate compounds, and the like.

The acrylic double bond contained in the binder of the present invention refers to residues (acryloyl group or methacryloyl group) of acrylic acid, acrylic ester, acrylic amide, methacrylic acid, methacrylic ester, methacrylic amide, etc.

The specific carboxyl group- and/or sulfone group-containing compound listed in L can be reacted through various processes. For example, when manufacturing raw material resins such as polyester polyols, polyalkylene glycols, and epoxy resins,
It can be used as one component thereof. In particular, when producing polyester polyol, the above C00M1SO
A compound represented by a 3M compound can be added and reacted at any stage before the completion of polymerization of the polyester polyol. From the point of view of operation 1- during production, it is preferable to add it after the transesterification reaction or after the esterification reaction.

Moreover, these specific compounds can be used as one of the raw materials for radiation-curable resins such as polyurethane acrylate resins, polyester acrylate resins, epoxy acrylate resins, and acrylate compounds. For example, a compound containing a hydroxyl group can be directly reacted with an iso/anate compound, a polyester polyol, or an acrylate compound to produce a polyurethane acrylate resin.

Furthermore, among the specific compounds of the present invention, diols may be used as chain extenders for polyurethane acrylate resins, dicarboxylic acids may be used as chain extenders for epoxy acrylate resins, and diols and dicarboxylic acids may be used as chain extenders for polyester acrylate resins. . Among these specific compounds, diol mono(meth)acrylate is used as a chain extender for polyurethane acrylate resin, and carboxylic acid monoethyl oxy/(meth)acrylate is used as a terminal stopper for Evoquin acrylate resin. Good too. Furthermore, a specific compound poly(meth)acrylate may be used as the acrylic compound.

The radiation-curable resin of the present invention is produced by mixing an acrylic di- or double-bond-containing compound and a raw material containing a specific compound and/or a raw material resin reacted with a specific compound in a solvent or without a solvent. It can be obtained by reacting with The molecular weight of the resulting resin is 500 to 100,000.
It is desirable that

It is appropriate to use the above-mentioned C00M or/and SO3M compound in a proportion of 0.5 to 30 mol% as a compound in the resin. On the other hand, if it exceeds the above range, it will result in an increase in hygroscopicity, a decrease in physical properties, and a decrease in adhesion to the thermoplastic resin film τ, making it less practical.

The laminated film of the present invention can be further improved in adhesion by performing corona discharge treatment in air or nitrogen atmosphere, ultraviolet irradiation treatment, etc. before and after lamination. I can do it.

The laminated film produced by the method described in 1- is used as an information recording film, a packaging film, an electrical film, and other films.

In particular, polyester films are used for other purposes such as magnetic recording base films, printing base films, capacitor base films, packaging films for foods, etc., and vapor deposition base films.

Furthermore, when used in these films, the radiation-curable resin layer contains colorants, antistatic agents, crosslinking agents, anti-blocking agents, lubricants such as inorganic or organic particles, ultraviolet absorbers, deterioration inhibitors, and other substances. It may be added to an extent that does not impair the effects of the present invention.

Coloring agents include water-soluble, organic solvent-soluble and oil-soluble dyes, pigments and insoluble dyes and pigments.

Antistatic agents include anionic, nonionic, and cationic surfactants, polyether groups, self-polymers with anionic and cationic groups, and conductive particles made of metals or metal oxides.Crosslinking agents include: Acroyl group, alkical group, iso7anato group, epoquine group, azilkyl group, (meth)acroyl group, alfkyl/alkyl group, etc., and a reactive group that can react with active hydrogen on two sides 1. Includes compounds that contain.

Anti-blocking agents include higher fatty acids and their salts, ester amides, amines, mineral oil, licorice, and fluorine compounds.Lubricants such as inorganic or organic particles include glue-based, calcium carbonate-based, kaolin-based, and barium sulfate-based. ,
Includes titanium-based, talc-based, bersoguanamine, polyolefin-based, melamine-based, polyacrylic ester-based, polyamide-based, polyether-based, polycarbonate-based, etc.

These may be surface-treated, and the particle size may be arbitrarily selected depending on the intended use.

Ultraviolet absorbers include benzophenone, saliflic acid ester, triazole, and others.

Deterioration inhibitors include phenolic, epoxy, sulfur-containing, phosphorus-containing, nitrogen-containing, metal-containing, conjugated bond-containing, and the like.

Contains anti-mosquito agents, flame retardants, and other substances.

In particular, when an organic titanate or an autosilane compound is included, the film strength and adhesion are improved.

Examples of resins that are compatible with the resin of the present invention include vinyl chloride resins, polyester resins, cellulose resins,
Examples include acrylic resin, epoxy resin, phenoxy resin, polyvinyl butyral, acrylonitrile-butadiene octapolymer, and the like.

However, depending on the purpose, resins other than "-2" may be used in combination. ' Other resins may be laminated or anchored onto the radiation-curable resin side of the laminated film before use for the above-mentioned purposes.

Methods for laminating a radiation-curable resin copolymerized with the compound of formula CI) on a base film include coextrusion coating, extrusion lamination, coating, dry lamination, and hot melt adhesion. It can also be laminated using the following method. Of course, it is clear that stretching or heat treatment may be performed before or after lamination.

The thickness of the lamination is arbitrary, but is not limited, although it is preferable for the external adhesive tj to be as thin as possible.

After lamination on a thermoplastic resin film according to a conventional method, the laminate is calendered if necessary and then subjected to radiation treatment. Calendar treatment can also be performed after radiation treatment. In particular, as the radiation to be irradiated, in addition to electron beams, ionizing radiation such as neutron beams and gamma rays can be used, and the irradiation dose is preferably about 1 to 10 Mrad, particularly about 2 to 8 Mrad.
It is preferable that it is ad.

(Function) In the present invention, by using a radiation-curable resin reacted with a compound containing a carboxyl group and/or a sulfonic acid group as at least one component of the laminated resin, it is possible to cure both hydrophilic polymers, hydrophobic polymers, and inorganic substances. It can provide good adhesion.

(Example) Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 In an autoclave equipped with a thermometer and a stirrer, 485 parts of dimethyl terephthalate and 4 parts of methyl isophthalate were added.
85 parts, 409 parts of ethylene glycol, 485 parts of neopentyl glycol, and 0.85 parts of tetrabutoxy titanate.
68 parts were charged and heated at 150 to 230°C for 120 minutes to perform transesterification, then 50.1 parts of sodium 5-sulfoisophthalate was charged, and 1 part was heated at 220 to 230°C to a river.
A time reaction was performed. The reaction system was then heated to 250°C for 30 minutes.
The pressure of the system was gradually reduced to 10 mm after 45 minutes.
The reaction was continued under these conditions for an additional 60 minutes. The amount of the obtained polyester film was 2,500.

After dissolving 72 parts of toluene, 772 parts of methyl ethyl ketone, and 100 parts of polyester diol A in a solution, 21 parts of 4,4'-diphenylmethane diiso7anate and 0.05 parts of butyltin laurate were added, and the mixture was reacted at 70 to 80°C for 3 hours. Ta.

Furthermore, 15 parts of pentaerythritol triacrylate was added, and the reaction was carried out at 70 to 80°C for 2 hours, and further 7.1 parts of 2-methyl-2dimethylamino-1,3-propanediol was added.
20% by weight and further reacted for 5 hours until the solid content concentration was 40% by weight.
A polyurethane acrylate resin solution was obtained. The molecular weight of polyurethane acrylate resin A was 15,000.

Further, a coated polyester film of 0.3 g/I/ was diluted with a mixed solution of toluene/methyl ethyl ketone (50150) to give a solid content concentration of 5% by weight, applied to a polyester film using an air knife method, and dried at 120°C. , 5 Mrad radiation treatment was performed.

The adhesive properties of HoIJmer are ■Polyvinyl alcohol, ■Polycarbonate, ■Alcohol tiJ-soluble nylon, ■
Gelatin, ■Cellulose acetate butyrate with a red dye that is highly compatible, was applied to a thickness of 3 μm.Nichino Co., Ltd. sellotape was applied and peeled off at a peeling angle of 180°. . Those with no peeling at all were ranked as 5, those with half of 1O1 peeled off, and those with all peeled off as 1.

The adhesion of metals was tested by immersing these films with aluminum vapor-deposited at 100°C for 30 minutes, taking them out, pressing the tape shown on the vapor-deposited surface, and rapidly peeling off the film 10 times. I gave a similar evaluation.

The adhesiveness of the magnetic agent is γ-Fe20:I differential powder-r250
part, 2 parts of dioctyl sulfonate, copolymerized polyester (terephthal 1!45 mol%, isophthalic acid 20 mol%
, Sepa 77M 32.5 mol%, pentasodium sulfoisophthalic acid 2.5 mol%, ethylene glycol 50 mol%
, 48 parts of neopentyl glycol (50 mol%) and 00 parts of cellotrub acetate were mixed using a ball mill to about 2
Mixed for 4 hours. Copolymerized polyester 4! to 400 parts of this mixture! 100 parts of fat, 30 parts of nitrocellulose, 70 parts of vinyl chloride-vinyl acetate copolymer, 30 parts of voriison anate, 400 parts of methyl ethyl ketone, and 400 parts of nclohexane were added and mixed again using a ball mill for about 70 hours. The film described in 1-1 was coated to a layer thickness of 2 μm.

Further, an adhesive tape was attached to the surface of the 100 cross-captured magnetic layer, and after uniformly adhering to the entire surface, the state was observed when it was instantly peeled off five times. The numerical value indicates the remaining number.

Comparative Example 1 'In Example 1, 35 mol% of terephthalic acid was used as the acid component in the polyester copolymer composition in the radiation-curable resin.
Same as Example 1 except that 35 mol% of isophthalic acid, 30 mol% of ampic acid, 50 mol% of ethylene glycol and 50 mol% of neopentyl glycol as glycol components were dissolved in toluene/methyl ethyl ketone (50 vt%, 150 vt%). A coated polyester film was obtained.

Comparative example 2 An uncoated/uncoated polyester film was provided.

Table 1 It can be seen that the present invention has better adhesiveness than the comparative example.

Example 2 Acid components include 70 mol% of terephthalic acid, 25 mol% of isophthalic acid, 5 mol% of adipine acid, and glycol components include 70 mol% of ethylene glycol, 26 mol% of glycol, and 4 mol of noaminopropionic acid. A radiation-curable resin solution was prepared in the same manner as in Example 1, and the solvent was distilled off in a mold to obtain particles of the resin.

300 parts of the above polymer and 140 parts of 11-butylcellonorb
part and stirred in a container at 150-170°C for about 3 hours,
A homogeneous and viscous melt was obtained, and 560 parts of water was gradually added to this melt, and after about 1 hour, a uniform pale white aqueous dispersion having a solid content concentration of 30% was obtained.

The solution was diluted by adding 4,500 parts of water and 4,500 parts of ethyl alcohol to obtain a coating solution with a solid content concentration of 3%.

This coating solution was applied to an unstretched polyester film to a solid content thickness of 1 g/tn',
It was stretched 3.5 times at 120°C, and then stretched 3.5 times in the transverse direction at 120°C.
Stretched 4 times, heat treated at 210℃, coat thickness O, 1g
/m' base layer 50μ polyester film 5M
rad radiation treatment was performed.

Next, screen printed A-1 Kyua KK Red (manufactured by Nagase Screen Co., Ltd.) to a printing thickness of 10 to 511 cm, and used a UV irradiation device with an integrated irradiation energy of 1500 aJ.
Irradiation was completed at /c+1t.

When Govant 1 of 100 grams was applied to this printed surface and a cellophane tape peeling test was performed, no peeling occurred.

(Effects of the Invention) It can be seen that the film of the present invention has good adhesive properties with hydrophilic polymers and hydrophobic polymers, and is useful for packaging and industrial purposes.

Claims (1)

[Claims] 1) A thermoplastic resin film laminate in which a radiation-curable resin made by reacting one or more carboxyl group- and/or sulfone group-containing compounds on at least one side of a thermoplastic resin film is laminated as at least one component of the laminate resin. .