JP2009235388A - Composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition laminated by sensing pressure or heat, after dried, capable of bonding a film to metal by curing the composition, and free from the risk of corrosion of the metal. <P>SOLUTION: This composition uses a monofunctional (metha)acrylate having a phenoxy group at its terminal, a polymer such as a vinyl butyral resin, acrylic resin, polyester resin, polyester polyurethane resin, polyamide resin and epoxy resin, and a solvent, and is laminated after dried up the solvent, to be cured by radiation. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a composition for laminating a film and a metal foil.

  Conventionally, as an adhesive used for laminated composite films such as various plastic films and metal foils, a so-called polyurethane adhesive mainly using an organic polyisocyanate compound having an isocyanate group alone or in combination with an organic polyol compound having a hydroxyl group. Is used. This polyurethane adhesive is extremely excellent as it can satisfy various functions required after bonding as a laminating adhesive, but it takes a long time for the curing reaction and is inferior in productivity. It is. On the other hand, although the curability is excellent, there are many that require equipment such as an electron beam and those that do not have a degree of freedom in resin design, and none that satisfy the required functions at the time of use.

  A polyester resin (A), a polyisocyanate, and a polyurethane resin having a hydrophilic group and having a hydroxyl group at the end, obtained by reacting a compound having a functional group capable of reacting with an isocyanate group and a hydrophilic group, were emulsified. A dry laminate adhesive composition for a metal film mainly comprising an aqueous polyurethane resin, wherein the polyurethane resin has an acid value of 3 to 15 mg KOH / g, and the polyester polyol (A) is a polycarboxylic acid. A dry laminate adhesive for metal films comprising a condensation structure of an acid and a polyol, and wherein the polycarboxylic acid comprises an aromatic polycarboxylic acid of more than 60% by weight and not more than 80% by weight based on the whole polycarboxylic acid The composition exhibits excellent adhesion and coating appearance to metal films and various films. , It is disclosed that further comprises a retort resistance. (Patent Document 1)

  A laminated adhesive body of a plurality of films, wherein at least two adjacent films have a prepolymer of at least 50% by weight having one or two radical polymerizable unsaturated bonds in the molecule, polyurethane resin 1 A laminate film characterized by being bonded by an electron beam irradiation cured product of an adhesive composition consisting of 45% by weight is disclosed. (Patent Document 2)

  A resin composition comprising a polyurethane resin having a radically polymerizable unsaturated group, a reactive diluent and a rosin having a (meth) acryloyl group, wherein the polyurethane resin is a dimer acid and / or a dimer acid derivative as a polymerization component And the polyurethane resin is a polyurethane resin obtained by reacting an organic polyol compound, an organic polyisocyanate compound and a (meth) acrylate having a hydroxyl group. An agent composition is disclosed. (Patent Document 3)

  (A) 10 to 90 parts by weight of a compound having an alicyclic epoxy group in the molecule, (B) a copolymer of a glycidyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer, 90 to 10 parts by weight of a copolymer having at least one glycidyl group and a glass transition temperature of 30 ° C. or higher, and (C) 0.01 to 20 parts by weight of a cationic polymerization initiator that generates cations by ultraviolet irradiation. It is disclosed that the ultraviolet curable adhesive composition characterized by containing a metal is excellent in adhesion between metal and plastic. (Patent Document 4)

However, adhesives made from polymer components derived from dimer acid are concerned about corrosion of metal materials due to acid, and in adhesives using cationic polymerization initiators, cations remain even after curing, resulting in corrosion of metal materials and electrical properties. The problem is concerned.
JP 2005-290285 A JP-A-56-159266 JP-A-10-36809 Japanese Patent Laid-Open No. 2004-210802 JP 2000-63767 A JP 2002-328470 A JP-A-10-293399

  The problem to be solved is to provide a composition which can be laminated by pressure or heat after drying, adheres the film to the metal by curing the composition, and does not cause the corrosion of the metal.

  The invention of claim 1 is a composition having pressure sensitivity or heat sensitivity after drying, comprising a monomer, a polymer, and a solvent, and being bonded by curing of the monomer after drying. The body is a composition that is a monofunctional (meth) acrylate having a phenoxy group at its terminal, and can be laminated with heat or pressure sensitivity. There is no damage due to corrosion, and adhesion is obtained.

  The invention according to claim 2 is the composition according to claim 1, characterized in that the adhesion is an adhesion between a metal and a film, is free from electrolytic corrosion and corrosion, withstands a metal etching process, and has high reliability. Can be used for bonding laminates.

  The invention according to claim 3 is the composition according to any one of claims 1 to 2, wherein the curing is by ultraviolet rays, the adhesive curing process is completed in a short time, and the in-process installation equipment is also provided. Smaller than electron beam curing and no film degradation.

  The invention according to claim 4 is characterized in that the polymer is any one of vinyl butyral resin, acrylic resin, polyester resin, polyester polyurethane resin, polyamide resin, and epoxy resin. It is a composition, and after drying, pressure sensitivity and heat sensitivity at the time of lamination can be obtained, and a cohesive force in the process leading to curing can be obtained.

  A fifth aspect of the present invention is the composition according to any one of the first to fourth aspects, wherein the polymer has an unsaturated group, and a higher adhesive force is obtained.

  With the composition of the present invention, laminating can be performed without imperfection by applying pressure or heating, the adhesive strength after curing is sufficient, there is no risk of metal corrosion in the laminate of film and metal, it can withstand etching processes, etc. The physical properties are also good.

  The composition of the present invention contains a polymer and a solvent, and is formed by evaporating and drying the solvent. By laminating the film, there is no air entrainment when laminating the solvent-free resin, and the defoaming or coating process of the resin. It has the feature that there is no load such as requiring equipment such as decompression laminating. The laminate after film formation is a pressure-sensitive laminate at room temperature or the coating film is heated at the time of lamination, and the heat-sensitive laminate is selected according to the subsequent curing process, and the phase of the polymer type, molecular weight, glass transition point, and monomer are selected. It is selected appropriately depending on the solubility and ratio, and the equipment used. These selections can adopt a generally known pressure-sensitive and heat-sensitive design method.

The monofunctional (meth) acrylate having a phenoxy group at the terminal used in the present invention is mainly ethoxylated phenyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxydiethylene glycol acrylate, phenoxyethyl acrylate, phenoxyhexaethylene glycol acrylate, phenoxytetraethylene. Glycol acrylate can be used. You may use these individually or in mixture of 2 or more types. In the composition, the monofunctional (meth) acrylate having a phenoxy group at the terminal can be blended in an amount of 10 to 90% by weight, particularly preferably 30 to 60% by weight, based on the solid content. In this range, the characteristics during lamination can be maintained without deteriorating physical properties.

  After preparing a laminate with a monofunctional (meth) acrylate having a phenoxy group at its end, particularly when etching a metal with an acid such as a ferric chloride solution, 2-hydroxy-3-phenoxypropyl acrylate, Phenoxyethyl acrylate is preferable in terms of less yellowing, and 2-hydroxy-3-phenoxypropyl acrylate is more preferable.

  A polymer is used in order to obtain a film forming property after drying and a cohesive force that prevents a shift to the next step after lamination. Examples of the polymer include vinyl butyral resin, acrylic resin, polyester resin, polyester polyurethane resin, polyurethane resin, polyamide resin, and epoxy resin. Depending on the resin type, degree of polymerization, etc., 3 to 50% by weight in the solid content can be blended. It is particularly preferable that 5 to 40% by weight is blended. If it is in this range, it contributes to the improvement of laminate properties, compatibility with the monofunctional (meth) acrylate having a phenoxy group at the end is no problem, and the viscosity does not increase too much and the workability is not significantly reduced. The performance is also good.

  Moreover, the adhesive force of the composition obtained can be improved by using the polymer which has an unsaturated group. The reason for this is not clear, but it is assumed that the monomer and polymer are copolymerized at the time of curing, the polymer is crosslinked, or the action of both. As a method for producing a polymer having an unsaturated group, if the polymer is produced by a method other than addition polymerization, a monomer having an unsaturated group may be used as a monomer for producing the polymer. That's fine. If the polymer is produced by addition polymerization, an unsaturated group may be introduced after the polymerization. Specifically, an unsaturated group can be introduced into a polymer by reacting a polyvalent isocyanate compound with a compound having an active hydrogen group and an unsaturated group, and reacting it with a polymer having an active hydrogen group. Examples of the compound having an active hydrogen group and an unsaturated group include 2-hydroxyethyl acrylate (2-HEA) and 2-hydroxyethyl methacrylate (2-HEMA). The method is not limited to the above method, and any method may be adopted as long as it can introduce an unsaturated group into the polymer.

  Furthermore, acrylic oligomers, polyester acrylates, epoxy acrylates, and urethane acrylates can be blended for the purpose of imparting flexibility and improving chemical resistance, if necessary.

  In addition to the above, a reactive diluent can be used to adjust the viscosity of the adhesive composition and allow the polymerization to proceed rapidly. Examples include monofunctional compounds such as methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate And polyfunctional compounds such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. You may use these individually or in mixture of 2 or more types. The upper limit is 70% by weight in the solid content, so that the characteristics of the composition of the present invention are not impaired.

  The composition of the present invention can be used depending on the type of curing radiation. If there is equipment, an electron beam can be used. In this case, it is not necessary to add an initiator, the penetration depth is large, and the curing can be performed most rapidly. Next, ultraviolet rays can be used for those that are high-speed, have little equipment burden, and do not need to consider the life of the resin. In the case of curing by heat alone, on the contrary, the equipment becomes large, but by using ultraviolet curing together with heat curing or anaerobic curing, the laminating process speed can be increased. The heat curing can be carried out by using a radical polymerization initiator, the anaerobic curing using a methacrylic monomer as the monomer, and a combination of an organic peroxide and a curing accelerator.

  Any solvent can be used as long as it can dissolve the polymer, is compatible with the monomer, and matches the ability of the drying process. Examples thereof include ethyl acetate, methyl ethyl ketone, isopropyl alcohol, toluene and the like, and those having a boiling point of 140 ° C. or less are preferable from the viewpoint of drying conditions. It dilutes so that it may become a solid content ratio of 20 to 50 weight% by the kind of coating machine and coating precision.

  In the case of laminating with an inorganic surface such as a metal foil or a metallized film, the following additives may be added as necessary for the purpose of improving adhesion. Examples of these additives include phosphorus compounds having a (meth) acryloyl group such as mono (2- (meth) acryloyloxyethyl) acid phosphate and mono (3-chloro-2- (meth) acryloyloxypropyl) acid phosphate. Phosphorus compounds such as orthophosphoric acid, polyphosphoric acid, monoethyl phosphite, tripropyl phosphite; titanium compounds having a (meth) acryloyl group such as isopropyl dimethacrylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, and isopropyl triisostearoyl Titanium compounds such as titanate; aluminum compounds such as acetoalkoxyaluminum diisopropylate; chlorosilanes such as vinyltrichlorosilane; n- (dimethoxymethylsilylpropyl) Amino silanes such as range amine, n- (triethoxysilylpropyl) ethylenediamine, γ-aminopropyltrimethoxysilane; epoxy silanes such as γ-glycidoxypropyltrimethoxysilane; silane couplings such as vinylsilane such as vinyltriethoxysilane These may be used alone or in combination, if necessary.

  Of these, phosphoric acid esters and titanic acid esters having a (meth) acryloyl group are particularly preferable in that they themselves contribute to curing and give excellent adhesion to metals. A ring agent having excellent adhesion to a metal is obtained and is particularly preferable.

  The amount of these additives used is about 0.01 to 2% by weight with respect to the solid content of the composition, and a sufficient effect is obtained.

  Fillers, softeners, anti-aging agents, stabilizers, radical polymerization inhibitors, adhesion promoters, leveling agents, antifoaming agents, adhesion improvers, plasticizers, inorganic fillers, tackifying resins, fibers, pigments and dyes Antioxidants and ultraviolet absorbers can be used as necessary for the purpose of improving the light resistance.

  In case of UV curing, 1-hydroxycyclohexyl phenyl ketone, 2,2′-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone are used as photoinitiators. 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6- Dimethoxybenzoyl) -2,4,4′-trimethylpentylphosphine oxide and the like can be used. Commercially available light initiator Darocure1116, Darocure1173, IRGACURE127, IRGACURE184, IRGACURE369, IRGACURE500, IRGACURE651, IRGACURE754, IRGACURE819, IRGACURE907, IRGACURE1300, IRGACURE1800, IRGACURE1870, IRGACURE2959, IRGACURE4265, IRGACURE TPO (more than Ciba Specialty Chemicals Inc., trade name ), Etc. can be used.

Examples of the laminate base material include plastic films such as polyester films and polycarbonate films; metal foils such as aluminum foil and copper foil, inorganic vapor deposition films such as aluminum vapor deposition films and silica vapor deposition films instead of metal foils, etc. There is. Above all, this composition provides excellent adhesion to polyester film and aluminum foil, and polyester film and copper foil. In addition, it is preferable that any one of the laminate base materials has a total light transmittance of 80% or more in a range of 350 to 400 nm.

  The composition of the present invention can be applied by a coating method such as roll coating, spray coating, brush coating, bar coating, gravure roll coating, roller coating or silk screen printing.

  Although the film thickness of an adhesive agent is determined by the specification of lamination | stacking, the film thickness 1-30 micrometers at the time of drying is preferable.

  As an example of curing, when ultraviolet rays are used, examples of the irradiation source include a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, and sunlight. A metal halide lamp is preferable among them, depending on the total light transmittance of the substrate on the irradiation side.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and demonstrated in detail about this invention, a specific example is shown and it does not specifically limit to these.

Example 1
R-128 (Nippon Kayaku Co., Ltd., trade name, 2-hydroxy-3-phenoxypropyl acrylate, solid content 100%) 60 parts by weight, TPGDA (Daicel Cytec Co., Ltd., trade name, tripropylene glycol diacrylate solid) 100%) 176.9 parts by weight, BM-2 (Sekisui Chemical Co., Ltd., trade name, vinyl butyral resin solid content 100%) 50 parts by weight, CD-9050 (Sartomer Japan, Inc., trade name) , Monofunctional phosphoric acid methacrylic ester, solid content 100%) 0.3 parts by weight, KBM-503 (Shin-Etsu Chemical Co., Ltd., trade name, silane coupling agent solid content 100%) 0.3 parts by weight, start 12.5 parts by weight of Irgacure 907 (Ciba Specialty Chemical Co., Ltd., photoinitiator) was added as an agent, and ethyl acetate was used as a solvent Give the solid content of 30% of the composition, and the composition of Example 1.

Example 2
The composition of Example 2 was obtained in the same manner as in Example 1 except that R-128 was changed to 150 parts by weight and TPGDA 83.15 parts by weight.

Example 3
The composition of Example 3 was obtained in the same manner as in Example 1 except that R-128 was changed to 270 parts by weight, BM-2 was changed to 15.65 parts by weight, and Irgacure 907 was changed to 13.75 parts by weight.

Example 4
BM-2 of Example 2 was added to 166.7 parts by weight of TPAE31 (Fuji Kasei Kogyo Co., Ltd., trade name, polyamide resin solid content 100%), ethyl acetate, ethyl acetate, toluene, isopropyl alcohol (mixing ratio 1: 2: 2) The composition of Example 4 was obtained in the same manner as in Example 2 except that the mixed solvent was used.

Example 5
TPAE31 of Example 4 was changed to 50 parts by weight of Hyperl M-6003 (Negami Kogyo Co., Ltd., trade name, acrylic resin solid content 100%), and the solvent was changed to a mixed solvent of ethyl acetate and toluene (mixing ratio 1: 2). The composition of Example 5 was obtained in the same manner as in Example 4.

Example 6
Hyperl M-6003 of Example 5 in Byron 240 (Toyobo Co., Ltd., trade name, polyester resin solid content 100%), solvent in ethyl acetate, toluene, methyl ethyl ketone (mixing ratio 1: 2: 2) mixed solvent The composition of Example 6 was obtained in the same manner as in Example 5 except that the composition was changed.

Example 7
BM-2 of Example 2 was added to Byron UR-1400 (Toyobo Co., Ltd., trade name, polyester polyurethane resin solid content 30%) 50 parts by weight, and the solvent was ethyl acetate, toluene, methyl ethyl ketone (mixing ratio 1: 2: 2) The composition of Example 7 was obtained in the same manner as in Example 2 except that the mixed solvent was used.

Example 8
The composition of Example 8 was performed in the same manner as Example 7 except that Byron UR-1400 of Example 7 was changed to jER1001 (Japan Epoxy Resin Co., Ltd., trade name, epoxy resin solid content 100%), and the solvent was changed to ethyl acetate. It was a thing.

Example 9
The composition of Example 9 was obtained in the same manner as in Example 2 except that CD-9050 and KBM-503 of Example 2 were not added.

Example 10
In the reaction apparatus substituted with nitrogen in the system, 5.2 parts by weight of Coronate HX (trade name, trimer of hexamethylene diisocyanate, manufactured by Nippon Polyurethane Industry Co., Ltd.), 2.2 parts by weight of 2-HEMA, SCAT -1 (manufactured by Sansha Kogyo Co., Ltd., trade name, butyltin compound) was added in an amount of 0.0015 parts by weight, and 498.9 parts by weight of methyl ethyl ketone as a solvent was added and heated to 60 ° C. for 1 hour. Thereafter, 137.4 parts by weight of AP-060 (manufactured by Ganz Kasei Co., Ltd., trade name, carboxyl group-containing acrylic polymer) was added, and the mixture was further reacted at 60 ° C. for 1 hour. After cooling to room temperature, 56.0 parts by weight of R-128, 6.0 parts by weight of CD9050, 2.0 parts by weight of KBM503, 7.0 parts by weight of Irgacure 819 were added, and the solid content was 30%. It was set as the composition of this.

Example 11
In Example 10, the addition amount of coronate HX was 5.4 parts by weight, and 2.0 parts by weight of 2-HEA was added instead of 2-HEMA. The composition of Example 11 was obtained.

Comparative Example 1
The same procedure as in Example 1 was conducted except that R-128 of Example 1 was changed to 30 parts by weight of IBXA (Osaka Organic Chemical Co., Ltd., trade name, isobonyl acrylate solid content: 100%), and TPGDA was changed to 206.9 parts by weight. The composition of Comparative Example 1 was obtained.

Comparative Example 2
A composition of Comparative Example 2 was prepared in the same manner as in Example 1 except that 284.4 parts by weight of R-128 of Example 1, TPGDA was not added, BM-2 was not added, and Irgacure 907 was 15 parts by weight.

Comparative Example 3
A composition of Comparative Example 3 was prepared in the same manner as in Example 1 except that R-128 of Example 1 was changed to 150 parts by weight, TPGDA was changed to 133.15 parts by weight, and BM-2 was changed to no blending.

Comparative Example 4
The composition of Comparative Example 4 was the same as Example 1 except that R-128 of Example 1 was changed to 84.9 parts by weight of IBXA, TPGDA was not added, BM2 was changed to 210 parts by weight, and Irgacure 907 was changed to 4.5 parts by weight. It was.

  In the table, the monomer type is a monofunctional (meth) acrylate having a phenoxy group at the terminal, and the other is x. The presence / absence of the polymer was evaluated as “◯” when the polymer was contained, and “X” when the polymer was not contained. The presence / absence of the additive was indicated as ◯ when CD-9050 and KBM-503 were added, and × when no additive was added.

The compositions obtained in Examples 1 to 11 and Comparative Examples 1 to 4 were applied to My foil (Sumi Light Aluminum Foil Co., Ltd., trade name, 25 μm thick aluminum foil, purity 99.7%) with a bar coater, It was dried at 80 ° C. for 30 seconds, A4300 (Toyobo Co., Ltd., trade name, polyester film, 100 μm thick, easy-adhesive product) was laminated on the adhesive, and UV irradiation machine LH6 (Fusion UV System Japan Co., Ltd.) ), A valve name electrodeless D valve), and ultraviolet treatment of 800 mJ / m ² (peak illuminance 800 mW / cm ^{2 in the} UV-A region) with MicroCure manufactured by EIT Co., Ltd. is performed, and an adhesive layer of 5 μm is laminated. Got the body.

Test / Evaluation Method Peel Strength: Universal Material Testing Machine Type 5582 (Instron) under the environmental conditions of temperature 23 ° C. and humidity 50% RH based on 180 degree peel adhesion strength test method based on JIS K6854-2 (1999 edition) In Japan, a sample having a width of 15 mm was pulled in a 180 ° direction at a speed of 200 mm / min, and the peel strength (N / 15 mm) was measured.

Holding force when uncured: In order to evaluate retention of the laminated state before lamination after lamination, the compositions of Examples and Comparative Examples were applied to A4300 so as to be 10 μm when dried, and then dried at 80 ° C. for 30 seconds at room temperature. Then, a test piece having a bonding area of 100 mm × 10 mm is prepared, and the weight is divided by the bonding area so that a weight is hung from the lower part so that shear stress is applied in the longitudinal direction of the bonding surface and does not fall for 30 seconds. The per weight (g / mm ² ) was measured. (See Figure 1)
When the composition of Claims 1-11 is used, it turns out that both peeling strength and uncured retention strength are favorable, and it has excellent adhesive performance. In particular, Examples 10 and 11 using a polymer having an unsaturated group have higher adhesion performance. On the other hand, in each comparative example not containing a monofunctional (meth) acrylate having a phenoxy group at the terminal or a polymer, sufficient adhesive strength is not shown.

  The composition of the present invention contains a monofunctional (meth) acrylate having a phenoxy group-terminated terminal, so that an adhesive force after curing is obtained. It is expressed and can be applied to the use of radiation curing after laminating metal and radiation transmitting material.

Illustration of holding force when uncured Right cross section

1 Load direction 2 Adhesive layer 3 Polyester film

Claims (5)

  A composition having pressure sensitivity or heat sensitivity after drying, comprising a monomer, a polymer, and a solvent, and adhering by curing of the monomer after drying, the monomer having a phenoxy group as a terminal A composition having a monofunctional (meth) acrylate. 2. The composition according to claim 1, wherein the adhesion is an adhesion between a metal and a film. The composition according to claim 1, wherein the curing is by ultraviolet rays. The composition according to any one of claims 1 to 3, wherein the polymer is any one of vinyl butyral resin, acrylic resin, polyester resin, polyester polyurethane resin, polyamide resin, and epoxy resin. The composition according to any one of claims 1 to 4, wherein the polymer has an unsaturated group.

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