JP2014237813A - Coating agent for cyclic polyolefin material, and laminate body - Google Patents

Abstract

A water-based coating agent capable of forming a coating film having good adhesion to the surface of a cyclic polyolefin material without special treatment and good chemical resistance, and lamination using the same To provide a body. An acid-modified polyolefin resin containing a (meth) acrylic acid ester component, a coating agent for a cyclic polyolefin material containing a basic compound and an aqueous medium, and the cyclic polyolefin material for at least one side of the cyclic polyolefin material. A laminate provided with a coating film obtained by removing an aqueous medium from a coating agent. [Selection figure] None

Description

  The present invention relates to an aqueous coating agent that can be suitably used for a cyclic polyolefin material, and a laminate produced by applying the coating agent to the surface of the material.

  Polyolefin materials represented by polyethylene and polypropylene have a good balance of physical properties such as mechanical properties and electrical properties, and are inexpensive, so they are widely used in various fields such as electricity, electronics, automobiles and packaging, and in large quantities. It is used. However, since polyolefin has low surface free energy, there are difficulties in wettability and adhesiveness. Among these, cyclic polyolefin materials are known as materials that are difficult to bond. Therefore, adhesives and coating agents specialized for cyclic polyolefin materials have been developed, and the surface of the material is also subjected to corona treatment and plasma treatment. For example, Patent Document 1 describes performing plasma treatment on the surface of a cyclic polyolefin material or the surface of a material to be bonded. However, in order to perform plasma treatment, it is necessary to introduce a special apparatus, and a method for adhering to an untreated cyclic polyolefin material with good adhesiveness has not been proposed.

  Also, since polyolefin materials are easy to repel water, conventional adhesives were mainly solvent-based, but in recent years, volatile organic solvents, especially aromatics such as toluene, are used from the viewpoint of environmental protection and workplace environment improvement. There is a tendency for the use of organic solvents to be restricted, and there is an increasing demand for aqueous adhesives. However, conventional water-based adhesives are limited in practical use because they have poor adhesion to polyolefin materials compared to solvent-based adhesives. Further, Patent Document 2 discloses a water-based adhesive and describes that it can be applied to a cyclic polyolefin material. However, there was room for improvement in terms of adhesion and chemical resistance of the coating film.

JP 2011-104886 A JP 2007-308588 A

  The present invention is an aqueous system that can form a coating film having good adhesion to the material and good chemical resistance without special treatment of the surface of the cyclic polyolefin material. It is intended to provide a coating agent and a laminate using the same.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a water-based coating agent that is environmentally friendly and uses a polyolefin resin having a specific composition, so that it can be bonded to a cyclic polyolefin material without special treatment. The present inventors have found that a coating film having good properties and excellent chemical resistance can be formed, and the present invention has been achieved.

  That is, the present invention is as follows.

(1) A coating agent for a cyclic polyolefin material comprising an acid-modified polyolefin resin containing a (meth) acrylic acid ester component, a basic compound, and an aqueous medium.
(2) The coating for cyclic polyolefin material according to (1), further comprising a polyurethane resin, wherein a solid content mass ratio of the acid-modified polyolefin resin and the polyurethane resin is 100 / 0.5 to 100/100 Agent.
(3) The cyclic polyolefin material according to (1) or (2), further comprising a crosslinking agent, wherein the mass ratio of the solid content of the acid-modified polyolefin resin and the crosslinking agent is 100/1 to 100/50 Coating agent.
(4) The coating agent for cyclic polyolefin materials according to (2), wherein the number average particle diameters of the polyolefin resin and the polyurethane resin are both 5 to 300 nm.
(5) Laminate characterized in that a coating obtained by removing an aqueous medium from the coating agent for cyclic polyolefin material according to any one of (1) to (4) is provided on at least one surface of the cyclic polyolefin material. body.
(6) The laminate according to (5), wherein a cyclic polyolefin material or another material is further bonded through a coating film.

  According to the present invention, it is possible to provide a coating agent suitable for obtaining a coating film having good adhesion to the cyclic polyolefin material without special treatment and having good chemical resistance. . Therefore, the coating agent of the present invention can be applied to various uses such as packaging materials, automobile materials, electrical materials, optical materials, and daily goods.

  The present invention will be described in detail below.

  The coating agent for cyclic polyolefin materials of the present invention contains an acid-modified polyolefin resin containing a (meth) acrylic acid ester component, a basic compound, and an aqueous medium.

  The olefin component that is the main component of the acid-modified polyolefin resin is not particularly limited, but an alkene having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 2-butene, 1-butene, 1-pentene, 1-hexene is preferable, Mixtures of these may be used. Among these, alkene having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene is more preferable, ethylene and propylene are further preferable, and ethylene is most preferable.

  The acid-modified polyolefin resin is acid-modified with an unsaturated carboxylic acid component. Examples of unsaturated carboxylic acid components include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, and the like, as well as unsaturated dicarboxylic acid half esters and half amides. It is done. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable. The unsaturated carboxylic acid component only needs to be copolymerized in the acid-modified polyolefin resin, and the form thereof is not limited. Examples of the copolymerization state include random copolymerization, block copolymerization, and graft copolymerization (grafting). Modification).

  The content of the unsaturated carboxylic acid component is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.5 to 4% from the balance of adhesiveness with the cyclic polyolefin material and other materials. % By mass is more preferable, and 1 to 4% by mass is particularly preferable. When the content is less than 0.01 mass, a coating film having sufficient adhesion to a metal material such as an aluminum foil among other materials may not be obtained. On the other hand, when it exceeds 10 mass%, when it is set as a coating film, adhesiveness with cyclic polyolefin material may fall.

  The acid-modified polyolefin resin in the present invention needs to contain a (meth) acrylic acid ester component. If this component is not contained, sufficient adhesion to the cyclic polyolefin material cannot be obtained when a coating film is formed. Examples of the (meth) acrylic acid ester component include an esterified product of (meth) acrylic acid and an alcohol having 1 to 30 carbon atoms, and (meth) acrylic acid and carbon number 1 from the viewpoint of easy availability. Esterified products with ˜20 alcohols are preferred. Specific examples of the (meth) acrylic acid ester component include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth ) Octyl acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. Mixtures of these may be used. Among these, from the viewpoint of easy availability and adhesiveness, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl acrylate, octyl acrylate are more preferable, ethyl acrylate, More preferred is butyl acrylate, and particularly preferred is ethyl acrylate. ("(Meth) acrylic acid-" means "acrylic acid- or methacrylic acid-".)

  The content of the (meth) acrylic acid ester component in the acid-modified polyolefin resin is 0.1 to 35% by mass from the viewpoint of improving the adhesion to the cyclic polyolefin and the chemical resistance when the coating film is formed. Preferably, it is 1-30 mass%, More preferably, it is 5-25 mass%, It is especially preferable that it is 8-25 mass%. When the content of the (meth) acrylic acid ester component is less than 0.1% by mass, the adhesiveness with the cyclic polyolefin tends to be reduced when the coating is used, and when it exceeds 35% by mass, Chemical resistance is reduced. Further, the (meth) acrylic acid ester component may be copolymerized in the acid-modified polyolefin resin, and the form thereof is not limited. Examples of the copolymerization state include random copolymerization, block copolymerization, and grafting. Examples include copolymerization (graft modification).

  As a specific example of the acid-modified polyolefin resin, an ethylene- (meth) acrylic acid ester-maleic anhydride copolymer is most preferable. The form of the copolymer may be any of a random copolymer, a block copolymer, a graft copolymer, etc., but a random copolymer and a graft copolymer are preferred from the viewpoint of easy availability.

The amount (layer amount) of the coating film after drying is not particularly limited. For example, preferably in the range of 0.01 to 50 g / ^{m 2,} more preferably from 0.1 to 20 g / ^{m 2,} more preferably from 1 to 15 g / ^{m 2,} 1 to 10 g / and particularly preferably m ^2. If it is less than 0.01 g / m ² , sufficient adhesion cannot be obtained, and if it exceeds 50 g / m ² , it is economically disadvantageous.

  The molecular weight of the acid-modified polyolefin resin is not particularly limited, but the higher the chemical resistance, the better the chemical resistance of the coating film. Accordingly, the melt flow rate at 190 ° C. and 2160 g load, which is a measure of molecular weight, is preferably 1000 g / 10 min or less, more preferably 500 g / 10 min or less, still more preferably 0.001 to 200 g / 10 min, ˜100 g / 10 min is particularly preferred. When the melt flow rate exceeds 1000 g / 10 minutes, the chemical resistance of the coating film tends to decrease. When it is less than 0.001 g / 10 minutes, there are restrictions on the production surface when the resin is made high molecular weight. receive.

  As will be described later, the coating agent of the present invention is preferably an aqueous dispersion of an acid-modified polyolefin resin. In this case, as a method for preparing the aqueous dispersion, for example, WO 02/055598 Listed in the issue pamphlet.

  The coating agent of the present invention may contain a resin other than the acid-modified polyolefin resin containing a (meth) acrylic acid ester component as necessary. Examples of other resins include polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, ethylene- (meth) acrylic acid copolymer, styrene-maleic acid resin, styrene-butadiene resin, Butadiene resin, acrylonitrile-butadiene resin, poly (meth) acrylonitrile resin, (meth) acrylamide resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyester resin, modified nylon resin, polyurethane resin, phenol resin, silicone resin, epoxy resin, etc. Is mentioned.

  Especially, it is preferable to contain a polyurethane resin from a viewpoint of the adhesive improvement to cyclic polyolefin material. The polyurethane resin is a polymer containing a urethane bond in the main chain, and is obtained, for example, by a reaction between a polyol compound and a polyisocyanate compound. From the viewpoint of improving adhesiveness, it is preferable to use a polyether type polyurethane resin. The polyol compound includes a polyether polyol. Examples of the polyether polyol include polyoxyethylene polyols such as polyethylene glycol, polyoxypropylene polyols such as polypropylene glycol, and polyoxyethylene / propylene polyols such as polytetramethylene ether glycol, among which polyethylene glycol and polytetramethylene glycol. Polyethermethylene glycol is more preferable because it is easy to obtain, and adhesion is improved. Although the molecular weight of polyether diol is not specifically limited, The thing of the range of 1000-10000 is preferable and 1000-5000 are especially preferable.

  As polyols other than polyether polyols, 1,3-butanediol, 1,4-butanediol, 1,2-propanediol, 1,3-propanediol, 1,6- Hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, methyl-1,5-pentanediol, 1,8-octanediol, 2-ethyl-1,3-hexanediol and the like may be used.

  On the other hand, as the polyisocyanate compound constituting the polyurethane resin, one kind or a mixture of two or more kinds of aromatic, aliphatic or alicyclic diisocyanates can be used. Specific examples of diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate, dimethyl diisocyanate, lysine diisocyanate. , Hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, dimerized isocyanate in which the carboxyl group of dimer acid is converted to an isocyanate group, and adducts, biurets, isocyanurates, etc. Isophorone diisocyanate is preferable from the viewpoint of improving the properties.

  In the coating agent of the present invention, the mass ratio of the solid content of the acid-modified polyolefin resin and the polyurethane resin is 100/0 from the balance between the adhesion to the cyclic polyolefin material and the chemical resistance when formed into a coating film. 5 to 100/100 is preferable, 100/1 to 100/80 is more preferable, 100/1 to 100/50 is further preferable, and 100/1 to 100/40 is particularly preferable. When the content of the polyurethane resin is less than 0.5 parts by mass, the adhesiveness is hardly improved. On the other hand, when the content exceeds 100 parts by mass, the chemical resistance of the coating film tends to decrease.

  The acid-modified polyolefin resin and the polyurethane resin are preferably uniformly dispersed or dissolved in the coating agent, and particularly preferably uniformly dispersed. When these resins are dispersed in the coating agent, that is, when prepared into an aqueous dispersion, the number average particle diameter of the resin particles is 500 nm (nanometers) from the viewpoint of improving the transparency of the coating film. The following is preferable, 5-300 nm is more preferable, 5-200 nm is more preferable, and 5-100 nm is the most preferable.

  A cross-linking agent for cross-linking the acid-modified polyolefin resin and / or the urethane resin may be added to the coating agent of the present invention for the purpose of enhancing adhesiveness. In particular, when a urethane resin is blended in the coating agent, the adhesiveness can be dramatically improved by using a crosslinking agent in combination. Examples of the crosslinking agent include isocyanate compounds, melamine compounds, urea compounds, epoxy compounds, carbodiimide compounds, oxazoline group-containing compounds, hydrazide compounds, zirconium salt compounds, silane coupling agents, and the like. The content of the crosslinking agent is preferably such that the solid content mass ratio between the acid-modified polyolefin resin and the crosslinking agent is 100/1 to 100/50, particularly preferably 100/3 to 100/30, and more preferably 100/5 to 100. / 20 is most preferred. When it exceeds 50 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin, the adhesiveness tends to decrease.

  In addition, additives such as inorganic compounds, wetting agents, and leveling agents may be contained.

  The coating agent of the present invention further contains a basic compound and an aqueous medium.

  Here, the aqueous medium is a medium composed of a liquid containing water as a main component, and may contain a water-soluble organic solvent described later.

  The basic compound is for neutralizing ionic groups such as carboxyl groups present in the polyolefin resin and polyurethane resin. In particular, when preparing into an aqueous dispersion, aggregation between resin particles is prevented by the electric repulsion between carboxyl anions generated by neutralization, and stability is imparted to the aqueous dispersion. The basic compound used in making the aqueous solution may be any compound that can neutralize the carboxyl group.

  As the basic compound, ammonia or an organic amine compound that volatilizes at the time of forming the coating film is preferable from the viewpoint of water resistance of the coating film, and an organic amine compound having a boiling point of 30 to 250 ° C, more preferably 50 to 200 ° C is particularly preferable. When the boiling point is less than 30 ° C., the rate of volatilization when the resin described later becomes aqueous may increase, and the aqueous formation may not proceed completely. On the other hand, when the boiling point exceeds 250 ° C., it is difficult to disperse the organic amine compound from the coating film by drying, and the water resistance of the coating film may deteriorate.

  Specific examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, and 3-ethoxypropylamine. , 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine and the like.

  In addition, the organic solvent used in the present invention is an atom having a Pauling electronegativity of 3.0 or more (specifically, oxygen) from the viewpoint of wettability to cyclic polyolefin material and dispersion stability of the resin. , Nitrogen, fluorine, chlorine) are preferably used in the molecule. Among them, those having a solubility in water at 20 ° C. of 5 g / L or more are preferably used, and more preferably 10 g / L or more.

  Specific examples of organic solvents that can be used in the present invention include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol. , Tert-amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol and other alcohols, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone, isophorone and other ketones , Ethers such as tetrahydrofuran and dioxane, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, isobutyl acetate, acetic acid-sec-butyl, acetic acid-3-meth Cibutyl, methyl propionate, ethyl propionate, diethyl carbonate, dimethyl carbonate, etc., ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate , Glycol derivatives such as diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate Further, 3-methoxy-3-methylbutanol, 3-methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate and the like are preferable. Among them, those having a boiling point of 30 to 250 ° C. are preferable. The thing of -200 degreeC is especially preferable. These organic solvents may be used in combination of two or more.

  In the coating agent of the present invention, the amount of the surfactant is preferably 5 parts by mass or less with respect to 100 parts by mass of the total resin, from the viewpoints of improvement in water resistance and adhesion, and reduction in contamination. Part or less, more preferably 1 part by weight or less, particularly preferably 0.5 part by weight or less, and most preferably 0.1 part by weight or less.

  Next, the laminate of the present invention will be described. In the laminate of the present invention, a coating film obtained by removing the aqueous medium from the coating agent is provided on at least one surface of the cyclic polyolefin material. The coating film obtained by the coating agent of the present invention has good adhesion to the cyclic polyolefin material.

  Examples of the cyclic polyolefin material include those described in JP-A No. 10-120768, JP-A No. 11-43566, JP-A No. 2004-51949, JP-A No. 2004-156048, and the like. Commercial products of cyclic polyolefin materials include “ARTON” (manufactured by JSR), “ZEONOR”, “ZEONEX” (manufactured by Nippon Zeon), “OPTOREZ” (manufactured by Hitachi Chemical Co., Ltd.), “APEL” (Mitsui Chemical Co., Ltd.).

  The shape of the material is not particularly limited, and examples thereof include films, molded articles, and woven fabrics. In the present invention, even if the surface of the cyclic polyolefin material is not subjected to special treatment such as corona treatment or plasma treatment, the coating obtained by the coating agent of the present invention can be adhered to the surface of the material with good adhesiveness. However, in order to further improve the adhesion, the surface of the same material may be previously subjected to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment and the like.

  In order to obtain the laminate of the present invention, for example, the coating agent may be applied to at least one surface of the cyclic polyolefin material and dried.

  As a coating method, a known method such as gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating, or the like can be employed. Application to the surface of the cyclic polyolefin material is generally preferably performed so that the thickness of the coating film is uniform, and after uniform application, set it near room temperature as necessary, and then for drying treatment or drying. A uniform coating film can be formed by subjecting to the heat treatment.

  In the laminate of the present invention, another material may be further bonded onto the coating film. As other materials to be bonded, paper, synthetic paper, thermoplastic resin film, molded product, plastic product, steel plate, aluminum foil, wood, woven fabric, knitted fabric, non-woven fabric, gypsum board, wood board, etc. may be used. it can. Among these, it is preferable to use a thermoplastic resin film.

  Examples of the thermoplastic resin film include polyethylene terephthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, and other polyester resins, polyglycolic acid, polylactic acid, and the like. Biodegradable resins typified by aliphatic polyester resins such as polyhydroxycarboxylic acid, poly (ethylene succinate), poly (butylene succinate), polyamide resins such as nylon 6, nylon 66, nylon 46, cyclic polyolefin ( Films made of thermoplastic resins such as polyolefin resins such as the above), polypropylene (PP), polyethylene, ethylene-vinyl acetate copolymer, polyimide resins, polyarylate resins or mixtures thereof. These laminates thereof. Among these, films made of polyester, polyamide, cyclic polyolefin, polyethylene, ethylene-vinyl acetate copolymer, and PP are suitable, and cyclic polyolefin is most suitable. These films may be unstretched films or stretched films, and their production methods are not limited. Also, the thickness of the film is not particularly limited, but it may be usually in the range of 5 to 1000 μm.

  The film surface may be subjected to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc. as pretreatment.

  The temperature at which the coating agent of the present invention is dried and the temperature at which the cyclic polyolefin material or other material is bonded through the coating film are not particularly limited, but considering the type of the material to be bonded, production efficiency, etc. What is necessary is just to set suitably.

  The laminate of the present invention can be applied to various uses such as packaging materials, automobile materials, electrical materials, optical materials, and daily goods.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

(1) Configuration of acid-modified polyolefin resin
^It calculated | required from < ¹ > H-NMR analysis (The product made by Varian, 300MHz). Orthodichlorobenzene (d ₄ ) was used as a solvent, and measurement was performed at 120 ° C.
(2) Melt flow rate (MFR) of acid-modified polyolefin resin
It measured by the method of JIS6730 description (190 degreeC, 2160g load).
(3) Average particle diameter of polyolefin resin and polyurethane resin The number average particle diameter was calculated | required using the Nikkiso Co., Ltd. make and micro track particle size distribution analyzer UPA150 (MODEL No. 9340).
(4) Amount of coating film (layer amount)
A predetermined amount of a coating agent was applied to a substrate whose area and mass were measured in advance, and dried at 100 ° C. for 2 minutes. The mass of the obtained laminate was measured, and the coating amount was determined by subtracting the mass of the base material before coating. The layer amount (g / m ² ) per unit area was calculated from the coating amount and the coating area.
(5) Haze (cloudiness value)
According to JIS K7105, “Haze (%)” was measured using NDH2000 “turbidity, haze meter” manufactured by Nippon Denshoku Industries Co., Ltd. A coating film was prepared by applying a coating agent to a PET film having a haze of 1.0% using a Meyer bar so that the thickness of the coating film after drying was 2 μm, and then drying at 100 ° C. for 15 seconds. did. Thus, the haze of the whole coat film produced was measured.
(6) Evaluation of adhesion of coating film A coating agent is applied on a molded plate of a cyclic polyolefin material (ZEONOR, manufactured by Nippon Zeon Co., Ltd.) using a Mayer bar so that the thickness of the coating film after drying becomes 2 μm And dried at 100 ° C. for 1 minute. After standing at room temperature for 24 hours, an adhesion test was performed by the method of JIS K5400 8.5.2. The coating layer was cut to produce 1 mm × 1 mm × 100 grid sections, which were peeled off with an adhesive tape, and evaluated by the number remaining without peeling in the 100 grids. “N / 100” indicates that n of the 100 grids remain without being peeled off, and “100/100” indicates that they are not peeled off at all and have the best adhesion.
(7) Adhesive strength On various substrates, the coating agent was applied using a Mayer bar so that the thickness of the coating film after drying was 3 μm, and dried at 100 ° C. for 1 minute. And it pressed at 120 degreeC with the heat press machine (sealing pressure 0.3MPa for 10 second) so that the coating-film surfaces of the obtained laminated body might contact | connect. The laminate after pressing was cut out with a width of 15 mm and left to stand for one day, and then a coating film was used at a tensile speed of 200 mm / min and a tensile angle of 180 degrees using a tensile testing machine (Intesco Precision Universal Material Testing Machine 2020). The heat sealability (heat seal strength) was evaluated by measuring the peel strength.
In addition, the following materials were used as a base material.
・ Cyclic polyolefin (COP) material film (ZEONOR film, thickness 100μm, manufactured by Nippon Zeon)
・ PET film (thickness 50μm, manufactured by Unitika)
・ Nylon (Ny) film (thickness 15 μm, manufactured by Unitika)
・ Unstretched polypropylene (CPP) film (thickness 50 μm, manufactured by Tosero)
・ Aluminum (Al) foil (thickness 25μm, manufactured by Mitsubishi Aluminum)
・ Unstretched polyethylene (PE) film (thickness 40 μm, manufactured by Tamapoly)
(8) Chemical resistance test On the cyclic polyolefin material film (ZEONOR film, manufactured by Nippon Zeon Co., Ltd.), a coating agent was applied using a Mayer bar so that the thickness of the coating film after drying was 2 μm. Dry at 100 ° C. for 1 minute. Thereafter, the laminate was allowed to stand at room temperature for 24 hours, then immersed in 5% by mass hydrochloric acid, 5% by mass sodium hydroxide aqueous solution or ethanol at 25 ° C. for 1 day, and washed with water. And the state of the application surface was evaluated visually.
○: No change.
Δ: Slight whitening is observed.
X: Whitening or dissolution is observed.

(Commercially available polyether type polyurethane resin aqueous dispersion U-1)
As U-1, NeoRezR-600 (solid content concentration 33 mass%, moisture 67 mass%) manufactured by Enomoto Kasei Co., Ltd. was prepared. The number average particle diameter was 50 nm.

(Polyurethane resin aqueous dispersion U-2)
U-2 was produced by the following method. A reactor equipped with a stirrer, thermometer, nitrogen seal tube, and condenser is charged with 345 parts by mass of polytetramethylene glycol having an average molecular weight of 1970, 77.8 parts by mass of isophorone diisocyanate, and 0.03 parts by mass of dibutyltin dilaurate. And reacted at 80 ° C. for 2 hours. Subsequently, after cooling this reaction liquid to 50 degreeC, 9.7 mass parts of dimethylpropanolamine, 10.85 mass parts of triethylamine, and 177 mass parts of acetone were added, and it was made to react. Further, 175 parts by mass of acetone was added to the reaction liquid and cooled to 30 ° C., 13.4 parts by mass of isophorone diisocyanate, 1.07 parts by mass of monoethanolamine, 87.9 parts by mass of isopropanol (IPA), A mixed liquid consisting of 1039 parts by mass was added and stirred at a high speed, and acetone and IPA were distilled off from this liquid to obtain an aqueous polyether type polyurethane resin dispersion U-2. The number average particle size was 350 nm.

(Polycarbonate-type polyurethane resin aqueous dispersion U-3)
As U-3, Takelac W-6010 manufactured by Mitsui Takeda Chemical Co., Ltd. (solid content concentration 30% by mass, moisture 70% by mass) was prepared. The number average particle diameter was 60 nm.

(Crosslinking agent: K-1)
Epocros WS-700 manufactured by Nippon Shokubai Co., Ltd. (an aqueous solution of an oxazoline compound obtained by polymerizing 2-isopropenyl-2-oxazoline, solid content concentration 40% by mass) was used.

(Crosslinking agent: K-2)
A solution prepared by dissolving ADH (adipic acid dihydrazide) manufactured by Otsuka Chemical Co., Ltd. in water to a solid content concentration of 8% by mass was used.

Example 1
Using a stirrer equipped with a heat-resistant 1 liter glass container with a heater, 60.0 g of acid-modified polyolefin resin (Arkema, Bondine HX-8210), 60.0 g of isopropanol, 3.0 g of triethylamine And 177.0 g of distilled water were charged into a glass container and stirred at a rotational speed of the stirring blade of 300 rpm. No sedimentation of resin particles was observed at the bottom of the container, confirming that it was in a floating state. It was. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 130 ° C. and further stirred for 120 minutes. Then, after putting in a water bath and cooling to room temperature (about 25 ° C.) while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) Thus, a milky white uniform coating agent E-1 was obtained. The number average particle size was 70 nm.

(Example 2)
A coating agent E-2 was obtained in the same manner as in Example 1 except that Bondin HX-8290 (manufactured by Arkema) was used as the acid-modified polyolefin resin. The number average particle size was 80 nm.

(Comparative Example 1)
Using a stirrer equipped with a hermetic pressure-resistant 1 liter glass container with a heater, 60.0 g of ethylene-acrylic acid copolymer resin (Doma Chemical Co., Primacol 5980I), 16.8 g of triethylamine (TEA) ) And 223.2 g of distilled water were charged into a glass container and stirred at a stirring blade rotation speed of 300 rpm. No sedimentation of resin particles was observed at the bottom of the container, indicating that it was in a floating state. confirmed. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 140 to 145 ° C. and further stirred for 30 minutes. Then, after putting in a water bath and cooling to room temperature (about 25 ° C.) while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) Thus, a slightly cloudy coating agent H-1 was obtained. At this time, almost no resin remained on the filter. The number average particle size was 30 nm.

  Table 1 shows the composition of the acid-modified polyolefin resin used for the production of the coating agents E-1, E-2, and H-1.

(Examples 3 to 21, Comparative Examples 2 to 4)
Each coating agent was obtained by mixing at room temperature using the types and amounts of polyolefin resin, polyurethane resin and cross-linking agent so that the blending ratios shown in Tables 2 to 4 were obtained.

As in Examples 1 and 2, when an acid-modified polyolefin resin containing a (meth) acrylic acid ester component was used, good adhesion to the cyclic polyolefin material was exhibited. On the other hand, Comparative Example 1 using a resin containing no (meth) acrylic acid ester component showed some adhesion to polyethylene and polyethylene terephthalate, but had little adhesion to cyclic polyolefin material. .
Furthermore, the adhesiveness with cyclic polyolefin material improved by containing a predetermined amount of polyurethane resin (Examples 3-8). When the addition amount exceeded 100 parts by mass, the effect of improving the adhesiveness tended to decrease, but showed an appropriate adhesiveness (Example 9).
Moreover, when the polyether type thing was used as a urethane resin, the adhesive improvement effect with cyclic polyolefin material was larger than the polycarbonate type thing (comparison of Example 3 and 5). Moreover, when the polyurethane resin with a large particle diameter was used, even if the addition amount was the same, the haze increased and the transparency of the coating film deteriorated (Example 4).
As in Examples 10 to 19, the adhesion to the cyclic polyolefin material was remarkably improved by further blending a crosslinking agent into the coating liquid containing the acid-modified polyolefin resin and the polyurethane resin. This effect is specific when considering that, as in Examples 20 and 19, only the cross-linking agent is added to the acid-modified polyolefin resin, the adhesive force tends to decrease.
As in Comparative Examples 2 to 4, even when a polyurethane resin and / or a crosslinking agent was blended with an acid-modified polyolefin containing no (meth) acrylic acid ester component, the adhesion to the cyclic polyolefin material was hardly improved. .

Claims (6)

  A coating agent for cyclic polyolefin material, comprising an acid-modified polyolefin resin containing a (meth) acrylic acid ester component, a basic compound, and an aqueous medium.   The coating agent for cyclic polyolefin materials according to claim 1, further comprising a polyurethane resin, wherein the solid mass ratio of the acid-modified polyolefin resin and the polyurethane resin is 100 / 0.5 to 100/100. The coating agent for cyclic polyolefin materials according to claim 1 or 2, further comprising a crosslinking agent, wherein the mass ratio of the solid content of the acid-modified polyolefin resin and the crosslinking agent is 100/1 to 100/50.   The number average particle diameter of both polyolefin resin and polyurethane resin is 5-300 nm, The coating agent for cyclic polyolefin materials of Claim 2 characterized by the above-mentioned.   The laminated body provided with the coating film obtained by removing an aqueous medium from the coating agent for cyclic polyolefin materials in any one of Claims 1-4 on the at least single side | surface of cyclic polyolefin material.   Furthermore, the laminated body of Claim 5 which bonded together cyclic polyolefin material or another material through the coating film.