KR100923451B1 - Adhesive composition with eco-friendly for aqueous dry lamination and hot stamping foil - Google Patents

Abstract

PURPOSE: An adhesive composition for environment-friendly aqueous dry lamination for thermal transfer printing is provided to avoid environmental contamination and bad effects on the health of consumer and operator. CONSTITUTION: An adhesive composition for environment-friendly aqueous dry lamination for thermal transfer printing comprises a water-dispersible resin composition, a water soluble hydrazine compound, an aqueous acryl emulsion and styrene acrylic copolymer resin, polyethylene wax, inorganic filler and antisagging agent. The water-dispersible resin composition comprises active carbonyl-containing polymerizable unsaturated monomer, acidic group-containing polymerizable unsaturated monomer, and other polymerizable unsaturated monomer. The aqueous acryl emulsion includes an emulsifier, a water soluble free radical polymerization initiator and a chain transfer agent.

Description

Adhesive composition with eco-friendly for aqueous dry lamination and hot stamping foil

The present invention relates to an environmentally friendly aqueous dry lamination adhesive composition for thermal transfer printing, and more particularly to an active carbonyl group-containing polymerizable unsaturated monomer (a), an acid group-containing polymerizable unsaturated monomer (b), and other polymerizable unsaturated monomer (c). It relates to an environmentally friendly one-component aqueous dry lamination adhesive composition for thermal transfer printing containing an aqueous acrylic emulsion comprising a water-dispersible resin composition (A), a water-soluble hydrazine compound (B), an emulsifier, a water-soluble free radical polymerization initiator and a chain transfer agent.

Dry lamination is applied to the surface of base material such as plastic film or aluminum foil by applying adhesive solution dissolved in organic solvent, evaporating and drying the solvent by hot air or heating, and adhesive surface is slightly hardened due to uncured In a state of excitation, the second base material film is polymerized to be laminated by pressure bonding, which is then wound to complete curing of the adhesive and to be laminated. It is a method of apply | coating an aqueous solution and an emulsion to a material mainly, bonding a breathable 2nd material, and drying and laminating | stacking. Dry lamination is not required for breathability for transpiration in the second base material and is therefore applied for bonding a wide range of films and metal foils.

Hot stamping generally refers to thermal transfer printing, and is a kind of heat printing method that transfers various patterns and characters by applying a thermal transfer paper and a heated front plate to a transfer object such as paper, plastic, fiber, leather, metal, and glass.

Stamping foil structure is generally a film (polyethylene terephthalate film having good heat resistance) to act as a carrier (Carrier), the cellulose resin, acrylic resin, Montan wax, Carnauba wax, etc. are coated on the support To form a release layer, coating a resin having excellent heat resistance and chemical resistance on the release layer to form a colored layer, and depositing a metal such as aluminum, chromium, copper, silver, and gold at a high vacuum on the colored layer. A deposition layer is formed, and a metal-based layer is formed by dry laminating a solvent type adhesive suitable for a transfer object on the metal deposition layer.

The use of such solvent-type adhesive is made by mixing a highly volatile fast-drying solvent (MEK, toluene), when the gravure coating has a large amount of solvent volatilized, causing the environmental pollution. In addition, the use of volatile organic solvents (VOC) has a high risk of fire, and when inhaled, various disorders such as anesthesia, central and autonomic nervous system disorders, kidney and liver disorders, and inflammation of the skin or eyes appear on the human body. Has adversely affected the health of people. In the conventional dry lamination adhesive market, the high performance and high performance of the adhesive are required, and the aqueous adhesive cannot satisfy the physical properties that can be used for the purpose, and the solvent adhesive market is monopolizing. There has been an urgent need for an aqueous adhesive that can replace such volatile organic solvents with aqueous and have a dramatic effect on preventing air pollution and improving the global environment.

Accordingly, the present inventors have diligently researched to overcome the problems of the prior art, and as a result, the active carbonyl group-containing polymerizable unsaturated monomer (a), acid group-containing polymerizable unsaturated monomer (b), And an aqueous acrylic emulsion composed of a water-dispersible resin composition (A) comprising a polymerizable unsaturated monomer (c), a water-soluble hydrazine compound (B), an emulsifier, a water-soluble free radical polymerization initiator, and a chain transfer agent. In the case of hot stamping foil, it has excellent adhesion, cutting, adhesion, and blocking resistance that transfer should not occur to the back side (opposite side) while being wound with film. It was confirmed that the present invention can be suitably used, and the present invention was completed.

Therefore, the main object of the present invention is to replace the conventional solvent-type adhesive, it can be used, environmentally friendly water-based for thermal transfer printing having excellent adhesion and cutting (adhesiveness), and blocking resistance (blocking) to the adherend It is to provide a dry lamination adhesive composition.

Another object of the present invention by using the environmentally friendly water-based dry lamination adhesive composition for thermal transfer printing hot on a transfer object such as paper, plastic, fiber, leather, metal, glass with confidence without adversely affecting environmental pollution and health of consumers and workers. Stamping can be performed.

According to one aspect of the present invention, the present invention provides a water-dispersible resin composition (A) consisting of an active carbonyl group-containing polymerizable unsaturated monomer (a), an acid group-containing polymerizable unsaturated monomer (b), and other polymerizable unsaturated monomers (c). An environmentally friendly one-component aqueous dry lamination adhesive composition for thermal transfer printing containing an aqueous acrylic emulsion containing a water-soluble hydrazine compound (B), an emulsifier, a water-soluble free radical polymerization initiator, and a chain transfer agent. The aqueous dry lamination adhesive layer composition of the present invention is a water-based adhesive that replaces the conventional solvent-type adhesive, the amount of solvent volatilized, and diffuses into the air, replacing the solvent-type adhesive that causes problems such as environmental pollution by performing dry lamination 4 printing can be performed.

In the aqueous dry lamination adhesive composition of the present invention, the adhesive composition may further include a styrene acrylic copolymer, polyethylene wax, inorganic filler, and anti-settling agent. In the present invention, the styrene acrylic copolymer resin is included to improve the redissolution of the adhesive composition, the polyethylene wax is included to improve the slip properties of the coating surface of the adhesive composition, the inorganic filler is blocking and stamping It is included to impart cleavage, and the anti-settling agent is included to prevent particle sedimentation occurring in the adhesive composition.

In the aqueous dry lamination adhesive composition of the present invention, the polymerizable unsaturated monomer (a) is at least one selected from the group consisting of diacetone (meth) acrylamide, acetoacetoxyethyl (meth) acrylate, and acetoacetic acid vinyl ester. desirable.

In the aqueous dry lamination adhesive composition of the present invention, the acid group-containing polymerizable unsaturated monomer (b) is selected from acric acid, metaacrylic acid, crotonic acid, isocrotonic acid, α-ethylacrylic acid, β-ethylacrylic acid and β-propylacrylic acid. Acid, β-isopropylacrylic acid, itaconic acid, maleic anhydride, fumaric acid, β-carboxyethyl acrylate, p-vinylbenzenesulfonic acid, p-acrylamide propanesulfonic acid, t-butylacrylamide sulfonic acid, 2-hydro It is preferable that it is at least one selected from the group consisting of a phosphate monoester of hydroxy (meth) acrylate and a phosphate monoester of 2-hydroxypropyl (meth) acrylate.

In the aqueous dry lamination adhesive composition of the present invention, the other polymerizable unsaturated monomer (c) means a polymerizable unsaturated monomer except for the polymerizable unsaturated monomer (a) and the acid group-containing polymerizable unsaturated monomer (b), and Types include acrylate alkyl ester (c-1), styrene monomer (c-2), acrylonitrile (c-3), hydrolyzable silyl group-containing polymerizable unsaturated monomer (c-4), hydroxyl-containing polymerizable Unsaturated monomers (c-5), amide bond-containing polymerizable unsaturated monomers (c-6), epoxy group-containing polymerizable unsaturated monomers (c-7), polyfunctional vinyl group-containing polymerizable unsaturated monomers (c-8), and the like. have.

In the aqueous dry lamination adhesive composition of the present invention, the adhesive composition is 40 to 70% by weight of the aqueous acrylic emulsion, 15 to 35% by weight of the base soluble styrene acrylic copolymer, 5 to 10% by weight of polyethylene wax, 5 to 10 weight of the inorganic filler %, And 1 to 5% by weight of the particle sedimentation inhibitor.

Hereinafter, the aqueous dry lamination adhesive composition of this invention is demonstrated more concretely.

The present invention does not use a nonylphenol (Nonyl Phenol) -type surfactant that adversely affects the normal hormone action (endocrine disturbance action) to inhibit the reproductive function, and also does not use any volatile organic solvent (VOC), Provided is a one-component aqueous adhesive layer for dry lamination, which is mainly composed of an environmentally friendly aqueous acrylic emulsion containing no harmful substances such as lead, cadmium, mercury, and chromium.

The most important aqueous acrylic emulsions in the present invention are emulsion polymerization of monomer mixtures of specific compositions. The aqueous acrylic emulsion is emulsified by adding a chain transfer agent to a polymerizable unsaturated monomer mixture composed of an active carbonyl group-containing polymerizable unsaturated monomer (a), an acid group-containing polymerizable unsaturated monomer (b), and other polymerizable unsaturated monomers (c). The aqueous acrylic emulsion composition of 20 degreeC or more of glass transition temperature can be synthesize | combined using the water-dispersible resin composition (A) and water-soluble hydrazine compound (B) which were obtained by combining as a main component. Each of the above components is not necessarily limited thereto, but is preferably 0.1 to 10% by weight of an active carbonyl group-containing polymerizable unsaturated monomer (a), 0.1 to 10% by weight of an acid-containing polymerizable unsaturated monomer (b), and other polymerizable unsaturated monomers (c). Water-soluble resin composition (A) containing a copolymer resin obtained by adding a chain transfer agent to the polymerizable unsaturated monomer mixture composed of 80 to 99.9 wt% by emulsion polymerization and a total amount of the polymerizable unsaturated monomer mixture in an amount of 0.1 to 10% by weight. The hydrazine compound (B) can be mixed and synthesized.

 Examples of the active carbonyl group-containing polymerizable unsaturated monomer (a) include vinyl alkyl ketones having 4 to 7 carbon atoms such as diacetone (meth) acrylamide, acetoacetoxyethyl (meth) acrylate, and vinyl acetate acetoacetate (for example, vinyl). And polymerizable unsaturated group-containing ketones (keto group-containing polymerizable unsaturated compounds) such as methyl ketone, vinyl ethyl ketone, and vinyl butyl ketone. Among these, diacetone (meth) acrylamide is most commonly used, and the active carbonyl group The containing polymerizable unsaturated monomer (a) can be used individually or in combination of 2 or more types.

In addition, the active carbonyl group-containing polymerizable unsaturated monomer (a) is preferably used in combination with a water-soluble hydrazine compound (B) which is a crosslinking agent, which is a water-soluble carbonyl group of the active carbonyl group-containing polymerizable unsaturated monomer (a) during film formation. This is because the hydrazine compound (B) reacts with the hydrazine group to form a crosslinked structure at room temperature or at low temperature. Therefore, when manufacturing various plastic films, fibers, paper, artificial leather, etc., it exhibits excellent adhesive strength, heat resistance, solvent resistance, and the like. The amount of the active carbonyl group-containing polymerizable unsaturated monomer (a) is used in an amount of 0.1 to 10% by weight based on the total amount of the polymerizable unsaturated monomer mixture used in preparing the resin (A), preferably 0.5 to 7% by weight. If it is less than 0.1% by weight, the above effect cannot be obtained, and if it exceeds 10% by weight, the water resistance of the film may be lowered and poor adhesion may occur under high temperature and high humidity.

As the acid group-containing polymerizable unsaturated monomer (b), for example, an ethylenically unsaturated monomer compound having at least one acid group in a molecule such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group can be used.

Carboxyl group-containing polymerizable unsaturated monomers include acrylic acid, metaacrylic acid, crotonic acid, isocrotonic acid, α-ethylacrylic acid, β-ethylacrylic acid, β-propylacrylic acid, β-isopropylacrylic acid, itaconic acid, Maleic anhydride, fumaric acid, β-carboxyethyl acrylate and the like.

Examples of the sulfonic acid group-containing ethylenic polymerizable unsaturated monomer include p-vinylbenzenesulfonic acid, p-acrylamide propanesulfonic acid, t-butylacrylamide sulfonic acid and the like.

Examples of the phosphoric acid group-containing polymerizable unsaturated monomer include a phosphate monoester of 2-hydroxy (meth) acrylate, a phosphate monoester of 2-hydroxypropyl (meth) acrylate, and the like. Preferably, a carboxyl group-containing polymerizable unsaturated monomer is used. An acidic radical containing polymerizable unsaturated monomer can be used here individually or in combination of 2 or more types. The resin emulsion obtained by using an acidic radical containing polymerizable unsaturated monomer (b) for copolymerization becomes favorable in stability of storage, mechanical stability, and freezing stability. The amount of the acid group-containing polymerizable unsaturated monomer (b) to be used is 0.1 to 10% by weight, preferably 0.5 to 7% by weight based on the total amount of the polymerizable unsaturated monomer used to prepare the resin (A). If the amount of the monomer (b) is less than 0.1% by weight, the above stability is poor. If the amount of the monomer (b) is more than 10% by weight, the polymerization stability due to aggregation decreases, resulting in poor water resistance and poor heat and humidity resistance of the film.

Other polymerizable unsaturated monomers (c) include alkyl (meth) acrylic acid alkyl esters having 1 to 18 carbon atoms (c-1), styrene monomers (c-2), and (meth) acrylonitrile (c-3). , Hydrolyzable silyl group-containing polymerizable unsaturated monomer (c-4), hydroxyl group-containing polymerizable unsaturated monomer (c-5), amide bond-containing polymerizable unsaturated monomer (c-6), epoxy group-containing polymerizable unsaturated monomer (c- 7) In the polyfunctional vinyl group-containing polymerizable unsaturated monomer (c-8), at least one monomer and mixed monomer can be used.

Examples of the (meth) acrylic acid alkyl ester (c-1) having 1 to 18 carbon atoms in the alkyl group include methyl methacrylate (MMA), ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, and t-butyl meta. Acrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, nonyl methacrylate, dodecyl methacrylate, stearyl acrylate, and the like. It can be used in combination and it is preferable to use the C1-C10 (meth) acrylic-acid alkylester of alkyl.

Examples of the styrene-based monomer (c-2) include styrene, α-methylstyrene, vinyltoluene, and the like, and the monomers may be used alone or in combination of two or more thereof.

When the (meth) acrylonitrile (c-3) is used as the copolymerization monomer, the (meth) acrylonitrile (c-3) is oriented in the resin (A) by the cyano group in the molecule to improve the cohesion and heat resistance of the adhesive.

The hydrolyzable silyl group-containing polymerizable unsaturated monomer (c-4) is not particularly limited as long as it is an unsaturated monomer having a hydrolytic condensable group such as a silyl group. For example, γ- (meth) acryloxypropyltrimethoxysilane and γ -(Meth) acryloxypropyl methyldimethoxysilane, (gamma)-(meth) acryloxy diethoxysilane, (gamma)-(meth) acryloxypropyl triethoxysilane, etc. are mentioned. When the hydrolyzable silyl group-containing polymerizable unsaturated monomer (c-4) is used for copolymerization, the hydrolyzable silyl group is hydrolyzed by moisture in air or the like to form a crosslinked structure by siloxane bonds (wet-curing), and the active carbonyl group is contained. There is a synergistic effect of crosslinking structure by reaction with the polymerizable unsaturated monomer (a) and the water-soluble hydrazine compound (B), and the adhesive composition can promote crosslinkability at room temperature or low temperature. Due to this action, the solvent resistance, water resistance and heat resistance of the film are improved and weather resistance is excellent. In particular, it is possible to avoid the deterioration of the adhesive strength in the summer high temperature and high humidity environment.

The hydroxyl group-containing polymerizable unsaturated monomer (c-5) is not particularly limited as long as it is an unsaturated monomer having a hydroxyl group. For example, it contains hydroxyl groups, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl cimethacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate. Acrylic monomers etc. are mentioned. This is used 1 type or in combination of 2 or more types. When the hydroxyl group-containing polymerizable unsaturated monomer (c-5) is used as the copolymerization component, the hydrophilicity of the film is improved, and the adhesion to the material is improved.

Examples of the amide bond-containing polymerizable unsaturated monomer (c-6) include acrylamide, methacrylamide, α-ethylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methylacrylamide, N-methyl methacrylamide, N-metholacrylamide, N-methol methacrylamide, methylenebisacrylamide, methylenebisacrylamide, etc. are mentioned. The use of an amide bond-containing polymerizable unsaturated monomer (c-6) as a copolymerization monomer gives Newtonian liquid viscosity to improve leveling during application, thereby improving workability.

The epoxy group-containing polymerizable unsaturated monomer (c-7) is not particularly limited as long as it is a polymerizable unsaturated monomer having an epoxy group. For example, glycidyl acrylate, glycidyl methacrylate (GMA), glycidyl crotonate , Glycidyl aryl ether, β-glycidyl methacrylate, and the like. In addition to this, (3,4-epoxycyclohexyl) methyl methacrylate, 3-epoxycyclo-2-hydroxymethacrylate, and the like are used. You may use these individually or in combination of 2 or more types, Preferably glycidyl methacrylate is good. When the epoxy group-containing polymerizable unsaturated monomer (c-7) is used for copolymerization, crosslinkability can be promoted at room temperature or low temperature to improve solvent resistance, water resistance, and moisture resistance of the film.

Examples of the polyfunctional vinyl group-containing polymerizable unsaturated monomer (c-8) include divinylbenzene, ethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, polyethylene glycol (meth) acrylate, and pentaerythritol. A monomer, such as (meth) acrylate, is used 1 type or in combination of 2 or more types.

The amount of the (meth) acrylic acid alkyl ester (c-1) to be used is 30 to 100% by weight, preferably 50 to 100% by weight, based on the total amount of the monomer (c) in the water dispersible resin composition (A). The amount of styrene monomer (c-2) used is 0 to 70% by weight, preferably 0 to 40% by weight, based on the total amount of monomers (c) in the resin (A). The amount of the hydrolyzable silyl group-containing polymerizable unsaturated monomer (c-4) is preferably 0 to 5% by weight, preferably 0.5 to 3% by weight based on the total amount of the monomer (c) in the resin (A). The amount of hydroxyl group-containing polymerizable unsaturated monomer (c-5) to be used is preferably 0.1 to 20% by weight, preferably 0.2 to 10% by weight based on the total amount of monomer (c) in the resin (A). The amount of the amide bond-containing polymerizable unsaturated monomer (c-6) is 0.5 to 10% by weight, preferably 1 to 5% by weight, based on the total amount of the monomer (c) in the resin (A). The use amount of the epoxy group-containing polymerizable unsaturated monomer (c-7) is preferably 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the total amount of the monomer (c) in the resin (A). The amount of the polyfunctional vinyl group-containing polymerizable unsaturated monomer (c-8) is 0.1 to 5% by weight, preferably 0.1 to 3% by weight, based on the total amount of the monomer (c) in the resin (A).

The chain transfer agent used in emulsion polymerization moderates the molecular weight of the polymer produced during emulsion polymerization to enhance adhesion by exerting good wettability and affinity to various plastic surfaces with low surface tension as adhesive for laminates. A mercaptan compound is used as the chain transfer agent. The mercaptan compound includes α-methylstyrene dimer, methyl mercaptan, ethyl mercaptan, butyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-stearyl mercaptan, n- Dodecyl mercaptan, t-dodecyl mercaptan, 3-mercaptopropionate, etc. are used individually or in combination of 2 or more types. The amount of the chain transfer agent used in the emulsion polymerization is 0.2 to 3% by weight based on the total amount of the polymerizable unsaturated monomer in the water-dispersible resin composition (A). If the amount is less than 0.2% by weight, it is difficult to express sufficient adhesion. If it exceeds 3% by weight, the emulsion polymerization rate is low, resulting in a large amount of unreacted monomer, which is not good for environmental protection such as odor generation. Deterioration of heat and solvent resistance.

As the radical polymerization initiator, a water-soluble free radical polymerization initiator is used. Peroxides such as potassium peroxide, sodium persulfate, and ammonium persulfate are used. Redox initiators include hydrogen peroxide, oxidizing agent, sodium hydrogen sulfite, sodium thiosulfate, It is used in combination with a reducing agent such as longgarite.

The emulsifier used in emulsion polymerization uses non-reactive and reactive surfactants of non-environmental hormone type in which non-reactive general emulsifiers, especially environmental aspects, do not contain alkylphenyl groups (especially nonylphenyl groups) having endocrine disrupting action in the molecule of the substance. . Considering physical properties such as water resistance and adhesion, non-environmental hormone-type reactive surfactants are preferred.

The reactive surfactant of the non-environmental hormone type is not limited as long as it is a reactive surfactant having a group capable of expressing an interfacial action such as a nonionic hydrophilic group or an anionic hydrophilic group which does not contain a non-phenylphenyl group in the molecule. For example, a vinyl group, an aryl group, methacryl group, aryloxy group, acryloyl group, acrylooxy group, etc. are mentioned. The amount of non-environmental reactive surfactant used in emulsion polymerization is 0.3 to 6% by weight based on the total amount of polymerizable unsaturated monomers. If the amount is less than 0.3% by weight, the stability of the emulsion polymerization may deteriorate and small particles may be generated during the polymerization. In addition, if the content exceeds 6% by weight, water resistance, heat and humidity resistance, solvent resistance, etc. are lowered, and it is not good when considering economic problems.

The water-soluble hydrazine compound (B) uses pohoaliphatic dihydrazidecarboxylic acids having 2 to 18 carbon atoms such as dihydrazide adipic acid, dihydrazidemalonic acid, dihydrazide glutanoic acid and dihydrazide sebacic acid. The amount of the water-soluble hydrazine compound (B) is 0.1 to 10% by weight based on the total amount of the polymerizable unsaturated monomer mixture forming the resin (A). If the amount is less than 0.1% by weight, the reaction of the activated carbonyl group is insufficient, which causes a decrease in adhesion. Moreover, when it exceeds 10 weight%, the water resistance, moisture resistance, and adhesive force of an adhesive fall.

Copolymer resin obtained by adding a chain transfer agent to the polymerizable unsaturated monomer mixture composed of the active carbonyl group-containing polymerizable unsaturated monomer (a), the acid group-containing polymerizable unsaturated monomer (b), and other polymerizable unsaturated monomers (c). An aqueous aric emulsion composition was synthesized based on a water-dispersible resin composition (A) and a water-soluble hydrazine compound (B). The aqueous dry lamination adhesive composition was further prepared by further adding styrene acryl copolymer, polyethylene wax, inorganic filler, and particle sedimentation inhibitor.

The amount of the aqueous acrylic emulsion composition was used 40 to 80% by weight, preferably 50 to 70% by weight relative to the total weight of the aqueous dry lamination adhesive composition. If the amount used is less than 15% by weight, the adhesive force is lowered, and if the amount is more than 80% by weight, the cutting property is reduced.

The base soluble acryl styrene copolymer was used to improve the redissolution of the aqueous dry lamination adhesive composition. The amount of the styrene acryl copolymer resin was used in an amount of 15 to 35% by weight, preferably 20 to 30% by weight, based on the total weight of the aqueous dry lamination adhesive composition. If the amount of use is less than 15% by weight, the re-dissolution property is poor, and if it is 35% by weight or more, the adhesive force decreases.

The polyethylene wax was used to improve the slip property of the coating surface of the aqueous dry lamination adhesive composition. The amount of polyethylene wax used was 3 to 20% by weight, preferably 5 to 10% by weight. If the amount used is less than 3% by weight, the slip property is lowered, and if it is 20% by weight or more, the adhesive strength is reduced.

The inorganic filler was used to impart blocking resistance and cutting property during stamping of the aqueous dry lamination adhesive composition. The amount of the inorganic filler used was 3 to 30% by weight, preferably 5 to 10% by weight. If the amount of use is less than 3% by weight, blocking occurs, and if more than 30% by weight, the adhesion decreases.

The particle sedimentation inhibitor was used to prevent particle sedimentation of the aqueous dry lamination adhesive composition. The amount of the particle sedimentation inhibitor used was 0.1 to 10% by weight, 1 to 5% by weight. If the amount is less than 0.1% by weight, the particle settling speed of the inorganic filler is fast and the redispersibility is low. If it is more than 10% by weight, the leveling is not good, the coating state is not uniform.

The emulsion polymerization method generally includes a single continuous monomer homogeneous dropping method and a core-shell polymerization method using a multistage monomer feed method.

The aqueous dry lamination adhesive composition of the present invention thus prepared is applied on an aluminum deposition layer on a layer arranged in the order of a polyethylene terephthalate (PET) layer, a release agent layer, a colorant layer, and an aluminum deposition layer in order to form an aqueous lamination adhesive layer. Eco-friendly hot stamping foil (Hot stamping foil) was prepared. In the aqueous dry lamination adhesive layer, the coating amount of the adhesive layer is preferably coated with 0.7 g / m 2 to 1.3 g / m 2, and more preferably 0.9 g / m 2 to 1.1 g / m 2. If the coating amount is less than 0.7 g / m 2, blocking properties and cutting properties are increased, but adhesive strength is decreased. In addition, if the coating amount is more than 1.3g / ㎡ the adhesive force increases but the cutability and blocking resistance decreases and the manufacturing cost increases.

     Hereinafter, the present invention will be described in more detail with reference to Examples. Since these examples are only for illustrating the present invention, the scope of the present invention is not to be construed as being limited by these examples.

1-1. Preparation of Aqueous Aqueous Emulsion

1 g of a reactive surfactant (AQUARON KH-05; manufactured by Jeil Pharmaceutical Co., Ltd.) was added to 180 g of water in a reaction vessel for preparing a conventional acrylic emulsion equipped with a stirrer, a thermometer, a dropping device, and a reflux cooler, and the temperature was raised to 75 ° C. A monomer emulsion was prepared by homogeneously emulsifying a mixed solution of monomers, emulsifiers and water in a separate container using a homomixer as follows.

The monomer emulsion is 16 g of reactive surfactant (AQUARON KH-05; Cheil Industries), 25 g of activated carbonyl group-containing polymerizable unsaturated monomer (a) (Diacetone acrylamide), methyl methacrylate (c-1) (MMA, Methyl Metacrylate) 145 g, butyl methacrylate (c-1) (BA, Buthyl Acrylate) 327 g, β-carboxyethyl acrylic acid (b) (β-CEA, β-Carboxyl Ethyl Acrylate) 14 g, glycidylmethacrylic acid ( c-1) (GMA, Glycidyl Methacrylate) 5g, α-methyl styrene dimer (chain transfer agent) (α-Methyl Styrene Dimer) was prepared by mixing and 190g of water.

In a separate vessel, 1 g of ammonium persulfate (aqueous free radical polymerization initiator) (Ammonium Persulfate) and 20 g of water were uniformly emulsified using a homomixer to prepare a dropping initiator aqueous solution.

5% of the monomer emulsion prepared above and 5% of the prepared dropping initiator aqueous solution were added to a reaction vessel at 75 ° C., and an initial polymerization reaction was performed for 20 minutes. At this time, the internal temperature of the reaction vessel rose to 80 ℃. After completion of the initial reaction, 95% of the monomer emulsion remaining and 95% of the dropping initiator aqueous solution were uniformly dropped at 80 ° C for 3 hours. After completion of the dropwise addition, the mixture was cooled for 1 hour after aging. 4 g of ammonia water (25%) was added to the reaction vessel to terminate the emulsion polymerization to prepare an emulsion resin.

Thus, the aqueous resin emulsion was prepared by mixing 160 g of a 10% aqueous solution of hydrazide adipic acid (B) with 933 g of the emulsion resin thus prepared. The aqueous aqueous emulsion thus prepared has a physical content of 50.5% solids concentration, viscosity of 150 cps, pH: 7.3.

1-2. Preparation of Aqueous Aqueous Emulsion

Aqueous aqueous emulsion was prepared in the same manner as in Example 1-1, except that 145 g of methyl methacrylate was changed to 180 g and 327 g of butyl methacrylate was changed to 292 g in the method of Example 1-1. It was. The aqueous aqueous emulsion thus prepared has a physical content of 50.2% solids concentration, 130 cps viscosity, pH 7.4.

Example 2 Preparation of Aqueous Dry Lamination Adhesive Composition

The aqueous acrylic emulsion prepared in Example 1 (Examples 1-1, 1-2) as a main component, and further added to the styrene acrylic copolymer, polyethylene wax, inorganic filler, and particle sedimentation inhibitor to dry the aqueous Lamination adhesive compositions were prepared (Table 1).

TABLE 1

Experimental Example 1. Evaluation of Aqueous Dry Lamination Adhesive Composition

The properties of the aqueous dry lamination adhesive composition of the present invention prepared according to the above production examples were evaluated by dividing them into items of adhesion, blocking, and cutability.

The adhesive strength was measured by cutting the surface transferred to paper into 1 × 1 mm size (Cross cutting) and peeling off the cellophane tape. The measured value was expressed as follows.

○: Good adhesion, 90% or more transfer surface

(Triangle | delta): Adhesive state, 60-90% transfer surface is a state

×: Poor adhesion, less than 60% transfer surface

The blocking property is to put the stamping foil coated with the adhesive layer (wounded several sheets of pressure on the film) in a constant temperature and humidity chamber, and to stand at 60 ° C and 75% RH for 24 hours, and then visually determine the transition state to the back side. The measurement value was expressed as follows.

○: Good blocking resistance, less than 10% of the back before the occurrence

(Triangle | delta): Blocking resistance Normally, 10-40% of back electric shocks generate | occur | produce.

×: Poor blocking resistance, more than 40%

The cutting property was an automatic cylinder transfer machine. The cutting property was evaluated by the square lattice (0.3 mm, 0.6 mm, 1.0 mm) in the mold, and the resolution of the square pattern during transfer.

○: Good cutability, 0.3mm grid pattern resolution is good

(Triangle | delta): Cutability Usually, the resolution of a 0.6 mm grid is good, but the resolution of a 0.3 mm grid is poor.

×: Poor cutting, 1.0mm lattice resolution is good but 0.6mm lattice resolution is poor

The evaluation results for the adhesion, blocking, and cleavage items are shown in Table 2 below.

TABLE 2

As a result, excellent adhesion, cutting, adhesion, and winding of the film to the adherend, even with the conventional dry lamination adhesive of the present invention, without the use of conventional solvent-type dry lamination adhesives It was found that the blocking resistance that transfer should not occur on the back side (the opposite side) in the state of (Winding) was excellent.

As described above, according to the present invention, nonylphenol (Nonyl Phenol) -type surfactant, volatile organic, which adversely affects the reproductive function by disturbing the normal hormone action (endocrine disrupting action) conventionally used in the preparation of aqueous aqueous emulsion Eco-friendly hot stamping foil can be manufactured using environmentally friendly eco-friendly one-component aqueous dry lamination adhesive composition without using solvent (VOC) and harmful substances such as lead, cadmium, mercury and chromium. have.

In addition, the eco-friendly one-component aqueous dry lamination adhesive composition of the present invention is excellent in adhesion and cutting (cutting), adhesive strength to the adherend, and the transfer should not occur to the back (opposite side) in the state of winding with a film (winding) It has excellent blocking property and can be suitably used for the production of hot stamping foil.

Claims (6)

delete Water-dispersible resin composition (A) consisting of active carbonyl group-containing polymerizable unsaturated monomer (a), acid group-containing polymerizable unsaturated monomer (b), and other polymerizable unsaturated monomer (c), water-soluble hydrazine compound (B), emulsifier, water-soluble An environmentally friendly one-component aqueous dry lamination adhesive composition for thermal transfer printing, further comprising an aqueous acrylic emulsion containing a free radical polymerization initiator and a chain transfer agent, a styrene acryl copolymer, polyethylene wax, an inorganic filler, and a particle sedimentation inhibitor. The method of claim 2, wherein the polymerizable unsaturated monomer (a) is one or more selected from the group consisting of diacetone (meth) acrylamide, acetoacetoxyethyl (meth) acrylate, and acetoacetic acid vinyl ester Eco-friendly one-component aqueous dry lamination adhesive composition for transfer printing. 3. The acid group-containing polymerizable unsaturated monomer (b) according to claim 2, wherein the acid group-containing polymerizable unsaturated monomer (b) is acrylic acid, metaacrylic acid, crotonic acid, isocrotonic acid, α-ethylacrylic acid, β-ethylacrylic acid, β-propylacrylic acid, β Isopropyl acrylic acid, itaconic acid, maleic anhydride, fumaric acid, β-carboxyethyl acrylate, p-vinylbenzenesulfonic acid, p-acrylamide propanesulfonic acid, t-butylacrylamide sulfonic acid, 2-hydroxy (meth Eco-friendly one-component aqueous dry lamination adhesive composition for thermal transfer printing, characterized in that at least one selected from the group consisting of phosphate monoester of acrylate, and phosphate monoester of 2-hydroxypropyl (meth) acrylate. The said other polymerizable unsaturated monomer (c) is an acrylate alkyl ester (c-1), a styrene-type monomer (c-2), an acrylonitrile (c-3), and a hydrolyzable silyl group. Polymerizable unsaturated monomer (c-4), hydroxyl group-containing polymerizable unsaturated monomer (c-5), amide bond-containing polymerizable unsaturated monomer (c-6), epoxy group-containing polymerizable unsaturated monomer (c-7), and polyfunctional Eco-friendly one-component aqueous dry lamination adhesive composition for thermal transfer printing, characterized in that at least one selected from the group consisting of vinyl group-containing polymerizable unsaturated monomer (c-8). According to claim 2, wherein the adhesive composition is 40 to 70% by weight of the aqueous acrylic emulsion, 15 to 35% by weight of soluble styrene acrylic copolymer, 5 to 10% by weight of polyethylene wax, 5 to 10% by weight of inorganic filler, and particles Eco-friendly one-component aqueous dry lamination adhesive composition for thermal transfer printing, characterized in that the sedimentation agent 1 to 5% by weight.