TW574327B - A component of water base resin for coating purpose - Google Patents

Description

574327 V. Description of the invention (1) The present invention relates to a water-based resin composition for coating, especially a moisture resistance that can be improved. It mainly improves the dissociation property of waste paper regeneration. It is more excellent. A water-based resin composition for coating, and a method for manufacturing such a moisture-resistant coating (Coat) agent product. Lamina ted paper is widely used as a packaging paper that requires moisture resistance in the past. However, although such a case has excellent moisture resistance, it is considered from the aspect of resource saving after use. When it is used as old paper and it is intended to be reused, it has no dissociation property, so it becomes a big problem. It is also a recyclable, moisture-resistant coating agent with good dissociation properties, using a vinylidene chloride copolymer latex resin. However, paper products with such coatings are not ideal because they are not likely to produce harmful substances such as dioxin when burned. In contrast, as a coating water-based resin composition capable of obtaining dissociative moisture-proof coating paper, it is obtained by adding water-dispersible waxes to latex resins such as synthetic rubber latex and acrylic latex. Various components of this have been disclosed (see Annex 1: Japanese Patent Publication No. 55-2259, Annex 2: Japanese Patent Publication No. 62-28826, etc.). However, at this time, when compared with the laminated paper of polyene coated with the same thickness, although the same degree of value is obtained in terms of moisture resistance, when it is actually industrially produced, it is used to match the viscosity of the coating machine and The fluidity, and the addition of various complexes, its moisture resistance will be reduced, and the moisture-proof surface will overlap with each other, and the problems of lowering bolting resistance will occur. Therefore, its performance is inferior to that of thin laminated paper. The truth. In order to improve the use of synthetic rubber-based 1 a t e X, acrylic latex, etc.

V. Description of the invention (2) Moisture resistance of milk, =, and water-dispersible wax composition With U cloth :: Change the blended component #, but still be able to protect the mold against moisture resistance J = f Discuss and study. It is an effective method to simply make the water dispersible wax gp of S1 in the moisture-proof composition. However, this 2J has a problem of migration to the wax surface, that is, the problem of adhesion and fragility of the coating layer. As a method to match the situation of the coating machine, the thickening caused by the addition of water-soluble surface = and the improvement of the fluidity, but this will make the resistance to the humidity condition of 〇1 eking Reduced tendency. In addition, since these polymers are sensitive to moisture under high humidity conditions and will reduce water vapor permeability, it is common practice to minimize the amount of use or not to use them. Although various inorganic substances have been added, methods for improving the moisture resistance have also been disclosed (see Annex III, JP-A No. 9 Publication No. 7995 =). However, there are also cases where the moisture resistance is too high to be widely used. In addition, there are also people who have reduced the moisture resistance accompanying the thickening caused by the addition of water-soluble polymers and the improvement of fluidity. Published a method of drying the cloth at the time of fabrication, and let it be bridged to avoid water resistance, that is, moisture resistance, and a method of lowering (see Annex 4: JP 9-268494 A). However, ‘in fact’ the moisture-blocking resistance is insufficient, and the coating process is complicated, and the problems of poor stability of the composition need to be overcome. Please refer to the translation of Annex 5 for the aforementioned Annexes 1 to 4. The object of the present invention is to provide an aqueous resin composition for coating, which has the same or superior moisture-proof performance as the conventional method for laminating polyolefins. 574327 5. Description of the invention (3); in particular, Adjusting the drying speed, etc., is inferior in moisture resistance, and it is advantageous when recycling waste paper. In addition, the inventors made an effort to check the results of the moisture-proof coating of the composition, and found that the specific results are effective. Therefore, the present invention is based on the moisture-proof coating ingredients of which the main ingredient is fat-making. The pigments that are added to the composition are added to the composition, and a specific compound is added to produce moisture resistance. The moisture-proof property of the coated product of the present invention is even higher. The product of the composition can be compounded by a water-soluble polymer. Moisture-resistant coating made of crystalline water with a melting point of 25 ° C or less. The water-soluble chemical structure is made of crystalline water. The branch becomes a water-soluble state, and the coating machine can be used to increase viscosity and improve fluidity. Compared with the method of laminating a polyolefin, it is also excellent in properties, moisture bolting resistance, and dissociation resistance, and a method for producing such a moisture-resistant coating water-based resin product is also economically provided. The present invention is based on the improvement of the moisture resistance of various synthetic resin latexes. When a water-based latex resin layer agent with good moisture resistance is made, a moisture-proof coating composed of waxes based on water-based latex resins, modified for blocking properties, and plastic particles is added. Moisture-proof coating agent whose crystalline water-soluble polymerizability has been improved in the molecular weight range of the agent. In addition, in order to coat paper products with an aqueous resin composition, it has been found that when the coated aqueous resin of the present invention is stored under specific conditions, the crystallization of crystals can be promoted, and high-quality products can be provided. Manufacturing method. Above 130 ° C and below, molecular weight is above 50,000. 10 Soluble compound is a general term, that is, a polymer having a range of shapes when it is in a water-containing state mixed with a large amount of water, and above 25 ° c. 13

574327 V. Description of the invention (4) In the non-aqueous state below 0 ° C, the homogeneous crystallized part derived from its chemical structure will be a general name for the plutonium molecular compound formed in the molecule: More specifically, When the water-repellent coating resin composition with improved moisture resistance of the present invention is coated on paper, it does not show crystallinity under the condition of losing water, and the coated paper product is cooled under engineering and or storage conditions. It is necessary to crystallize. Therefore, in the coating water-based resin composition with improved moisture resistance of the present invention, the crystalline water-soluble polymer compound contained must have a melting point of 25 ° C to 130 ° C, and a melting point of 40 ° c or higher. A crystalline water-soluble south molecular compound with a melting point of 100 ° C is most desirable. The molecular weight of the crystalline water-soluble polymer compound must be more than 50,000 and less than 10 million. When the molecular weight is less than 50,000, it is likely to be water-containing under humid conditions, thereby reducing the moisture resistance. On the other hand, if the molecular weight is more than 1 million, the tendency of these crystalline water-soluble polymer compound aqueous solutions to adsorb other substances in the water: solution will increase, because the coating of the aqueous resin composition will be agglomerated ' It cannot be an aqueous resin composition which can be easily applied. Chemical structures that show water solubility and crystallinity include Cel lulose (cellulose) -based poiy-oxyethylene (polyethylene glycol) structures, and Hydroxyethyl cellulose (hydroxyethyl Cellulose), Hydroxypropyl cellulose (Carboxymeyl cellulose), and Polyethylene oxide (Polyoxygen) which ring-opens and polymerizes Ethylene oxide 'Propylene oxide' (Ii) 'Polypropylene oxide' and these Block copolymers. As a crystalline water-soluble polymer compound used in the present invention,

574327 V. Description of the invention (5) Polyoxyehtylene oxide (polyoxyethylene) with a molecular weight of 50,000 to 1 million. The use of a compound in which a part of the hydroxyl group (Hydroxyl group) at the end of Polyoxyethylene oxide is also effective for preventing a decrease in water resistance caused by the hydroxyl group. In the coating water-based resin composition of the present invention, the amount of the crystalline water-soluble polymer compound is also important, and it must be 5% or more and 5% or less. When the content is less than 0.05%, the improvement of moisture resistance caused by crystallization cannot be exerted. When the content is more than 0.05%, it is easy to be exposed to water when wet, and the effect of moisture resistance is large. reduce. Although a particularly desirable content depends on the composition of the water-based resin composition imparted with moisture resistance, the solid content of the water-based resin composition is 0.25%. When the paper-like thin-layer material is coated with the coating water-based resin composition of the present invention, in order to improve the moisture-proof performance to a high degree or to exhibit high thirst-proof property early, the coated object is preferably stored in the coating application of the present invention. Under the condition that the water-soluble polymer compound in the aqueous resin composition is easily crystallized. That is, the coated object that has been subjected to the drying process is usually excessively dried, and it takes a long time to crystallize. It can be promoted by giving humidity to the over-dried coated object under conditions of ^ V # J ^ 25 〇c ^ 5 ^ ^ ^ 'or more, and it can be easily achieved by storing for more than 100 hours. The paper product having the moisture-proof property of the present invention coated with a good coating water-based resin composition is dried, and the paper product having the properties of wetness and dissociation can be obtained by drying. The coating water-based resin composition of the present invention imparts the same water dispersion as the water-dispersible moisture-proof property, which is equal to or equal to > Shoshino and has high

Page 10 574327 5. Description of the invention (6) Degree of moisture resistance and good dissociation. Therefore, it is possible to eliminate the disadvantages of the conventional moisture-proof property and the moisture-proof property, which is difficult to achieve, and to provide the coating with a water-based resin. X ^ The water-based coating resin composition of the present invention refers to a kind of water dispersion resins collectively composed of one or more emulsions and latex, and if necessary, it is mixed to provide high moisture resistance. Μχ and various additives used to improve blocking properties. Paper products coated with these compositions are dissociated when recycled as waste paper. As a raw material for paper, they can be used as reusable products, so they have begun to be used in place of plastics such as laminated polyethylene films. The project within the technology has been done in the prior art: "Secondary"; 2. The coating water-based resin composition of the present invention is applied to various known moisture-proof properties described in this item: Add a melting point of 25t or more and 13 (rc or less) to a crystalline water-soluble polymer compound that has a melting point of less than or equal to # 2,000,000 or more; a coating water-based resin composition having improved wettability. In addition, the paper product coated with the water-resistant resin composition coated with an anti-invention coating: $ = =: f South-end moisture-proof property can be applied to a paper product coated with the & Preserved under specific conditions, you can get paper products with two = wetness. Also, the solid content of the anti-composition composition of the same degree is 5% or more and 5% or less in an aqueous solution. Material coating 3 you, add a melting point of 25 t or more and 130 o t or less, the molecular composition of the tree , Crystalline water-soluble polymer + & al 1% or less 10 00 000 a knife compound, measures can be easily obtained by the present mixing

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x tί: raw! Water-improved coating water-based resin composition. In order to save the coating water-based resin composition of the present invention, if the value of "if if ^%" is "highly improved in performance or high moisture resistance can be exhibited at an early stage ea ^ Z 2% or more" Over 100 hours, it is easy to impart a high degree of moisture resistance in a short period of time. [Examples] Although the present invention will be specifically described based on examples and comparative examples, the present invention is not limited thereto. In addition, in the examples, The amount and% each represent parts by weight and% by weight. [Production Example of Moisture-Proof Coating Coating with Water Resin Composition] Place 62 parts of Sty rene (styrene), 2-ethyl-hexy-lacry in a container in advance. 34.5 parts of iate (isooctyl acrylate), 3.5 parts of Methacry i ic acid, q.5 parts of Dodecylbenzene sodium sul-fonate and deionized water 6 〇Parts are stirred for emulsification. 40 parts of deionized water is placed in a reaction device equipped with a stirrer, a reflux cooler, a thermometer, a nitrogen introduction tube, and a dropping device, and the internal temperature is raised to 75 ° C. Water is dissolved into 10% Presulfuric ammo 20 parts of aqueous solution, hold for 10 minutes, and then take 4 hours to drop the emulsion adjusted in the aforementioned container beforehand. During this period, adjust the internal temperature of the reaction equipment to 73 ~ 78 ° C, and perform emulsion polymerization. The temperature was raised to 80 ° C at the same temperature, and after 2 hours of aging, it was cooled to room temperature, and then 1.5% of 25% ammonia water was added to obtain 45.6% solid content, ρΗ8.3, viscosity 130cp, and Tg 17 °. C, milky particles with particle diameter 0.2 5 // m

Page 12 574327 V. Description of the Invention (8) (Emulsion). 70 parts by weight of the resulting latex was mixed with 30 parts by weight of 3 cents latex "DS-6〇2" (manufactured by Dainippon Ink Co., Ltd.), and wax emulsion "EW-" (Paraffin wax, manufactured by Futaba Fine Co., Ltd.) 1. 5 parts by weight 'provides a water-resistant resin composition for imparting moisture resistance to a wide range of applications. [Preparation Example 2 of a water-resistant resin composition coated with moisture resistance] In a container, 62 parts of Styrene (styrene) and 2-ethy acrylate were placed in advance.

3.5 parts of acid (fluorenyl acrylic acid), 15 parts of Dodecylbenzene sodium sul-fonate and 60 parts of deionized water, stir and emulsify. Put 40 parts of deionized water in a reaction device equipped with a stirrer, a reflux cooler, a thermometer, a nitrogen introduction tube, and a dropping device, and let the internal temperature | rise to 75 ° C. 20 parts of an ammonium persulfate aqueous solution which was previously dissolved in deionized water to 10% was added, the temperature was maintained for 10 minutes, and the emulsified product adjusted in the aforementioned container was dripped for 4 hours. During this period, the internal temperature of the reaction equipment: was adjusted to 7 3 ~ 7 8 ° C, and the emulsion polymerization was performed. After the dropping was completed, the same temperature was raised to 80 ° C, and after ripening for 2 hours, it was cooled to room temperature, and then 1.5% of 25% ammonia water was added to obtain a solid content of 45.7%, pH 8. 4 、 Latex (Emu 1 si on) with a viscosity of 170cp, Tgl7 ° C, and a particle diameter of 0 · 11 // m. 70 parts by weight of the resulting latex was mixed with 30 parts by weight of SBR latex "DS-602" (manufactured by Dainippon Ink Co., Ltd.), Wax emulsion "EW-500" (Paraffin wax, manufactured by Futaba Fine Co., Ltd.) 1 β 5 parts by weight, A water-repellent resin composition for imparting moisture resistance to a wide range of applications can be obtained. [Example 1]

P.13 574327 V. Description of the invention (9) 101 · 5 parts of water-repellent resin composition and water-soluble polymer p〇lyethylene 〇xi-de (poly Ethylene oxide) "Alkox R-400" (melting point 65 ~ 67 ° C, molecular weight 180,000 ~ 250,000, manufactured by Mingcheng Chemical Industry Co., Ltd.), 5 parts by weight of 5% water solution, producing a coating with improved moisture resistance Covered with water-based resin composition. When using a wi re rod bar to apply by hand to a commercially available ppc paper, the coating water-based resin composition is applied, and the coating amount is 16 g / m2 based on the solid content, and then immediately dried at 1 30 ° C for 1 minute. , You can make moisture-proof paper. The paper which has been coated with a moisture-proof coating agent is regarded as a moisture-proof paper, and the results are shown in Table 1. [Example 2] The crystalline water-soluble polymer p 〇 1 y e t h y 1 e n e oxide "Alkox R-400" was replaced in Example 1. When the crystalline water-soluble polymer was mixed

5 parts by weight of 5% aqueous solution of Polyethylene oxide "Alkox R-150" (melting point 65 ~ 67 ° C, molecular weight 100,000 ~ 170,000, manufactured by Meisei Chemical Industry Co., Ltd.) can be coated with improved moisture resistance Use an aqueous resin composition. When a commercially available ppc paper is coated with this coating water-based resin composition by hand coating using a wire rod bar, the coating amount is 16 g / m 2 'on a solid basis, and then immediately at 1 3 0 ° C Drying for 1 minute can produce moisture-proof paper. The performance of this moisture-proof paper was evaluated, and the results are shown in Table 1. [Example 3] The crystalline water-soluble polymer Poly ethylene oxide "Alkox R-400" was replaced with that of Example 1. When the crystalline water-soluble polymer was mixed

Polyethylene oxide "Alkox R- 1 0 0 0" (melting point 65 ~ 67 ° C, min.

Page 14 574327 V. Description of invention (ίο) 250,000 to 300,000, Ming Cheng Chemical Industry Co., Ltd., can produce a coating with improved moisture resistance hi &, ^ u & 广 幻 踅 cover Use an aqueous resin composition. When = r =: a is applied to a commercially available paper, this coating is coated with an aqueous resin composition. The amount of coating is _2 ', and then S13G C is dried for 1 minute without moisture. The properties of this moisture-proof paper are shown in Table 1. [Comparative Example 1] h Replaced with the crystalline water-soluble polymer polyethylene oxide. "Alkox R-400" of Example 1, when the crystalline water-soluble polymer Polyvinyl alcohol (polyvinyl alcohol) PVA-117 [(strain ^ "Made by order". 5 parts by weight of a 5% aqueous solution can be used to produce a moisture-proof coating agent. When using a wire rod bar to apply by hand to a commercially available ρρ. Paper coated with this coating water-based resin The composition, based on the solid content, was coated at 16 g / m2, and then dried immediately at 1 30 C for 1 minute to produce a moisture-proof paper. The performance of this moisture-proof paper was evaluated. The results are shown in Table 1. [Comparative Example 2] The crystalline water-soluble polymer p 〇1 yethy 1 ene oxide "Alkox R-400" was replaced with that of Example 1. When the crystalline water-soluble polymer was mixed

Polyethylene oxide "Alkox E-60" (melting point 65 ~ 67 ° C, molecular weight 1 million to 1.2 million, manufactured by Mingcheng Chemical Industry Co., Ltd.) in a 5% aqueous solution of 5 parts by weight can produce a moisture-proof coating agent. This coating water-based resin composition has a high viscosity 'to form agglomerates. Water was added to the coating with the water-based resin composition. 10 weight: After diluted in parts, the wire-bar bar was used to manually apply the aforementioned material to a commercially available PPC paper. The coating amount was i6g /

Page 15 574327 V. Description of the invention (11) m2, and then immediately dried at 1 30 ° C for 1 minute, then moisture-proof paper can be manufactured. The performance of this moisture-proof paper was evaluated, and the results are shown in Table 1. [Comparative Example 3] A wire rod bar was used to manually apply paper to the water-repellent property-imparting coating water-based resin composition prepared in Production Example 1. The coating amount was 16 g / m2 in terms of solid content. Immediately dry at 130 ° C for 1 minute, then moisture-proof paper is made. The performance of this moisture-proof paper was evaluated, and the results are shown in Table 1. [Example 4] The water-repellent property imparted to the coating resin composition 1 0 1 · 5 parts and the crystalline water solubility were mixed in Production Example 2. Polymer 〇iyethy 1 ene oxide "Alkox R-400" (melting point 65 ~ 67 ° C, molecular weight 180,000 ~ 250,000, manufactured by Mingcheng Chemical Industry Co., Ltd.) 5 parts by weight of a 5% aqueous solution to produce moisture resistance Improved coating water-based resin composition. When a commercially available PPC paper is coated with this coating water-based resin composition by hand coating using a wire rod bar, the coating amount is 16 g / m 2 in terms of solid content, and then immediately at 130 ° C. Drying for 1 minute can produce moisture-proof paper. The performance of this moisture-proof paper was evaluated, and the results are shown in Table 2. [Example 5] The crystalline water-soluble south molecule P 〇1 ygthy 1 ene oxide "Alkox R-400" in Example 4 was replaced. When the crystalline water-soluble polymer was mixed, that is, the hydrophobic Polyethylene oxide "Paogen EP-15 ”(Melting point 55 to 57 ° C, molecular weight 100,000 to 170,000, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), 5 parts by weight of 5% aqueous solution can be used to produce water-resistant coating resins with improved moisture resistance.

Page 16 574327 Description of the Invention (12) Composition. When a commercially available pp C paper is coated with this coating water-based resin composition by hand coating using a Wire Rod bar, the coating amount is 16 g / m2 in terms of solid content, and then immediately at i3 (rc drying) In minutes, a moisture-proof paper can be manufactured. The performance of this moisture-proof paper is evaluated, and the results are shown in Table 2. [Comparative Example 4] The crystalline water-soluble polymer polily oxide "Alkox" replaced in Example 4 "R-400" can be produced by mixing 5 parts by weight of a 5% aqueous solution of a water-soluble polymer Hydroxy-ethyl cellulose (Hydroxyethyl cellulose) "Nat〇r〇s〇1 mr_5〇〇" (manufactured by Hercules) For coating

The water-based resin composition was evaluated in the same manner as in Example 4. The results are shown in Table 2. [Comparative Example 5] A wire rod bar was applied by hand to the paper. A water-based resin composition was pre-coated, and the coating amount was 16 g / m2 in terms of solid content, and then K13 (rc was dried for 1 minute to produce a moisture-proof paper. The performance of the moisture-proof paper was evaluated, and the results were obtained. As shown in [Test method and evaluation method]

Various test methods used in the present invention are summarized and described. [Moisture resistance evaluation method] A commercially available ppc: paper cloth is coated with an aqueous resin composition by hand coating using a wire rod bar, and the coating amount is g / i based on the solid content, and then immediately at 13G ° C After drying for 1 minute, moisture-proof paper was produced. The paper coated with the moisture-proof coating agent was subjected to the test in accordance with JIS-z 〇2〇8 within 5 hours.

Page 17 574327 V. Description of the invention (13) " ---- Evaluation of the vapor permeability, the result is taken as the moisture resistance just after drying. The water vapor permeability was measured in a constant temperature bath at a temperature of 25 ° C and a relative humidity of 60% and a temperature of 30 ° C and a relative humidity of 80% for a predetermined period of time. Its value is divided by a commercially available one measured simultaneously in the table? 〇176 七] ^ 16116 Water vapor permeability of laminated paper (that is, paper obtained by laminating Polyhtylene fiim of 152/1112), so that the moisture resistance of Polyethylene laminated paper is taken as a relative value of 1. 〇 [Simple dissociation test] After coating and drying, the coated paper stored at 25 ° C relative humidity 60% or more and stored for more than 1 week is cut to a width of 2.5 cm each. The paper was put into a household juice maker with 0.5 liters of warm water at 60 ° C, and stirred and mixed for 15 minutes. The discrete aqueous dispersion in the aforementioned project was placed on a barbed wire with an aperture of lm m and washed with sufficient water. Evaluate the number or area of paper or membranes remaining on the wire mesh. When the number is 50 or less, it means that the dissociation property is good. ^ According to the foregoing, the present invention has industrial applicability and practicability, and completely meets the requirements of σ invention Nandu technology thought. It has filed an application for an invention patent according to law.

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Claims (1)

574327γ Announcement VI. Scope of patent application 1 A coating water-based resin composition is a crystalline water-soluble compound containing a melting point of 25 ° C to 13 ° C and a molecular weight of 50,000 to 10,000. It is characterized by the addition amount of 5% to 5% of the solid content of latex (Emulsion). 2 The water-based resin composition for coating according to item 1 of the scope of patent application, wherein the latex is mainly an acrylic copolymer latex. 3. The coating water-based resin composition according to item 1 of the scope of the patent application, wherein the crystalline water-soluble compound is a compound having a polyoxyethylene chain (for example, Alkox R-4 of Mingcheng Chemical Co., Ltd.). 〇, R_15〇U 000, etc.), in addition, a part of the end of the polyethylene oxide chain can be replaced with a hydrophobic group (such as Paogen EP-15, etc.). "" 4 = = item; item / kg of the coating water-based resin composition, ",": Fengshe said a resin composition, the product method after coating is characterized #. * K Manufacturing of moisture-proof properties 1 The coating fee m as described in item 4 of the scope of patent application, wherein the manufacturing method promotes the crystallization of the conditional lipid composition at a degree of m or more and stored for 100 hours: its ^ Relatively wet