TW473486B - Potentially hydrophilic resins and compositions comprising the same - Google Patents

Abstract

A potentially hydrophilic resin comprises at least monomer units readily saponifiable under alkaline conditions to form carboxyl groups, carboxyl-containing monomer units, and hydroxyl-containing monomer units. A potentially hydrophilic resin composition comprises, in a liquid medium, the potentially hydrophilic and an adhesive component or film-forming component. A recycling method is provided for an article with a coating applied on a surface thereof. According to the recycling method, the coating on the surface of the article is formed with the potentially hydrophilic resin composition, and subsequent to use of the article, the article is treated with alkaline water to saponify methyl acrylate in the coating such that the coating is caused to swell, and the coating so swollen is removed from the article.

Description

473486 A7 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs __B7_ V. Description of the invention () [Field of the invention] The present invention relates to a "potentially hydrophilic resin and a resin containing the resin", and Contains the composition of this resin and how to use it. [Explanation of the previous technology] In recent years, plastic products have been used in various containers and packaging bags. The surface of many plastic products has printing or sheet-shaped printing on the surface of the article. However, plastic products are low-decomposers in nature, and some plastic products are usually separated or recycled using segregation or recycling methods in order to consider their energy saving and economic factors. However, plastic products still contain some coatings. Printings or the like must be recycled in the whole or color-added recycled materials. The economic value of recycled plastic products is reduced and in many cases it may not even be possible to reuse them. In some cases, this recycled plastic product will have disadvantages at the joint. Many plastic products are coated with a layer of pigment or similar products on the surface. It is exposed to incineration by combustion, which causes environmental pollution due to incineration to produce dioxide, and even causes social problems. As a result, the use of this method on printed coated plastic products or similar products will reduce their recycling and reuse rates. Cause loss of interest. For the loss of plastic products mentioned above, some methods have been proposed to remove colored plastic products so that the plastic products can be used again, for example; the method disclosed in JP 52-26549; this printed plastic product is used to Organic solvent treatment decomposes and peels off the paint applied on the product or printing to produce discoloration. In addition, organic solvents are used to remove _2 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back before this page)

、 1T line 473486 A7 _____________B7__ 5. Description of the invention () In the color treatment, 'often consumed in liquid, so the recovery and separation of organic solvents are required'. Organic solvents are dangerous and flammable, so they must be reliable solvents. To solve many problems, it is necessary to install explosion-proof equipment and management accordingly. On the other hand, the method of using alkaline water to solve printed plastic products is simple and economical, but it is not easy to separate the coatings by using alkaline water treatment. The film formed by the applied coating contains hydrophilic components, such as; urethane resins, acrylic resins, cellulose-base resins, rosin, or ethylene -Ethylene-vinyl acetate copolymer. A better method is discussed in Japanese Patent Publication No. 58-152913. This method uses the addition of an alkaline-condition-soluble resin or a hydrophilic resin to the printing ink used in printed matter. "This product printed with ink is used to remove the surface of the object by alkaline water treatment. The advantage of this method is that under alkaline conditions, it will be combined with the physical properties of the ink to cause peeling. The method of ink can solve a limited range, for example; printing ink may suffer from floc_cculati〇n or thickening or reduce gloss and transparency during printing. This lack of characteristics will also be regarded as Printing ink is used, among other things. When alkali-based resin is added, the compatibility between the resin and the printing ink should also be considered. — However, when the resin has no elastic properties in the printing ink, even if an alkaline cold-cooling resin or a hydrophilic resin is added, it is not easy to peel off even if it is peeled off. In addition, the separation of the fragments will turn into a pulverized state. Dispersed in the treatment solution, however, recovery requires expensive filters. (Please read the precautions on the back before this page) Order Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

V. Description of the Invention ([Problems to be Solved by the Invention] The above-mentioned problems are solved by using the prior art. The potential hydrophilic resin of the water species of the present invention makes it as much as possible to be used for testing. Coating on plastic products Printing layer or similar layer or adhered to the P brush film layer made of plastic, to restore the plastic product to its original color (colorless), to make it dissolve, or to contain the resin component and the method used by the component; make it easy It is separated from the film layer of coating printing or printing. [Means for solving the problem] β The above-mentioned subject is mentioned in the following of the present invention, and the potential hydrophilic resin (a potent iaUy hydrophiUc resin) (hereinafter referred to as the resin of the present invention) is at least composed of monomer units that are easily saponified under experimental conditions to form a bond; a carboxyl monomer unit, a monomer unit containing the same, Potential hydrophilicity = lipid component (hereinafter referred to as the resin component of the present invention), the resin (especially printing ink), adhesive and primer (pH post) or the like are also mentioned The method of use with resin components. Printed by the Consumers' Club of the Intellectual Property Bureau of the Ministry of Economics The present invention is a resin containing printing ink and has excellent characteristics because it does not contain any water-soluble resin that can dissolve itself. To remove the printing coating layer, it is only necessary to prepare a printing ink in advance and treat the coating in an alkaline solution. As a result, methyl acrylate (methy 丨 acry late) is used for printing coating, and is easily generated in alkaline solutions. Saponification, so that the use of hydrophilic resins in printing coatings will gradually increase, and the surface of the printed coatings will be swollen. 'It will be easily peeled from the surface of the coatings, so the printed coating layer is dissolved in alkali. In solution, it will also form fine fragments, such as thin paper. The paper size is suitable for Zhongguan Jiazheng (CNS) M specifications (2 Shu 297 public envy> 473486 A7

The film-like detachment allows easy separation of the alkaline solution used for printing and coating. The invention consists of a resin containing an adhesive component, and does not include any water-soluble resin that can be dissolved by itself. When the printing film is adhered to the article with an adhesive, the printing film has durability against moisture and dew condensation. Removal, only need to use alkaline solution for simple treatment on the article. In this way, methyl acrylate is used for adhesive coating, and saponification is easy to occur in alkaline solution. Such hydrophilic adhesive is used for coating. Gradually increasing the 'coating agent coating will produce a moistening phenomenon, so that the printed film layer is easily separated from the surface of the article, so the adhesive coating layer will dissolve in the test solution' while forming fine fragments, so it can The printed films adhered together are easily separated, so the separated adhesive coating layer and the printed film layer can be easily separated in the separation treatment liquid. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs when the article has a primer coating on the surface (prime CC) at, which includes: the resin of the present invention, the primer coating attached to the surface of the article, and printing The film is an undercoat layer that adheres to the surface of the article. The undercoat layer has durability against wet condensation. The primer itself does not contain any water-soluble resin. Or the removal of the printed layer of the film 'as long as the article is placed in a test water treatment'. As a result, the methyl acrylate is used on the undercoat layer, and saponification is easy to occur in the lye. Therefore, it is hydrophilic. The use of adhesives in the undercoat layer will gradually increase, and the undercoat layer will have a moisturizing phenomenon. In this way, the printed coating or the combined layer of the printed film layer and the undercoat layer can be easily separated. Therefore, the undercoat layer is Dissolved in lye water, at the same time _ 5 This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) '-473486 Printed by A7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs __B7 V. Description of the invention () Fine fragments are generated and separated from the printed coating layer or printed film layer, so the undercoat layer and the printed coating layer or the printed film layer are separated more easily after being treated by the treatment liquid. The three use methods described above are all based on the properties of the resin that will cause cross-linking; therefore, (a) macromonomers; (b) cross-linking agents and the resin of the present invention (C) forming a coating structure; for example, the printing coatings are combined with each other to use a cross-linking agent to act on the formed coating structure, or the above-mentioned characteristic technologies (a) to (c) are combined to improve The permeability of alkaline water (penet-rability) makes the alkaline water and the coating layer contact each other. Therefore, the separation method described above can be used to improve the separation of various coatings. According to the potential hydrophilic resins, components and methods of the present invention, an lye is used to remove the printed coating or similar layer on the plastic or the printed film layer adhered to the article, so that the plastic product is produced under colorless conditions. Recovery and regeneration, and after treatment with the treatment liquid, it is easier to coat or print the film. [Detailed description of the present invention] The following describes the specific details of the present invention. The properties of the potential hydrophilic resin of the present invention are at least composed of monomer units that are liable to produce saponification under alkaline conditions to form a carboxyl chain. Contains a carboxyl monomer unit and a warp monomer unit. The monomer is easy to saponify and form a carboxyl chain under alkaline conditions. Even though the acrylic acrylate has an excellent saponification rate under alkaline conditions, polymerizable unsaturated carboxyl compounds are also used because of their low alkyl esters. Article description_6_ This paper size is applicable to Chinese National Standard (CNS) A4 specification (21〇ί 297 ^ cent) (Please read the precautions on the back before this page) —Packing—

1T line 473486 A7 B7 V. Description of the invention (1) It is stated that fluorenyl acrylate is used as a representative monomer which is easily saponified under alkaline conditions to form a carboxyl chain. When a monomer group is contained, even though aery 1 ic acid or methacryl ic acid has an excellent copolymerization with ethyl acetic acid, it can polymerize unsaturated carboxyl groups in the past. All of the compounds may be used, and the following description refers to acrylic acid or methacrylic acid as examples containing carboxyl unit units. When it contains hydroxyl monomers, all its hydroxyl-containing monomers are user-friendly. However, hydroxylalkyl (meth) acrtlate and methyl acrylate will produce excellent results. Copolymerization reaction, because hydroxylalkyl (meth) acrylic acid (meth) acrtlate contains ethylene, propylene, butene (1), 716 and the like Alkenyl chain (311 ^ 161 ^ groups). The following is an example in which hydroxylalkyl (fluorenyl) acrylate ((meth) acrtlate) is used to represent a monomer containing a vinyl group. A preferred specific example of the present invention is that the macromonomer is generally composed of the above-mentioned monomers. All the useful macromonomers in the past have been in a certain range, which includes: the terminal is a double bond during polymerization, It is considered that a better macromonomer is included. For example, a hydrophilic resin is located at an end group and contains a polymerized macromonomer. Its molecular weight is from 4,000 to 30,000, which is proved to be a polystyrene resin and a polyacrylic acid ester. Resin (polymethacrylate ester resin) (the carbon number of the ester residual chain is 1 to 17), and its polymerizable chain is at a terminal group such as a methacryloyl group (methacryloyl groups). The above description is better. This paper size is applicable to China National Standard (CNS) 8 4 _ (21GX297 public attack) '(Please read the precautions on the back before this page) |

, 1T Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs J ^ -ΟΌ V. Description of the invention (A7 B7 generation of voluminous carcass unit 'The following is a description of the monomer of the resin of the present invention in a weight ratio. % By weight, in other words, fluorenyl methacrylate: 20 to 90% by weight, and preferably 30 to 80% by weight, (fluorenyl) acrylic script is 0.5 to 35% by weight, which is preferably 1.0 To 20% by weight, hydroxyalkyl t methyl) acrylate is 0.5 to 35% by weight, which is preferably 1.0 to 20 'macromonomer unit is 0 to 30% by weight, which is preferably 1 to 20% by weight % 'The other monomer component or composition is 5 to 75% by weight, preferably 5 to 50% by weight. Generally speaking, if it contains less than 20% by weight of methacrylic acid esters, only the effect of tritium will be produced. Its hydrophilicity is not enough to cause dissolution and cause the coating layer to be separated from the object to be coated. Acrylic acid is more than 90% by weight. For the coating layer of the resin after saponification, excessive south water solubility will cause the penetration of the lye into the coating layer to become slow and the time to remove the coating layer. Increase, and the above-mentioned maximum range containing methacrylate is not suitable. Generally speaking, when the content of (meth) acrylic acid is less than 0.5% by weight, the crusting produces sufficient hydrophilicity for the coating of the resin layer, so it takes time for the saponification treatment with methacrylate, but for coating The cloth layer is not enough to cause separation. When the content of (meth) acrylic acid is more than 35% by weight, the coating will produce excessive water and disintegrate, which may cause various physical properties of the coating layer, such as waterproofness. Generally, when it contains less than 0.5% by weight of hydroxylalkyl (meth) acrylate, the result is that the Chinese National Standard (CNS) A4 specification (210X297 mm) is applied to the coating layer at the methacrylic paper size. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 8 3 7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _______B7 V. Description of the Invention () Saponification of esters requires a period of time, but not enough to cause separation When S containing hydroxylalkyl (meth) acrylic acid is higher than 35% by weight, it may lead to the production of unsaturated resin products, so it may not be very practical. The resin product of the present invention is a series of water, hydroxyalkane Hydroxylalkyl (meth) acrylic acid S is intended to be used as an emulsifier during polymerization. Therefore, it is possible to obtain a resin with excellent stability and dispersion as much as possible. When the resin of the present invention is a non-aqueous series, its hydroxyalkyl ester The (hydroxyl-alkyl) (meth) acrylic acid ester unit is suitable as a reactive cross-linking agent, and the cross-linking agent will produce a cross-linking effect on the resin coating. When the giant single system is composed of the above-mentioned monomer components of the present invention, it is used from 0.1 to 35% by weight, and the macromonomer contains more than 30% by weight, which will cause the coating to be hydrophilic and water to enter the coating. The layer permeability does become very slow, so it takes time to fully saponify the methacrylate, and removing it from the coating layer also requires a period of time, and it is also considered unsuitable in the above maximum range. In the future The resin product of the present invention is a non-aqueous series, and its macromonomer improves the stability of the polymerization system. Therefore, it is a goal to obtain a resin with a high concentration solution as much as possible. The total weight% of fluorenyl acrylate and (fluorenyl) acrylic acid in the resin of the present invention is very important. When each of the monomer units represented is within the above range, the resin of the present invention is assumed to be 100% by weight, but usually All are in the range of 25 to 95% by weight, and the best range is 30 to 80% by weight. When it is less than 25% by weight, it is not enough to produce hydrophilicity and separate the coating from the article after saponification treatment. In other words, the weight% When it is higher than the above range, the resin will be excessively hydrophilic, which will result in resin coating removal rate_9_ This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) (Please read the note on the back first (Notes on this page)

, 1T line 473486 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. The description of the invention (removal rate) is not good. In addition, when the coating layer is removed or dissolved, it will turn into tiny fragments and lose the original It looks like this, so it is difficult to handle the solution and cause the paint to be separated and removed. The resin of the present invention has the above-mentioned composition of the monomer 'having one or more monomers to copolymerize the resin of the present invention, for example; the monomers include ... which have (meth) acrylic acid lower than others Alkyl esters and other methyl-acrylate; such as methyl methacrylate (MMA), ethyl methacrylate, n-propyl ( Fluorenyl) n-propyl (meth) acrylate, isobutyl methacrylate and tert-butyl methacrylate; maleic acid succinate (Dialkyl (Cl-C5) maleates) and maleic esters of monosuccinic acid (monoalkyl (Cl-05) 1118163 ± 63); methacrylic acid (11161: 1 ^ (^ 71 & -111111 (16), for example Ν, Ν'-Difluorenyl-fluorenyl acrylamide and N, Ν'-diethyl-fluorenyl acrylamide; the molecular weight of a single methacrylate of polyethylene glycol is 200 ~ 600; styrene ; Α-metyl styrenen; vinyl acetate and vinyl choride, which can be used alone It is estimated that 100% by weight of the entire monomer unit is mixed, and 0 to 50% by weight can be used, preferably 10 to 35% by weight. The present invention is performed with a polyfuctional ethylammonium monomer. Copolymerization, and part of the resin of the present invention is cross-linked and its cross-link density can be adjusted. When a polyfuctional ethylene monomer is added, its polyfuc-tional vinyl monomer The body unit component accounts for the entire 10 paper sizes. The national standard (CNS) A4 specification of the rich countries (21G X 297). ----- * ---------------- Order- -------- Line (Please read the note on the back? Matters before filling out this page} 473486 A7 B7 V. Description of the invention (Resin is 0 ~ 5% by weight, the best range is 0.1 ~ 3. 5% by weight. The use of a polyfu-ctional ethylammonium monomer allows the resin of the present invention to increase its cr-osssl inking degree as much as possible, and therefore, it will cause a beneficial effect in the future. The polyfuctional ethenyl monomers are as follows: divinylbenzene, ethyl diethyl acrylate ene glycol di (meth) acrylate), polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene dimethacrylate Among the esters (polyol) _pylene glycol di (meth) acrylate and tri- or tetra-methacrylic acid, the 'divinyl benzene' is particularly considered to be better. The resin of the present invention is described as a combination of monomers, which can be obtained by conventional polymerization methods. For example, the monomers are polymerized by emulsion polymerization, dispersion polymerization, or similar polymerization. : The above-mentioned polymerization method is considered to be a good method. The average molecular weight is about 10,000 to 100'000, the acid value is 8 to 25, and the hydroxyl value is 4 to 140. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Earth and Earth (please read the precautions on the back before filling out this page) Line: The resin composition of the present invention is composed of the components of the present invention or the components of the film described above with liquid as When the medium acts on the tree g, the ingredients will dissolve or disperse. The form is not unrestricted. For adhesives, e-alloys, etc., all inks, primers and similar layers will be like shirts. This resin, When the overall composition assumes 11 this paper size applies to China's National Standard "CNS" A4 (210 X 297 public love

It is 100% by weight, its solid content is 5 and its resin is 10 ~ 90% by weight. It is considered to be potentially hydrophilic. The horse is best to be 20% ~ not to weigh 詈%. Please go to 箪, please read the note on the back first. Please fill in this page again for the contents) Ingredients or film ingredients are the dosage of 85% by weight, and the other ingredients are 0.5 ~ 20% by weight β / 2, and 2% ~ 75% by weight. Straight $ / °, it is considered that the best is 1 ~ 15 weight. Its adhesive component or film component includes: protein, brisket, glue and: then: glue, polyisoprene rubber, neoprene rubber, butadiene "' , Ben: ene-butadiene copolymer rubber, acrylonitrile copolymer, ethylene acetate, ethylene diene copolymer, polyurethane, polyurethane, polyvinyl acetate, polyethylene, polypropylene and chlorine Chemical products, Min butyraldehyde resin, frog oxygen resin, coumaris s / g, J ', polyvinyl condensation and cyclized rubber.… Clear resin, ketone resin, chlorinated rubber mentioned liquid media can dissolve or disperse Adhesives of the resins of the present invention = ingredients or film ingredients, for example; water, methanol, ethanol, isopropyl alcohol-line: and, ethyl ethyl ketone, methyl isobutyl ketone, methylbenzyl, dihexanone or The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the resin of the present invention described above. When the pigment is added, it will form a traditional printing ink similar to that of the future. Adding adhesive ingredients to form an adhesive, use it. Agent as a base, but it must be formed Appropriate #_ ingredients become the ingredients of the bottom layer, in addition, there are plasticizers (such as dicyclohexyl phthalate, dioctyl phthalate, phthalate) Dibutyl acid, dibutyl adipate and other additives can be added. ________ 12 This paper size is applicable to & S A4 specification (χ Norwegian public hair-A7 A7 Intellectual Property Bureau, Ministry of Economic Affairs Printed by the employee's consumer cooperative. V. Description of the cloth, which is the method of collecting the material. It contains printed or painted articles. The resin components must include the pigment and dry resin components. Use of test water to generate interest and nails; Peng Run effect: brush coating layer 'so the coating will be hydrophilic and separated., 11 mesh Hairun's effect causes paint and articles to peel off the hair ^^ \' s recovery Another method of the present invention includes: coating tree moon g wounds on the object 0 矣 to form a coating surface, and then drying the resin component surface pattern or the printing characteristics of the ink, or coating with printing ink The saponification of the cloth and the printing on the surface of the sack layer, followed by thorough verification Brush production i :: This coating will be used for printing coatings and film agents to describe the method of the towel. The best method is considered to use cross-linking, ^ chain to complete 'that is, the reaction of the rhyme chain of the hair Printing coating layer or undercoat layer and adhesive layer, so that the coating or coating has excellent durability under normal conditions = resistance to wetting or dew condensation, in order to remove the coating layer, its cross-linking will promote alkaline water It penetrates into the coating layer, but in order to maintain the original appearance of the coating layer after removal, it is necessary to promote the separation of the solution, such as polyisocyanate compounds, polyoxo compounds, amino resins, and glutaraldehyde. Specific examples of polyisocyanate compounds include: bisurethan of diisocyanate, for example; toluene diisocyanate (TDI), 4, 4, ~ diphenylmethane diisocyanate (MDI), diphenylbenzene diisocyanate (XDI ), 13 (please read the precautions on the back before filling out this page) I * 丨 Line: This paper size is applicable _ Home Standard (CNS) A4 size (χ 29? Public issue) 473486 Employees of Intellectual Property Bureau of the Ministry of Economic Affairs Cooperation Printed clothing A7 B7 V. Description of the invention () Imidylene diisocyanate (HMDI) and isophorone diisocyanate (ipdi); the adduct of the above-mentioned diisocyanate phenylphenyl diisocyanate (TDI) Glycols and the like; polyisocyanates such as the terpolymer of diisocyanate (imer); block polyisocyanates are alcohols (ethanol, isopropanol, n-butanediol), phenol derivatives (phenol, nitrophenol) , Cyclic amidine (caprolactam) or active amyl compounds (diethyl malonate, ethyl acetate, ethyl acetate, acetone), in addition, carbon dioxide Ann crosslinking agents are also used from the above, and diisocyanates and derivatives are also mentioned. Examples of polyepoxides are triglycidyl isocyanurate, 3,4-epoxycyclohexylmethyl, and 3,4-epoxycyclohexylmethyl Ester (3, 4-epoxy-cyclohexanecar-boxylate), the amino resin of which is dimethylol urea, methylol melamine, butylated methylol melamine, except In addition, gluta-raldehyde, silane coupling agent, teraisopropyl titanate, acetyl acetotitanate, aluminum alcoholate ( Aluminum alcoholates) and aluminum chelates are also mentioned. Examples of the resin composition of the present invention include: various plastic products, for example; containers and wrapping films, glass products, wood products, and iron products. There is no mandatory restriction on the shape of these articles, and the dry coating of printing or coating thereof The thickness ranges from 0.01 to 20 μm. The thickness of the printed or coated layer is less than 〇 " m 疋 It is difficult to achieve uniform printing or coating. When the thickness of the printed or coated layer is higher than 20 // m Mine is uneconomical and impractical. 14 ϋ Zhang scale is applicable ^ National Standard (CNS) A4 specification (210 X 297 public love) I-(Please read the precautions on the back before filling out this page) · Line: Employees' Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printing V. Description of the invention ς) — ~~~~ — The method for printing or coating the resin composition of the present invention is traditional, and the methods include: gravure printing, surface coating, roller coating, transfer Coating, spraying, or similar coating lithography, or coating and printing of resin in segments, the invention does not mean continuous coating on articles, and the printing or coating will directly affect the object] Limiting printing may affect the adhesion of the coating on the surface of its articles. The surface of σ is also used in the method of the present invention. Will affect the coating removal of the present invention, for example; forming and forming of plastic films, similar products, patterns and similar printing or the adsorption of the two-phase type according to the present invention is broken into tiny fragments, and impregnated with plastic films and plastics Container, spring ^ j tear methacrylic acid brewing unit is saponified and tested at a low concentration ^, the shell ^ will produce a swelling phenomenon, for example; coating printing on the article or film printing adhered to the article is considered better Removal method is to put the item in alkaline water and keep the temperature of the good and mixing ~ g (TC, which is considered to be the best alkaline with caustic soda and sodium carbonate Water or similar saponification agent makes the coating resin swell. For saponification, it uses the organic solvent of methanol or ethanol to promote the saponification reaction. The present invention will be illustrated by the following examples and comparative examples, unless There are special instructions, and "" part " or " parts " and" both "refer to basis weight. Example 1] (Synthesis Example of the Fatty Acid A of the Invention) Ester (b utyl meth-acrylate) (20 parts), acrylic acid (5 parts), 2-fluorenyl acrylic acid u 7, m 15 This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) ----- --------------- tT --------- ^ # 1 ^ Jing first read the unintentional matter on the back before filling in this page) 473486

A7 B7 V. Description of the Invention () (2-hydroxyethyl methacrylate) (5 parts), polymerizable dioxysynthyl polyethylene (10 parts' molecular weight: about 6000), ethyl acetate (please read the precautions on the back first) Fill in this page) Ester (210 parts), isopropyl alcohol (90 parts), and azo-isobutyl (1.2 parts) are all put into a container and reacted in a nitrogen environment for 8 hours at 75 ° C. This mixed polymerization is distributed in a very finely dispersed state and has a solid content of 25% by weight. The average molecular weight of the resin is 20,000, the acid value is 38.9, and the hydroxyl value is 23.1. Before and after the saponification treatment, the resin of the present invention was analyzed by an infrared spectrophotometer and a gas chromatograph composed of a spectrophotometer. The results confirmed that when butyl methacrylate was combined with the residue, the methyl acrylate was selected as the saponification. The treatment agent is based on the monomer formulation table described in Table 1 for analysis and comparison of the present invention (A ~ F, Η) and the comparative resin (I ~ J): X Jincheng Example 2] ( Synthesis example of resin G of the present invention, methyl acrylate (66.5 parts), ethyi methacryl (22.1 parts), acrylic acid (6.7 parts), 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate) ) (3_3 parts), divinyl benzene (1.3 parts), (sodium dodecylbenzenesulfonate) (0.1 parts), potassium persulfate (0_3 parts) and deionized water (200 parts) are all Put it in a reaction container, and polymerize it in a nitrogen environment for 8 hours 7 (rc, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and the polymerized polymer polymerization pH is adjusted to 8 to impregnate the water-like caustic soda After 1 hour at medium temperature, its The resin's wetness will increase by 200 times (volume ratio). According to the comparison of resins in Table 1 of the monomer formulation, the same method is described. The results of the resin of the present invention listed in Table 2 are: Standard (CNS) A4 specification (21〇X 297) 473486 A7 _B7_ V. Description of the invention () [Table 1] Monomer formula table Resin monomer monomer ratio (weight) Solid content (° / 〇) Solvent A mmh / mmh / m 60/20/5/5/10 25 EtAc / iPA (7/3) B MA / St / AiVHBM / MS 50/20/10/15/5 50 Tol / iPA (1/1) C MA / St / NMA / AA / HEMA / MS 35/15/15/15/5/15 45 Tol / iPA (1/1) D MA / St / AA / HEMA4K 70/5/10/10/5 25 ME MA / M / M / HEMM1S / DVB 45/10/20/10/15 / 1.5 45 MF MA / iBA / AA / HEMA / MS 50/20/10/15/5 45 Tol / iPA (1/1) G MA / EMA / AA / HaiA / DVB 66.5 / 22.1 / 6.7 / 3.3 / 1.3 30 Water system Η MA / BIA / AA / HEMA 45/20/30/5 45 Tol / iPA (1/1) I BA / nDA 70 / 30 45 Tol / iPA (1/1) J St / AA 70/30 45 Tol / iPA (1/1) K St / nDA / BA 30/30/40 50 Water system Note: ΜΑ: methyl acrylate, BW [A: butyl methacrylate, AA: acrylic acid, HEMA: hydroxyethyl methacrylate , MS: the terminal group of polystyrene is acrylfluorenyl (molecular weight: 6000), Li A: methyl methacrylate, BMA: methyl butyl acrylate, ST: styrene, iBMA: isobutyl methacrylate, BT: butyl acrylate, nDA: dodecyl n-acrylate, DVB: divinylbenzene, EtAc: ethyl acetate, IPA: isopropyl alcohol, Tol: toluene, MEK: methyl ethyl ketone (please read the back first) Please note this page before filling in this page) I 111 丨 —Order • 丨 丨 11111-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 17 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ^ / 3486 Α7 90.9Π1ίΤ ^ 1 ----- B7__f na Description of the invention () ----- [Table 2] Results of the resin physical properties of the present invention Resin weight average molecular weight acid value, mg (KOH) / g hydroxyl grave value, mg ( KOH) / g A 20000 38. 9 23. 1 B 30000 77. 8 34. 6 C 25000 84. 9 11. 6 D 20000 77.8 34. 6 E Unmeasurable—155. 6 34. 6 F 30000 77. 8 34 6 G Unable to measure 52. 1 15. 2 Η 25000 233. 3 11.6 I 30000 0 0 J 20000 233. 3 0 K. 70000 0 0 Example 1 and Comparative Example 1 In the case of ink, the ink is composed of azo pigment (10 parts), acrylic copolymer (priming monomer: y lx ester, 12 parts), cellulose resin (3 parts), and polyethylene wax (3 parts). 2 parts), isopropyl alcohol (27 parts), propyl acetate (27 parts), and ethyl acetate (6.5 parts) (this ink was used in Comparative Example 1) 'For the printing ink of the present invention, the following is used The resin component (15 parts) replaces the resin component (15 parts) in the above ink. Example 1-1 The above acrylic copolymer 6 parts of cellulose resin 1.5 parts of resin A (invention) 7. 5 parts 18 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 cm) ( (Please read the notes on the back before filling out this page)

-Install ----------- Order ------ II Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 473486 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7! -------- -B7 90. 9. i 〇 Revised year a. 5. Description of the invention () Example 1-2 The above acrylic copolymer 6 parts of cellulose resin 1.5 parts of resin B (invention) 7. 5 parts of example 1- 3 parts of the above acrylic copolymer 6 parts of the cellulose resin 1.5 parts of the resin C (the present invention) 7. 5 parts of Examples 1-4 6 parts of the above acrylic copolymer of the cellulose resin 1.5 parts of the resin D (the present invention ) 7 · 5 parts block polyisocyanate (crosslinking agent) 0 · 15 parts Example 1-5 The above acrylic copolymer 6 parts cellulose resin 1.5 parts resin E (invention) 7. 5 parts Example 2 Example 2 An ink for gravure printing is prepared, which is composed of a titanium oxide pigment (32 parts), a urethane resin (23 parts), a cellulose resin (1 part), turpentine (0.4 parts), and polyethylene wax (0.55). Parts), toluene (26 parts), ethyl ethyl ketone (14.5 parts), ethyl acetate (8.4 parts), and isopropyl alcohol (7 parts) (this ink It is used in Comparative Example 2-1). For the printing ink of the present invention, the following resin component (24.4 parts) was used instead of the resin component (24.4 parts) in the above-mentioned ink. Example 2-1 The above amino aminoethyl resin 11.5 parts cellulose resin 0.5 part rosin 0_ 2 parts resin A (invention) 19 12. 2 parts I Γ -------- order- --------. ^ 91 (Please read the notes on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210 χ 297 mm) 473486 Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by Consumer Cooperative A7 B7 V. Description of the Invention (2) Example 2-2 The above amino aminoethyl resin 11.5 parts cellulose resin 0.5 part turpentine 0.2 part resin B (invention) 12. 2 parts Example 2-3 The above-mentioned urethane resin 11.5 parts of cellulose resin 0.5 part of turpentine 0.2 part of resin C (invention) 12.2 parts Example 2-4 of the above-mentioned urethane resin 11.5 parts of cellulose resin 0.5 parts of turpentine 0.2 parts of resin D (invention) 12. 2 parts of butylated melamine 12.2 parts Example 2-5 above-mentioned urethane resin 11. 5 parts cellulose resin 0.5 part 0.2 parts of turpentine resin E (invention) 12.2 parts of Comparative Example 2-2 Ethyl aminophosphonate Resin 11.5 parts cellulose resin 0.5 part turpentine 0.5, 2 parts comparative resin J 12.2 parts The following will describe the case of printing and coating using the above-mentioned ink. The printing and coating must have release, water resistance and adhesion properties. For testing. 20 (Please read the notes on the back before filling this page)

This paper size is in accordance with Chinese National Standard (CNS) A4 specifications (2) 0 X 297 mm. Description of the invention () But brush coated hibiscus # Ink each uses # 4 coating machine to coat polyester film to obtain The thickness of the dry film is in the range of m, and then it is performed at 80 ° C for 10 minutes (in the example 2-4, it is 15 °. (: It is dried for 30 seconds). Test method (1). Test of the separation printing film The temperature is controlled by immersion in a 1.5% sodium hydroxide aqueous solution, 85 C. After a period of pretreatment, the film is taken out of the warm-mixing heart solution, and the printed coating layer will be separated. The results are shown in Table 3. Medium. 〇p brush coating layer is completely separated, its poly film is the same as before printing. △: The printing part remains on the polyester film. X: The printing coating is completely left on the polyester film. (2). Waterproof test printing film is immersed in 85t of deionized water for 30 minutes to replace the test treatment solution to check whether the printing depends on separation. (3). Cellophane (cel lophane) tape does not separate the printed film during peel test. 473486 A7 B7 5 DESCRIPTION invention () Table 3 (1). Separation Test Results

Ink impregnation time (minutes) 5 15 30 Example 1-1 〇〇〇 Example 1-2 Δ 0 〇 Example 1-3 〇〇〇 Example 1-4 〇〇〇 Example 1-5 X Δ 〇 Comparative Example 1 XXX Example 2 -1 Δ 〇〇 Example 2-2 Δ 〇〇 Example 2-3 X Δ 〇 Example 2-4 〇〇〇 Example 2-5 〇〇〇 Comparative Example 2-1 XXX Comparative Example 2-2 XXX (Please read the back first (Please note this page before filling in this page) -3 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (2). The results of the waterproof test will not be separated in all cases. (3). Results of the adhesion test The print coating does not separate in all examples. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) /. 473486 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () Example 3 and Comparative Example 3 Adhesive X Thermal Viscosity adhesive (solid content: 50%) is based on the above resin K, glycerol tribenzoate and trimthylpropane tribenzoate with a solid weight ratio of 1.2 / 1.0 / 1.0 mixed. The adhesive Y is an adhesive used for the resin I described above. The composition of the adhesive is shown in Table 4. It is coated on paper labels. Aluminum is adsorbed by evaporation. It can obtain a thickness of 10 # m and then dried. The paper label and polyester film are l00. ° C is hot-pressed to adhere to each other. The composition of its adhesive uses glass plates, and glutaraldehyde is used as a catalyst and paratoluenesulfonic acid is 1% and 0.5%. Mix and add to adhesive solids. The adhesive composition was coated on a paper label in the same manner as above and dried, and dried on a glass plate at 150 ° C for 30 seconds. The results are shown in Table 4. Adhesion 0: exert X: no exertion Separability Each adhered sample is impregnated with 5% caustic soda solution at 70 ° C until the label is separated from the article and the elapsed time is calculated. (Please read the precautions on the back before filling this page)-* _0% This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) /. A7 B7 V. Description of the invention (, first 10H base materials, other He Zhu · Li Laizhi was removed, and it was classified as follows after 10 seconds of water ：: Koda 6 X: Adhesive coating completely peeled off △: About half of the adhesive coating remained: 0: The adhesive coating remained completely [Table 4] Example Adhesive Composition Resin A / Adhesive X (weight of solid content) Comparative Example 3 0/100 Example 3-1 10/90 Example 3-2 15/85 Example 3-3 30/70

The tendency of the adhesive to stay PET GLASS XX 0 0 0 0 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs f Example 4 and the age of you 丨 4 1 Let resin a 'D_G, J / adhesive X or Y be a constant 40/60 (Heavy ^ The comparison between the invention and the adhesive composition is made up of the different ingredients, and the adhesive composition is compared. In Example 3, it is presented in Table 5 below. Applicable to China National Standard (CNS) A4 specification (210 X 297 mm). -------- Order --------- ^ AW (Please read the precautions on the back before filling this page) 4/3486 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and the invention description (Table 5)

Example Resin / adhesive viscosity reaches the day of separation (minutes)-'~ -1 Adhesive retention tendency ~~ r ---- PET Glass PET Glass PET ~~ ----- Glass Example 4-1 G / X 0 0 12 10 — ~ 〇— — 〇 Example 4-2 ~ ---- Α / Υ 0 0 5 3 ----- ------ 〇Convention Example 4-3 D / Y 0 〇5 3 —〇— — Example 4-4 17Ϋ ---- 0 0 〇5 2 0 -------- 〇— 〇 Example 4-5 UU ^ Jr.) Λ F / Y ΤΤΓτ- 〇〇15 10- ---- 〇tufscify 4 J / Y -------- 1 0 0 60 60 Χ-Δ ~ —--—, X (Please read the precautions on the back before filling out this page} In addition, indicate Resin D is a polyisocyanuric acid vinegar adduct added to the solid component in an example of 0.-, 1T_ 及 and ^ 发 发 卿 ㈣] has a low degree of swelling without sufficient separation and retention tendency of the adhesive Example 5 and Comparative Example 5 Resin AE is used for the undercoat, and IJ is on the table! There is a narrative line = (thickness: 25mm, case, and then the case where the printing ink Γ is placed on the surface. 丨 to soil (1 ) · The formation of the undercoat layer, ^ H, Η is a very finely dispersed solution coated on a plastic film, as shown in Table 6, and the dry film formed by the thickness of the moon is 乂And after 5 minutes at a temperature of 80 C, the 顼 屮 夂 grade + right Λ is shown. The description of various 溥 films is shown in Table 6 as follows: HDPE: High-density polyethylene but Bu PET: Treated ethyl terephthalate Diester (CNS) A_ · (1 ^ 29¾ 473486 A7 B7 V. Description of the invention () (Please read the precautions on the back before filling in this page) S-PET: Shrinking polyester S-PS: shrinkable polystyrene OPP: biaxially stretched polypropylene (2). Preparation of the ink The composition of the ink is Cyanine Blue (10 parts), polyimide (15 parts), Low nitrogen nitric acid (pyroxylin) (3 parts), additives (10 parts) and solvents (toluene / alcohols / ethyl acetate 62 parts). (3). Printing to the undercoat layer, the ink is applied on the surface of the undercoat layer Its dry coating thickness is 5 # m. If no primer layer is needed, the ink is coated on the plastic film with a dry film thickness of 5 / zm. The above-mentioned ink is coated on the film, and its separation, waterproofness and adhesion The test results are shown in Table 6. (1). The separation test printing film was immersed in a 1.5% sodium hydroxide aqueous solution and the temperature was controlled at 85 ° C. It can be observed that the printing coating layer causes separation. Mixing time of printing and immersion of employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs makes the printing coating of each film completely separated in 40 minutes (in other words, no solution is needed when immersed) Take out the film from the outside, just need to apply external force, such as; place the printed coating layer in running water or rub the printed coating layer), when the self-separation will not occur, as shown below. X: The undercoat layer and the printed fabric layer stay completely, and there is no separation when rubbed. (2) Water resistance test The printing film is immersed in deionized water at a temperature of 85 ° C for 30 minutes. You can observe whether the printing film will separate. The results are as follows: This paper is in accordance with China National Standard (CNS) A4 specifications ( 210X297 mm) 473486 A7 B7 V. Description of the invention () 0: When exposed to running water, the undercoat will not separate. X: The primer layer will separate when exposed to running water. (3) Adhesion test Before the separation test, the tear test of the printed film using cellophane tape as the print coating will not produce separation. On the contrary, if the common ink is used, the printing coating will be separated. (Please read the precautions on the back first_Ma this page)

, Va line-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics 27 This paper size applies to China National Standard (CNS) A4 (210X297 mm) 473486

__B7_ί_ Supplementary wear, 丨 V. Description of the invention () Printed clothing by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Table 6] Example 5 1 2 3 4 5 6 7 8 9 Primer resin AAABBBDDD Plastic film PET OPP HDPE PET OPP HDPE PET OPP HDPE separability 1 1 1 7 7 7 2 1 3 Water resistance 0 〇 0 〇 0 0 0 0 0 Example 5 10 11 12 13 14 Primer resin CEHHH plastic film PET PET PET OPP HDPE separability 20 10 30 30 30 Water resistance Properties 0 0 〇〇0 Comparative Example 5 1 2 3 4 5 6 Primer resin IIIJJ No plastic film PET opp Ί HDPE PET OPP HDPE Separability X x Π X ------- 120 120 X Water resistance 〇0 〇Δ " Δ 〇 Resin B and resin D add 0_ 5% polyisocyanate adduct (crosslinking agent) to the solid component. (Please read the precautions on the reverse side before filling out this page) 28 ^ This paper size applies Chinese National Standard (cns) A4 specification (210 X 297 mm) [Effects of the invention] Hydrophilic resin, composition specially made on this day The parts and methods are both called the printing layer or similar layer on the plastic product or the printing film layer adhered to: It makes the plastic products recover in a colorless state, and it is easier to print after treatment with the treatment liquid. Coated or printed film layer. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs on consumer cooperation. Printed on paper Rule #: Home I 7 7 2

Claims (1)

r The existing hydrophilic resin, under the conditions of yttrium with yttrium, and the main yttrium, the premature body is earlier than the alkali, please read the notes before you fill in this page) ί formation A monomer unit of a carboxyl group and a monomer unit having a retarding group: ΪΓΓΪ monomer unit. Among them, the monomer unit that forms several groups under alkaline conditions is methyl acrylate, and the monomer unit with soil is The (meth) acrylic acid is assumed to be _ trips, the proportion of each unit is as follows: the overall early body early methyl propionate methyl vinegar unit: 20 ^ 90 «% (meth) propionate acid unit: 0.5 5 35 *% Hydroxyalkyl (meth) acrylate unit: 0.5 to 35% by weight η, body unit: 5 to 75 ㈣ :: As for the scope of patent application! The resin according to the item, wherein the macromonomer Zaofan is included, and if the overall monomer unit is assumed to be 100% by weight, the macromonomer occupies 0.5 to 35% by weight. 3. The resin described in item 2 of the scope of the patent application, in which the monomer units including polyfunctional groups, the total monomer units of which are assumed to be Δ⑽ ^%, the monomer units having more than one Lu Zhi group account for 0.1 to 10 weight%. 4. The resin according to item 3 of the scope of patent application, wherein a polyfunctional monomer unit is divinylbenzene. Printed by the Ministry of Economic Affairs ’Smart Consumer Finance Co., Ltd. 5. A kind of latent hydrophilic resin composition, in which the liquid medium contains: 凊 Patent I. Any of items 1 to 4 of latent hydrophilic resin and adhesive Or film-forming ingredients', where the composition is assumed to be 100% by weight, the solid content range is 5 to 75% by weight, and the solids are 100% by weight. The weight of each unit is as follows: Potential hydrophilicity Resin: 10 ～ 90% by weight This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 × 297 mm). Patent application scope B8 C8 D8 Patent application scope amendment-.. 2001/7/6 Adhesive component or film component : Bu 85% by weight ^: Ingredients: 0.5 ~ 20% by weight The composition described in item 5 of the scope of the South patent application, which includes cross-bonding 7. The composition described in item 5 or 6 of the scope of patent application, # Including toner. = A kind of potential hydrophilic resin composition as described in item 7 of the §f benefit range of the article = The method of recovering the articles coated on the surface of the articles, using the test water to cause the methyl acrylate to process the articles, so that the coating The layer produces a clear vision and the removal of the object due to the surge. = The method described in the eighth patent application, wherein the coating layer is cross-linked using a cross-linking agent. 10 ·-Potentially hydrophilic trees as described in the 5th or 7th of the scope of the application. = The method of recycling the articles coated on the surface of the article, which is to make the surface of the printing guide or the surface of the coating layer. Adhesive printed film uses qualitative water and removes the product due to Changrun. —Like the method described in item 9 of the scope of the patent application, which comprises applying a chain agent for cross-linking. In the method described in item 9 or 10, the cross-linking agent is an atmospheric resin, a polyisocyanate compound, or glutaraldehyde. The second method of the ΗU project, whose article is the paper of the husband, K / t, applicable to the national standard of the country (ovs > 8 4 specifications (2 丨 (ix2〇V 公 舞) Please read the precautions on the back before filling in this page ) 10 、 1T Economy Zou Zhicai 4- Printed by PT Employee Consumer Cooperative