TWI269805B - Surface coating material - Google Patents

Abstract

The present invention relates to an aqueous coating material useful for applying to a steel sheet and the like, and to a surface coating material by baking such composition. More particularly, a coating composition is obtained by incorporating specific lubricants into an aqueous emulsion formed by copolymerizing a vinyl polymerizable and self-crosslinkable monomer, and a surface coating material is formed by baking such composition at 60 to 300 DEG C to give a film. The film obtained from the composition according to the present invention has a high hardness, and the lubricity is stable at temperatures varied from ordinary temperature to high temperature. A surface coated steel sheet having said film can be subjected to a continuous drilling process.

Description

1269805 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printed 1 V. Inventive Note () Field of the Invention The present invention relates to a polyoxonane compound and fluorine mixed in a self-crosslinking type of water-strip emulsion. a composition for coating a water bar of a lubricious compound in which a strip compound or a polyethylene strip compound is contained, and a composition containing an acidic compound, even if the composition is baked at 60 to 300 ° C, and has a high hardness, A surface coating material excellent in stain resistance, excellent in lubricity at normal temperature and high temperature. [Prior Art] A liquid medium dispersion called an emulsion, a suspension, a latex, etc., has been widely used as an aqueous coating, an adhesive, a paper coating agent, a quality adjuster for leather, a cement mixture, and the like since ancient times. Film smoothing agent, fiber bonding agent, and the like. When a water-based paint is applied to a copper plate or a resin plate or the like to form a coating film, scratch resistance, stain resistance, thickness resistance of the coating film, non-sticking between the plates or the resin sheets, and good properties are required. Appearance, recently, it is necessary to lubricate oil for omission of machining. In addition, solvent resistance and alkali-resistant dissolution are required depending on the application. In order to satisfy these requirements, it is necessary to make the coating film hard and to improve the lubricity, but it is difficult to make the coating film hard by the conventional water-strip emulsion. Further, in order to improve the lubricity, it is considered that the lubricant is easily mixed in the water ray emulsion, but the lubricant which is generally used has poor miscibility with the aqueous emulsion, and is often agglomerated after several hours or instantaneously. In addition, when machining is continuously performed, when the processing machine is heated to a high temperature, the coating film cannot be accompanied by high-temperature lubricity, there is a problem of scratching, or it is necessary to change the processing conditions of the maple. Therefore, the cross-linked paper with melamine, epoxy, polyurethane, etc. is currently applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) - ϋ n I i^i ϋ ϋ .ϋ One, ^ ϋ II (please read the note on the back and fill out this page) Line 1269805 A7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Β 7 2 V. Invention Description () Organic solvent strip coating for sexual ingredients in 2 〇 0 Ό~3 0 (The TC is baked at a high temperature to obtain a hard and lubricious coating film, but it is necessary to recover the volatile organic solvent or to use a larger furnace 3 for high temperature. The invention shown in the publication No. 11-80485 is a self-crosslinking water-strip emulsion, but the self-crosslinking monomer of the invention has low reactivity, poor baking at low temperatures, and does not indicate any lubrication. [Problem to be Solved by the Invention] The object of the present invention is to solve the above-mentioned drawbacks of the prior art, and to provide a high hardness and good stain resistance when baked at a full water bar and at a low temperature. Appearance, excellent lubrication performance at normal temperature and high temperature The film coating composition and the surface coating material coated with the film. [Means for Solving the Problem] In order to solve the above problems, the present invention is constituted by the following constitution. In other words, the present invention is to make 2 ~30% by weight of ethylene polymerizable self-crosslinkable monomer and other copolymerizable monomers copolymerized in the presence of non-polymeric emulsion, the aqueous strip emulsion of the acrylic strip copolymer, and the above water strip emulsion The solid content is 2 to 10% by weight: "The lubricity compound selected from the group consisting of a polyoxane strip compound, a fluorine strip compound, and a polyethylene strip compound is an essential component. In addition, the composition is in the upper layer. The solid content of the water bar emulsion also contains 0.5 to 10% by weight of an acidic compound selected from the group consisting of a phosphate strip compound, sulfuric acid, nitric acid, and hydrochloric acid, and the self-crosslinkable monomer is pseudo selected from the group consisting of a hydrazine-hydroxyalkyl group ( Methyl) acrylamide, Ν-methoxyalkyl (meth) propyl decylamine, (meth) propylene acrylate. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297) UNI) ----------1 ----- Γ (Please read the Notes on the back to fill out this page) I - set ---- ---- Ί line ®- 12698〇5 A7

The Ministry of Economic Affairs, the Intellectual Property Office, the employee consumption cooperative, can print the aggregator, and there is no particular limitation to use one or more selected from the group consisting of (meth) acrylate, styrene, (meth)acrylic acid, and hydroxyl-containing steroids. The resulting monomer is preferred. The total amount of these other copolymerizable monomers is assumed to be 70 to 98% by weight in addition to the self-crosslinkable monomer. Examples of the (meth) acrylate include (methyl) methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate. Butyl ester, isobutyl (meth)acrylate, 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. The alkyl ester or cyclohexyl (meth) acrylate. These monomers may be used singly or in combination of two or more. The above hydroxyl group-containing monomer refers to an alkyl group of (meth) acrylate. If the chain has one or more hydroxyl groups, the hydroxyl group-containing monomer may, for example, be 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate or the like. These hydroxyl group-containing monomers may be used singly or in combination of two or more. (Meth) acrylate monomer, styrene, (meth)acrylic acid, hydroxyl group-containing monomer 傺 70~98 as above % by weight. If less than 70% by weight, the stability of the water bar emulsion is not good, and When it is more than 98% by weight, the obtained film has poor pencil hardness, stain resistance, solvent resistance, ytterbium resistance, and high temperature, and therefore cannot be used. The present invention is a copolymer of the water mixture. The emulsion is a non-polymerizable emulsifier used in the copolymerization. The non-polymerizable emulsifier refers to a functional group having a high molecular weight and good compatibility with water, and is not applicable to the Chinese National Standard (CNS). A4 size (210 X 297 mm) -III I--IIIII ___I l· I l· I ^ 0 II 1.1 (Please read the note on the back and fill out this page) II ί Line 1 05 8 96 2 A7 _____B7___— An X 5 i, the invention describes () an addition polymerizable functional group such as a polyvinyl group, and the monomer of the upper oxime monomer is incapable of entering the polymerization main chain formed by polymerization. The presence of the non-polymerizable emulsifier is a sputum The stability of the composition of the invention is extremely effective. The non-polymerizable emulsifier is, for example, an anionic surfactant or a nonionic surfactant such as sodium dodecylsulfonate, a polyoxyethylene having a molecular weight of about 20,000, and a polyethylene glycol. ,Polyacrylic acid, A water-soluble protective colloid of methacrylic acid or polyacrylamide, or a composition obtained by polymerizing a hydroxyl group, a sulfonic acid group, a thiol group, a steroid, etc. These non-polymerizable emulsifiers may also be used in combination. In the case of a non-polymerizable emulsifier, agglomerates are generated in the acrylic acid emulsion in the polymerization stage, and as a result, the stability is deteriorated and the polyxanthene compound, the fluorine-containing compound, and the polyethylene are mixed with the water & emulsion. The mixing stability of the compound and the like is deteriorated, so it is necessary to use the emulsifier. # The amount depends on the polymerization conditions, and is about 1 to 5 parts per 100 parts by weight of the monomer mixture. Lubricity added to the water bar emulsion The compound (hereinafter referred to as lubrication _ > 傺 is selected from the group consisting of a polyxane alkane compound, a fluorine strip compound, a polyethylene % compound, and these may also be used in combination, for example, polyoxyalkylene strips & Pesticide 51 (Lake Niko Agia (trans) (share) system), KM - 862 (Shinjuku polyoxyalkylene (stock) system), polyethylene compound Kemppi beta stomach (transliteration) 700 (Mitsui Chemical Industry Co., Ltd.), KSL-240Α (Futa Fainken Mikaru (share) system, Mercatix HP-5D (Mingcheng Chemical Industry 1 (share) system), Saif (transliteration) CL Α - 3 (Sanyo Chemical Industry Co., Ltd.), Fluorine compound Fruen (transliteration) AD-1 (asahi 1C (transliteration) system), polyfluoron (transliteration > LDW4Q (Lai Jing (transliteration) industry (share) system) and so on. Add this paper scale to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) Order · Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Print π Ministry of Economics Property Bureau Staff Consumer Cooperative Printed 1269805 A7 B7 -----6 V. INSTRUCTIONS () The lubricant form in the water strip emulsion is 1 0 # m in the case of '^之丨丨^^ Preferably, the method of addition may be to add a small amount of lubricant under stirring of the water bar emulsion. The lubricant must contain 2 to 10 weights: δ for the solid content of the water bar emulsion. If it is less than 2% by weight, the lubricity is not good at normal temperature and high temperature, and if it is more than 10% by weight, agglomeration occurs in the water-strip emulsion in the composition, and as a result, the stability of the composition itself is deteriorated. Further, when the lubricant other than the lubricant of the present invention is used as a lubricant, for example, a linear alkanoic acid compound such as a stearic acid bar compound, it is mixed with the water slug emulsion of the present invention even when the amount is 2 to 1 D% by weight. At the time, the composition agglomerates within a few turns. Further, the coating composition of the present invention has a lubricant of 2 to 1% by weight of the water-striped emulsion and a solid component thereof, and may be added with a rust inhibitor, a tackifier, an acidic compound of the lower jaw, or the like. Other ingredients. Containing 0.5 to 10% by weight of an acidic compound to the solid component of the water emulsion of the upper layer to promote the crosslinking reaction of the self-crosslinking monomer, even when baking at a lower temperature of 60 to 12 G ° C, A surface coating material having good solvent resistance and alkali dissolution resistance can be obtained. When it is less than 0.5% by weight, the effect as a promoter is weak, and as a result, the solvent resistance and alkali-resistant dissolution property of the surface coating material are poor when baked at a low temperature, and if it is more than 10% by weight, the coating composition is The pH of itself will be significantly reduced and the operation stability will be poor. The acidic compound 僳 is selected from the group consisting of a phosphate strip compound, sulfuric acid, nitric acid, and hydrochloric acid, and has a dissociative hydrogen ion. Phosphate strip compounds can be used in China, such as ammonium dihydrogen phosphate, sodium dihydrogen phosphate, sodium monohydrogen phosphate, trisodium phosphate, sodium pyrophosphate, sodium polyphosphate, sodium polyphosphate, sodium methyl phosphate, and phosphoric acid. Standard (CNS) A4 specification (210 X 297 mm) ;---·----------4----l· (Please read the notes on the back and fill out this page) — l· I Book·---- Line shoulder 1269805 A7 B7 7 V. Description of invention () Magnesium hydrogen, aluminum phosphate, hypophosphorous acid, orthophosphoric acid, poly-ortho acid. These acid compounds may be used singly or in combination of two or more. (Please read the precautions on the back and fill out this page.) The method of preparing the coating composition described in the above section is not limited, as shown below. In other words, the quantified non-polymerizable emulsifier and deionized water were placed in a reaction tank to raise the liquid temperature to 70 °C. In which the oil-soluble polymerization initiator, or the monomer mixture tree and the aqueous solution of sodium persulfate and the aqueous sodium sulfite solution are dissolved in the quantitative monomer mixture simultaneously in 2 hours, and stirred continuously. After mixing at 7 () ° C for 2 hours and carrying out polymerization, a water bar emulsion can be obtained. Then, for example, there is a method in which a composition of a wet lubricant is added in a small amount in a water-repellent emulsion of 10 to 5 (TC, about 100 r pm), and added to 10 to 50 when an acidic compound is added. 〇 方法 〇 l l l l l l l l l l l l l l 约 约 约 约 约 约 约 约 约 。 。 。 。 。 。 。 。 。 。 约 。 约 。 约 约 约 约 约 约 约 。 。 。 。 。 约°C. If the baking temperature is less than 6 G °C, the moisture of the solvent is not easily removed, the cross-linking of the self-crosslinking monomer portion in the copolymer is insufficient, the pencil hardness of the film, the appearance of the film, and the room temperature. And the lubricity at high temperatures is not good. If it is more than 300 °C, there will be a problem that the decomposition of the film starts to burn slowly, or a huge heating device, and the processing material is forced to cool the equipment, which is not desirable. The film formed by the composition of the present invention thus obtained has a pencil hardness of 6H or more and good stain resistance, and the number of dynamic friction images at 25 ° C is 0.15 or less and at 12 (the dynamic friction pseudo number of TC is less than 25°). C of 1· 2 Excellent physical properties. Moreover, this paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1269805 A7 B7 V. Invention description (depending on the use of surface coating, solvent resistance or hydrazine resistance is required) Dissolution property. When the coating composition of the present invention containing no acidic compound is used for this requirement, it is necessary to have a baking temperature of 1 2 (TC or higher, but a coating composition containing an acidic compound). At a baking temperature of -120 °C, a film having excellent solvent resistance (four or more levels of evaluation method as described below) and alkali-resistant dissolution (hereinafter, the evaluation method is 10% or less) can be obtained. The material to be coated is, for example, a cold-rolled steel plate, an aluminum plate, an aluminum alloy plated steel plate, a zinc plate, a galvanized pin plate, an ABS resin plate, etc., especially when applied to a steel plate, the low-temperature and high-temperature lubricity of the upper coating film. Preferably, the effect of the continuous press processing or the like is also large. [Embodiment] The present invention will be described in more detail by way of examples in the hem. Moreover, each evaluation in the examples is given by the following method. Determination and evaluation. 1 . Composition stability 30 ml of a water-based emulsion-based composition was added to a 50-ml glass bottle, sealed, and allowed to stand at 5 (TC for 1 month). The state of the emulsion after one month was visually evaluated. β 〇: no condensation , viscosity increase, precipitation, separation, false good - qualified will produce condensate and sediment ................ unqualified gelation ..... ......................Failed 2. Lubricity (dynamic friction pseudo-number) After the composition of the water-striped emulsion is applied to the substrate , let it stand in the hot air dryer to the specified reaching temperature, and bake the coating film. In the room cooled to normal temperature at a certain speed in the room adjusted to 25 °C (10 cm / 10 paper scale applies to China) Standard (CNS) A4 size (210 X 297 mm) (Please read the note on the back and fill out this page) ---I l· I h I Book ίιιι---I 1 -

△ X Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing π 1269805 A7 B7 9 V. Invention description () points) The hammer is slid down to determine the load generated by friction at this time. The dynamic friction coefficient is calculated by the following formula. Further, regarding the high-temperature lubricity, an electric heater was placed under the substrate, and the coating film was preheated to 120 °C, and the above-described method was used to measure the number of dynamic friction turns. (JIS K-7125) Number of dynamic friction images = weight of hammer (g) / load due to friction (gf) 3. Pollution resistance is caused by applying a stick of water-based emulsion to the substrate, in hot air The inside of the dryer was allowed to stand at a predetermined reaching temperature, and the baking coating film was dropped with 2 ml of a 10% carbon black aqueous dispersion on a film cooled to normal temperature, and left in an 81TC hot air dryer for 24 hours. The sample was taken out, wetted with pure water, and the carbon black was dropped, and the state of the black adhesion on the coating film was visually judged. ® : No adhesion.........Qualified 〇: Adhesive condition with a slight degree of visibility.....Quality △: Visibility of visible degree.........Failed X: Obvious Ground adhesion situation..................Failed XX: Apparently adhered to the situation, and spread to the surrounding - unqualified 4. Pencil hardness is coated with a stick of water-based emulsion After the substrate, it was allowed to stand in a hot air dryer to a predetermined reaching temperature, and the coating film was baked. The coating film cooled to a normal temperature was ruptured with a pencil of different hardness, and the pencil hardness which did not damage the coating film was read. 5. Solvent resistance After applying the composition of the water bar emulsion to the substrate, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applied to the hot air -11- paper scale --- -----I — I - III l· I l· I · II —r (Please read the notes on the back and fill out this page) Line 1269805 A7 B7 10 V. Invention description () The machine is allowed to stand until The coating temperature is set and the coating film is baked. The film which was cooled to a normal temperature was rubbed back and forth 5 times with a load of about lfcg, or the like, which was dyed with ethanol. Then, the change in appearance on the coating film was visually observed. 5 (level): no appearance change 4 (level): confirmed by visual angle change 3 (level): slight change 2 (level): obviously change, 1 (level): film peeling 6. alkali resistance The elution property is measured by measuring the weight of the substrate in advance, and applying a composition stick mainly composed of a water bar emulsion to the substrate such as a steel sheet, and then standing in a hot air dryer to a predetermined reaching temperature, and measuring the baking coating film. The weight A of the coating film was determined by cooling to the weight of the coating film containing the substrate at normal temperature. Then, the aqueous solution of the base of the Syracuse SD280MZ (manufactured by Peyton, Japan), which was previously adjusted to 2% by weight, was maintained at 43 ° C, and the coating film containing the substrate was placed therein. Dip for 2 minutes. After 2 minutes, it was taken out and gently washed with water, and dried in a hot air drying base at 50 °C until there was no water. Then, the weight of the coating film containing the substrate was measured, and the coating film weight B which was retained on the substrate after the hydrazine treatment was determined, and the 鹸 dissolution rate (%) shown by the following formula was obtained. Alkali dissolution rate U ) = [ 1 - ( B / A ) ] X 1 0 0 7 · The appearance of the coating is applied to the substrate after the composition of the water bar emulsion is applied to the substrate, and then allowed to stand in a hot air dryer to a predetermined temperature. To reach the temperature, bake the film. The appearance of the surface of the coating film cooled to normal temperature was visually evaluated. -12- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) -----r--^-订·--- .---Γ-·Line 1 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printing Agriculture 1269805 A7 B7 11 V. Invention Description () 〇: No discoloration △: slight discoloration X: Significant discoloration Example 1 (non-polymerizable Synthesis of emulsifier) 991 parts by weight (parts by weight, all of the following > deionized water, 100 parts of the monomer shown in the composition column, 3 parts of ammonium persulfate, 4 parts of acidic sodium sulfite are placed in the reaction) The inside of the tank was stirred and the liquid temperature was raised to 70. 0. The polymerization was further carried out by stirring at 70 ° C for 12 hours to synthesize the non-polymerizable emulsifiers a to c satisfying the present invention. As a non-polymerizable emulsifier of the present invention, commercially available surfactants, etc. d ~ f 0 Table 1 (Please read the back note first and then fill out this page) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed non- Polymeric composition remarks A MAA/ VVS=70/30 B MAA/ SPSS=70/30 C MAA/ VSS/HEA=70/20/10 D PVA-217 (polyethylene glycol) E 〇T-7Q manufactured by Claret Co., Ltd. (anionic surfactant Sanyo Chemical Industry Co., Ltd. F Yemaruken 130K (nonionic surfactant) Kao shares limited Company system

* MAA : Ice VSS : * HEA : ^ SPSS Sodium hydroxy acid 2-propane sulfonyl ethene propionate sulfonyl ethylbenzene 43 ester Ethyl paper size applicable to China National Standard (CNS) A4 specification (210 X 297 mm) Pack-----„--------------,-line ^^1 1269805 A7 __B7_____ V. Description of the invention (^) Example 2 (Water strip emulsion Synthesis) 49 parts (parts by weight, all of the same) deionized water, 5 parts of the non-polymerizable emulsifier shown in Table 2 were placed in the reaction tank and the liquid temperature was raised to 7 〇 ° C. Into 97 parts of deionized water, 2 parts of other copolymerizable monomers dissolved in Table 2 were dissolved in 2 hours to form a monomer mixture of the composition shown in the composition, 3 parts of ammonium persulfate, and 96 parts of deionized water. After dissolving 4 parts of the liquid of acidic sodium sulfite, the mixture was stirred at 7 (TC for 2 hours) to carry out polymerization to synthesize the water-strip emulsion No. Α~Ρ satisfying the present invention. Polymerization ratio synthesis In addition to the present invention, the water strip emulsion N 〇. Q~V is used as a comparative example. The "emulsion stability" in Table 2 is used to make these water emulsions In a closed container, and visually evaluated to stand at 50 °C for 1 month, 0: no aggregation, adhesion, precipitation, separation, shape, 傺, △: will produce aggregates and precipitates, X : Gelation. (Please read the notes on the back and fill out this page) -_ Install-----^---^1 Order*---一------Line. Ministry of Economics Intellectual Property Bureau employee consumption cooperatives printed agriculture 4 paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1269805 A7 _B7 V. Invention description () Table 2 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing water emulsion Other co-polymerizable monomers constitute self-crosslinking monomer species self-crosslinking monomer% Non-polymeric emulsifier emulsion stability remarks water emulsion A i-BMA/n-BA=62/36 N-MAM 2 a eucalyptus invention water emulsion B MMA/n-BA=51/44 N-MAM 5 · hydrazine emulsion C MMA/n-BA=49/41 N-MAM 10 b hydrazine emulsion D MMA/2=19/61 N-MAM 20 a Hydrazine emulsion E MMA/n-BA=38/32 N-MAM 30 e Hydrazine emulsion F MMA/n-BA=53/45 GMA 2 a Hydrazine emulsion G i-BMA/2EHMA=30 /65 GMA 5 d 〇 Water emulsion Η CHMA/n-BA=54/36 GMA 10 a Hydrazine emulsion I MMA/n-BA=38/32 GMA 30 f Hydrazine emulsion J MMA/CHMA/n-BA= 29/30/39 N- MMAM 2 c 〇水 emulsion Κ MMA/n-BA=51/44 N-MMAM 5 d 〇Water emulsion L MMA/n-BA=49/41 N-MMAM 10 b 〇水 emulsion Μ MMA/n-BA=38 /32 N-MMAM 30 b Water-based emulsion Ν St/n-BA/MAA= 35/45/15 N-MMAM 5 e Water-based emulsion 〇MMA/n-BA/HEA= 48/37/10 N-MMAM 5 d 〇Water emulsion Ρ MMA/n-BA/MAA/HEA= 28/42/15/10 N-MMAM 5 f Hydrazine emulsion Q MMA/n-BA=53/46 N-MMAM 1 a 〇Comparative example paper The scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) pill — — — — — — — — II (Please read the note on the back and fill out this page) --Line · [269805 A7 HB7 · 14 V. INSTRUCTIONS (aqueous emulsion R MMA/n-BA=35/30 N-MAM 35 a X water emulsion S MMA/n-BA=53/46 GMA 1 b hydrophobic emulsion T MMA/n-BA= 51/44 N-MAM 5 (SPSS) 0 Water emulsion 1 liquid U MMA/n-BA=51/44 (DvB) 5 b Hydrophobic emulsion V ΜΜΑ/π-ΒΑ=51/44 N-MMAM 5 △ Ministry of Economic Affairs wisdom Produced by the staff of the production bureau * MMA: methyl methacrylate * n-BA · n-butyl acrylate * i-BA · isobutyl methacrylate * 2EHMA · 2-ethylhexyl methacrylate * CHMA: cyclohexyl methacrylate * St : styrene * MAA: methacrylic acid * HE A : 2-hydroxyethyl acrylate * N-MAM: N - hydroxymethyl acrylamide * N-MMAM: N- Methyl methacrylamide amide * GMA : glycidyl methacrylate * DvB : divinyl benzene As shown in Table 2, the water bar emulsion a to P which meets the requirements of the present invention, the stability of the emulsion formed by polymerization Excellent. In addition to S, the self-crosslinking monomer is R, and the non-polymerizable emulsifier is not V, and the emulsion itself lacks stability. Q and S which are too small in cross-linking, T of SPSS using a polymeric emulsifier, u which uses DvB which does not have a cross-linking monomer, water strip--1 6 - (Please read the note on the back of the J first. Fill in this page) 卜 — l·—订--------1-线». This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1269805 A7 B7 15 V. Invention Description () There is no problem with the stability of the emulsion itself. However, there are disadvantages when it contains the composition of the lubricant described below. Examples 3 to 7 and Comparative Examples 1 to 3 using the water bar emulsion C shown in Table 2, and various lubricants shown in Table 3 for the solid content of the water bar emulsion, as shown in Table 3 < The respective amounts were mixed to adjust to a coating composition (hereinafter simply referred to as a composition), and the composition was coated on an aluminum plate to form a coating having a thickness of 3 # hi, and then a coating was obtained. Table 3 shows the evaluation results of the stability of the surface coated steel sheet composition and the surface characteristics of the steel sheet having the coating composition film having a baking reaching temperature of 130 °C. (Please read the notes on the back and fill out this page)

Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed Table 3 Lubricant mm Lubricant Weight % Composition Stability Coating Appearance Dynamic Friction Coefficient 120°C /25〇C Dynamic Friction Coefficient I Pollution Word Hardness Solvent Alkali Dissolution Rate % 25〇C 120°C Implementation of Pein Tower 2 〇〇0.080 0.095 1.188 ◎ 7H 5 0 Example 3 51 51 Implementation of Pein Tower 5 〇〇 0.049 0.057 1.163 ◎ 7H 5 0 Example 4 51 51 Implementation of Pein Tower 10 〇〇 0.049 0.056 1.143 ◎ 7H 5 0 Example 5 顿 51 Implementation of PTFE 5 〇〇 0.055 0.063 1.145 ◎ 7H 5 0 Example 6 LDW40 - Implementation of 赛里伏 5 〇〇 0.057 0.067 1.175 ◎ 7H 5 · 0 Example 7 CLA3 Comparison of Peinta 1 〇〇0.160 0.195 1.218 ◎ 6H 5 0 Example 1 51 51 Comparison of Pein Tower 12 Δ Example 2 51 51 Comparison of stearic acid 5 X Example 3 series of compounds 丨 This paper scale applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -17- 丨定· --Line · 1269805 A7 B7 16 V. Illustrative () It can be seen from Table 3 that Examples 3 to 7 satisfying the requirements of the present invention have a high-alkali resistance and a high temperature agent and a temperature-difference resistance, and a heterogeneous excellent dyeing and staining resistance/i. It is hard to use this. The difference between the number of coatings for lead and slipperiness is less than that of the body. , the external matter of the addition of the sulphate acid refers to the hardening of the slab. The slab is better than the slab of the slab. The slab of the slab is less than the smear of the smear. Ti solidified milk bar water to adjust to / liquid milk J4N 糸 case K is more than water eb® sex sb-7K slip 2 -22 CO of the surface temperature example with high application and real - mixed 5 things Baked 胄 5 $ 合 吏 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ The group is used to cover the cover of the steel coated sheet of the coated coated board. °c (please read the note on the back and then fill out this page): #装----III· — Table such as the body profile of the evaluation of the plate and the sex 13 is set to the temperature of the degree Material reached C to group display I---------Line - Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed This paper scale applies China National Standard (CNS) A4 specification (210 X 297 mm) 1269805 A7 B7 V. INSTRUCTIONS (/?) Table 4 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printing Water System Emulsion Composition Stability Raw Material Coating Appearance Dynamic Friction Coefficient Dynamic Friction Coefficient Corrosion Resistance Pencil Hardness Solvent-Resistant Alkali Dissolution Rate 25〇 C 120 ° C Example 8 Aqueous emulsion A 〇 Raw material 1 〇 0.071 0.084 1.183 〇 6H 4 0 Example 9 Water emulsion B 〇 Raw material 1 〇 0.055 0.065 1.182 〇 7H 4 0 Example 4 Water emulsion C 〇 Raw material 1 〇 0.049 0.057 1.163 ◎ 7H 5 0 Example 10 Water emulsion D 〇 Raw material 1 〇 0.048 0.056 1.167 ◎ 8H 5 0 Example 11 Water emulsion E 〇 Raw material 1 〇 0.050 0.057 1.140 ◎ 8H 5 0 Example 12 Water emulsion F 〇 Raw material 1 〇 0.068 0.079 1.162 〇6H 4 0 Example η Water emulsion G 〇 Raw material 1 〇 0.061 0.072 1.180 〇6H 4 0 Example 14 Water emulsion 〇 Raw material 1 〇0.058 0.068 1.172 〇6H 5 0 Example 15 Water system Emulsion I 〇 Raw material 1 〇 0.055 0.063 1.145 ◎ 7H 5 0 Example 16 Water emulsion J 〇 Raw material 2 〇 0.069 0.079 1.145 〇6H 4 0 Example 17 Water emulsion 〇 Raw material 2 〇 0.060 0.070 1.167 〇7H 4 0 Example 18 Water emulsion L 〇 raw material 2 〇0.057 0.066 1.158 ◎ 7H 5 0 This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -19- -------------- - Packing--- (Please read the notes on the back and fill out this page) --- Order - 1269805 A7 B7 V. Invention Description Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing

Example 19 Water-based emulsion 〇 〇 Raw material 1 〇 0.053 0.061 1.151 ◎ 8 Η 5 0 Example 20 Water-based emulsion 〇 Raw material 1 〇 0.058 0.067 1.155 〇 711 5 82.4 Example 21 Water-based emulsion 〇〇 Raw material 1 〇 0.052 0.061 1.173 〇 7 Η 4 0 Example 22 Water-based emulsion 〇 Raw material 1 〇 0.055 0.062 1.127 〇7Η 5 100 Comparative Example 4 Water-based emulsion Q 〇 Raw material 1 〇 0.120 0.165 1.375 Δ 4Η 3 0 Comparative Example 5 Water-based emulsion S 〇 Raw material 1 〇 0.145 0.195 1.345 X 4Η 3 0 Comparative Example 6 Water-based emulsion U 〇 Raw material 1 〇 0.155 0.198 1.277 X 4 Η 2 0 Comparative Example 7 Water-based emulsion VX Comparative Example 8 Water-based emulsion Τ X ※ Raw material 1 ※ Raw material 2 Aluminum plate galvanized steel plate - 20 - This paper scale applies China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the back and fill out this page) Order A7 1269805 ___B7___ V. Invention Description () From Table 4, the implementation of the requirements of the present invention is satisfied. Examples 8 to 22 have excellent coatability, pencil hardness, stain resistance, and lubricity of dynamic friction coefficient at normal temperature and high temperature. . Further, in addition to Examples 2 and 2, it also has excellent solvent resistance and mash resistance. In Examples 20 and 22, the dissolution was poor. This cockroach contains too much cockroaches, but it is practical to use only other applications that are excellent in performance and do not require alkali-resistant dissolution. In Comparative Examples 4 and 5 in which the lubricant amount was too small, and Comparative Example 6 in which DvB having no self-crosslinkable monomer was used, the stability of the composition itself was not problematic, but the lubrication resistance, pencil hardness, normal temperature and high temperature lubrication were lacking. Comparative Examples 7 and 8 which did not use a non-polymeric emulsifier lacked the stability of the composition mixed with the lubricant. Example 2 3 to 3 2 and Comparative Examples 9 to 1 1 Using the water bar emulsion C shown in Table 2, to adjust the solid content of the water bar emulsion, 5 parts by weight of a Peinton 51 (polyoxane gas) was mixed. a coating composition for the strip compound), and coating the composition stick on the aluminum plate to a thickness of 3 # m after baking, and then coating the coated baking temperature as shown in Table 5 The pin plate is covered with the surface of the composition film. The evaluation results of the stability of the composition and the surface characteristics of the pin plate are shown in Table 5. (Please read the notes on the back and then fill out this page) --Border. Line 1 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed - 21 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 PCT) 1269805 A7 B7 V. INSTRUCTIONS (2〇) Table 5 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printing Acid Compound Composition Stability Bake Temperature °C Coating Appearance Dynamic Friction Coefficient 120°C /25〇C _ Friction Coefficient ratio pollution resistance* Pencil hardness Solvent-resistant alkali dissolution rate % Operational type addition amount % 25〇C 120°C Example 23 - - 〇60 〇0.085 0.095 1.118 〇6H 3 26.5 〇Example 24 - - 〇80 〇0.067 0.078 1.164 ◎ 7H 3 20.4 〇Example 25 Sulfuric acid 0.2 〇80 〇0.047 0.055 1.170 ◎ 7H 3 10.8 〇Example 26 Orthophosphoric acid 0.5 〇80 〇0.047 0.054 1.149 ◎ 7H 4 0 〇Example 27 Sulfuric acid 1 〇80 〇 0.045 0.053 1.178 ◎ 7H 4 0 〇 Example 28 orthophosphoric acid 2 〇 80 〇 0.046 0.053 1.152 ◎ 7H 5 0 〇 Example 29 Sulfuric acid 5 〇 80 〇 0.044 0.051 1.159 ◎ 7H 5 0 Example 30: orthophosphoric acid 10 〇 80 〇 0.045 0.052 1.156 ◎ 7H 5 0 〇 Example 31 - - 〇 120 〇 0.055 0.065 1.182 ◎ 7H 4 5.5 〇 Example 4 - - 〇130 〇 0.049 0.057 1.163 ◎ 7H 5 0 〇 Example 32 - - 〇270 〇0.043 0.051 1.186 ◎ 8H 5 0 〇Comparative Example 9 - - 〇50 Δ 0.110 0.145 1.318 X 5H 2 29 X Comparative Example 10 - - 〇320 X - Comparative Example 11 orthophosphoric acid 12 〇80 Δ 0.043 0.050 1.163 ◎ 7H 5 0 X -22- (Please read the note on the back and fill out this page) This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1269805 A7 B7 Ministry of Economics Intellectual Property Bureau employee consumption cooperative printing 5, invention description (21) It can be seen from Table 5 that Examples 23 to 32 satisfying the requirements of the present invention have excellent coating properties, pencil hardness, stain resistance, dynamic friction at normal temperature and high temperature. The lubricity of the number. Further, Examples 4, 31, and 32 in which the baking temperature was 120 ° C or more had excellent solvent resistance and ytterbium resistance, and Example 2 6 to 3 G in which an acidic compound was mixed, even at 8 (TC) It has good solvent resistance and alkali-resistant dissolution at the baking temperature in the lower temperature range. Moreover, the solvent and leaching-resistance straws of Examples 23 to 25 are not good, but only other properties are required. The use of excellent and not required alkali-resistant dissolution is very practical. In addition, in Comparative Example 9 in which the baking temperature is too low, satisfactory film hardness, poor stain resistance, and high baking temperature are not obtained. G, the surface coating material and the lubricant may decompose and the coating film evaluation may not be completed. In Comparative Example 11 in which the mixing amount of the acidic compound is too large, the coating appearance after baking is not good, and the pH of the composition is remarkably lowered. The safety of the operation is remarkably poor. [Effect of the Invention] The present invention can provide a package of a lubricity stabilizer film which is high in hardness and low temperature to high temperature, which is excellent in safety and environment. Overlying the composition and the skin Membrane-coated surface color covering material stomach. When the composition is applied to a plate or the like, for example, the pin plate does not have a problem that the lubricity is lowered at a high temperature, and the drilling can be continuously performed by adding X ^ -23 - The paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page)

Chinese Surface Coating Material (Revised on December 27, 1993) Invented New Name English

SURFACE COATING MATERIAL Name Nationality. Fukugawa Yukang • Takahashi Chiji 2, Japan 2. Japanese Inventor Creation and Residence 1. Okayama City, Okayama 959, No. 5, Okayama, Okayama, Okayama, Okayama, Okayama, Okayama, Okayama If the name (name) Toyobo Co., Ltd. (Toyobo Co., Ltd.) The Ministry of Finance of the Ministry of Finance and Finance 锜g (The Ministry of Industry and Commerce Co., Ltd. prints the nationality of Japan III. The applicant's residence, residence (office) Representative name Osaka City North District Island 浜 2 Chome 2 Fan No. 8 Tsumura Bimoto This paper scale applies Chinese National Standard (CNS) A4 specification (210X297 mm) 1269805 V. Invention Description (3) Moreover, the present invention is included so that the composition is at 60° It is prepared by baking at C~300 °C, has a pencil hardness of 6H or more, and has good stain resistance. The dynamic friction coefficient at 25 ° C is 0.15 or less and the dynamic friction coefficient at 120 ° C is 1.2 times or less at 25 ° C. The surface coating material coated with the film. [Form of the invention] The self-crosslinking single system as described above is selected from N-hydroxyalkyl (meth) acrylamide, N-methoxyalkyl (methyl) Acrylamide and glycidyl (meth)acrylate are preferred. Moreover, the self-crosslinking single system of the present invention has N- 1 hydroxyalkylguanamine, N-methoxyalkylguanamine. The epoxy group is a valer group, and the carboxyl group or the (meth)acrylic acid of the other copolymerizable monomer used in the copolymerization of the functional group or the functional group in the copolymer of the present invention. The group of the above-mentioned compound is represented by a hydroxyl group of a hydroxyl group:: a compound group of the above-mentioned compound, for example, a hydrazine-hydroxymethyl (meth) acrylamide, a hydrazine-hydroxyethyl group (for example) A modified to amide, acrylamide, hydrazine-hydroxypropyl (meth) acrylamide, hydrazine-hydroxybutyl

jcX methyl) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxyindolyl (meth) acrylamide, N-methoxypropyl (methyl) The alkyl group such as acrylamide or methoxybutyl (meth) acrylamide is (^~〇4. These | self-crosslinkable monomers may be used singly or in combination of two or more. Moreover, the (meth) propylene sulphuric acid ~ indicates that the methyl propyl storage acid ~ or acrylic acid ~ (the same below). Self-crosslinking single system using the total amount of monomers forming the emulsion 2 ~ 30% by weight. If less than 2% by weight, pencil hardness, stain resistance, lubricity at normal temperature and high temperature are not good, and if it is more than 30% by weight, the stability of the aqueous emulsion is not good, so it cannot be used. As long as the monomer is compatible with the above-mentioned self-crosslinking monomer

Claims (1)

1269805 六^, Shenyan cream special spear lj 聋色弟弟89112298 "surface coating material" patent case (revised on December 27, 1993) Λ patent application scope: 1. A surface coating material 'a system of The coating composition is baked at 6 01: 〜3 001:, has a pencil hardness of 6H or more, and has good stain resistance. The dynamic friction coefficient at 25 ° C is 〇 15 or less and the dynamic friction coefficient at 120 ° C The coating composition is 1.2 times or less at 25 ° C, and the coating composition is such that 2 to 30% by weight is composed of N-hydroxyalkyl (meth) acrylamide, N-methoxyalkyl group. Copolymerization of an ethylene polymerizable self-crosslinkable monomer selected from (meth)acrylamide and (meth)acrylic acid propylene acrylate with other copolymerizable monomers in the presence of a non-polymerizable emulsifier The aqueous emulsion of the acrylic copolymer and the lubricating compound selected from the polyoxyalkylene compound, the fluorine compound, and the polyethylene compound in an amount of 2 to 10% by weight based on the solid content of the aqueous emulsion, and The solid content of the above aqueous emulsion contains 0.5 to 10% by weight - The above acidic compound selected from a phosphoric acid compound, sulfuric acid, nitric acid, and hydrochloric acid is an essential component.