TWI290943B - Single component non-solvent free-radical curable polymer coating system - Google Patents

Abstract

Anti-corrosion steel coatings are obtained from free-radical curing process with various ratios of HEMA-POH, EPOXY-POH, reactive diluents and free-radical initiators, and then cured by thermal or UV irradiation processes accordingly. These anti-corrosion coats have excellent adhesion on the steel surface due to the presence of phosphoric acid as the polymer side chain, which reacts with steel surface and forms iron phosphate linkages between coated film and steel surface. The cured epoxy coated film has excellent water and solvent resistance, and their excellent properties, such as salt spray, water-proof, solvent resistance, impact strength and etc. as a perfect steel protective film. This steel coating process combined two processes of anti-corrosion and protective coating into one. Furthermore, this steel coating recipes and curing process produce neither solvent emission nor waste water discharge. This steel coating procedure is an environmental friendly clean production process.

Description

1290943 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a polymer coating system, in particular to a non-solvent type single-liquid acid-filled side chain free radical crosslinking polymer coating system for steel surface Double anti-corrosion process for sulphate filming and primer treatment. [Prior Art] Traditional phosphate filming system uses Parker filling surface treatment (parker

Phosphatizing Process). The anti-corrosion primer of the metal (steel) is coated with a phosphoric acid aqueous solution containing a second 'and treated with a south temperature to produce a water-insoluble sulphate crystal, which is then treated with a chromate solution to increase the adhesion strength and surface hardness to the metal surface. At the same time, the anti-corrosion surface treatment such as the conductive property is reduced; the surface treatment of the phosphate produces a large amount of phosphorus and chromate wastewater in the cleaning of the steel sheet, which causes environmental problems. Holes are usually formed on the surface of phosphate-treated steel, and the surface is still treated with a resin coating for another layer of anti-corrosion coating. The corrosion of metals is caused by the electrochemical reaction of the surface, and the presence of moisture, electrolytes and oxygen in the environment promotes the riding of the metal oxide. Most of the metals (in addition to gold, platinum, etc.) are present in oxygen in the domain conditions; the cone of steel is spontaneous in the soil (ie, the change in free energy is less than zero), Especially in the humid environment, the oxygen in the metal reading enthalpy enters the Weihua (4) chemical reaction, and the f is the thief-free gold riding compound, which is the surface layer to prevent the insulation of the water-tight gas, oxygen rolling and the like to protect the rhyme. The main cause; regardless of the inorganic or organic coating film, usually used to separate the surface of the gold county to contact the outside water, oxygen or electrolytes, and 1290943. Does not cause electrochemical corrosion. In order to prevent metal oxidation (ie, metal anti-retention), it is necessary to form a complete protective film on the metal surface and have good adhesion to the metal surface. The strength can effectively prevent the metal from contacting oxygen, water vapor and electrolyte. , ^ steel surface anti-skinning anti-square 'in the current traditional phosphate filming. Department of Parker _ chemical surface treatment, in addition to impregnation of phosphoric acid and high temperature heat treatment to produce phosphate crystals, 'have to be treated with chromate solution The system is made of chromate-filled steel surface--phosphoric acid treatment. The two treatments are all (4) re-cleaned and dried to remove the electrolyte salts that may remain in the process, which not only produces a large amount of toxic hexavalent network. f water, often consumes a lot of energy and water resources; in addition, the current surface treatment of phosphatized steel does not produce continuous and complete protection. There are still small holes, and it is still necessary to apply another layer of water-based or oil-based resin to protect the coating film. As a primer for steel, it can be used to prevent the steel from initial (four) functions. This is a two-stage steel tamper-proof treatment, which requires quite complicated procedures. It is easy to cause environmental and resource consumption problems. It is a trend in the world to make Guanhua and have a clean production process. In the process disclosed in the US Patent (10)^ (10), the process of adding organic phosphorus-acid and dissolution coating is applied on the surface of the steel, and after drying and hardening the solvent evaporation coating, the organic squaric acid only It can form a phosphate film on the surface of the steel. It does not produce any chemical bond with the oil. It has only a wattage and cannot be part of the film. Therefore, in the high temperature or oil (4) environment for a long time, the protective coating film may separate the acid film from the organic film, and reduce the corrosion protection function of the steel surface. ^ [Summary of the Invention] 6 1290943 The present invention is related to the present invention, the single-liquid non-solvent type phosphoric acid-containing side chain free-radical cross-linked polymer green "seam" anti-sewn material is coated on the surface of the steel, wherein The oligomer is polymerized by free radical polymerization to form a continuous guarantee _, and at the same time, it is chemically bonded to the surface of the steel to produce phosphoric acid and iron crystals, which increases the _ and the surface of the steel surface, and can complete the phosphate film formation and the bottom of the steel surface at one time. Double treatment, no solvent evaporation during the treatment process and no waste water discharge, and simplify the anti-corrosion treatment process. ······················································· a novel compound of a monomer and an oligopolymer, which is a mixture of the monomer and the oligopolymer in different proportions, and the free radical reaction monomer is used as a reactive diluent to adjust the viscosity and coating of the coating. Crosslinking density; the appropriate (thermal decomposition or ultraviolet light-initiating type) initiator is used to prepare a single-liquid non-solvent type phosphoric acid side chain free radical crosslinked polymer coating ## system, applied to steel surface Phosphate filming anti-corrosion treatment and primer treatment simplify the process and provide dual anti-corrosion coatings. • The present invention performs an addition chemical reaction with phosphorus pentoxide and a reactive (including double bond) monomer and oligomer respectively to produce a reaction type (including double bond) monomer and oligomeric group containing a phosphate group. The material, as a substrate material for the steel undercoating, can be used as a crosslinking agent in combination with a reactive diluent, and then a suitable free radical initiator (thermal initiator - or photoinitiator) ), a single-liquid anti-corrosive coating made of non-solvent type single-liquid phosphoric acid side chain 1290943 free radical cross-linking polymer coating system'·This coating is applied to the surface of steel, and then heated or UV-rayed, fine The hardening reaction of the coating can form a protective coating film for the steel, and the phosphorus-containing coffee chain contained in the molecule and the crystalline film of ferro-iron on the surface of the surface. - In this way, the polymer coating (4) of the present invention can perform double anti-corrosion treatment such as sulphate film coating and primer coating on the steel surface. When the surface of the steel material is treated, the radical-hardening type phosphoric acid-containing reaction type (including double bond) monomer and the epoxy resin oligomer are used as the ruthenium, and the sulphur acid contained in the resin formulation is contacted with The surface of the steel can be subjected to a phosphate membrane reaction at a normal temperature, and the viscosity of the coating can be adjusted by using a reactive diluent having an acrylate group (including a double bond), and the father of the coating film can be controlled, and an appropriate initiator can be introduced to form a suitable initiator. Solvent-free coating, applied to the surface of steel, heated or irradiated with ultraviolet light to produce a free radical hardening reaction, so that the coating on the surface of the steel can be quickly dried to form a film; after drying and hardening, a continuous polymer protective coating film is formed, and at the same time, the resin is coated. The phosphoric acid contained in the film forms a phosphate film reaction with the surface of the steel material, thereby forming an anti-corrosion protective layer of a continuous organic high Lulu molecular protective coating film having a phosphate film on the metal surface. The single-liquid solvent-free coating formulation of the invention can treat the surface of the steel at one time to replace the complicated anti-corrosion treatment method of the surface of the traditional steel and may cause phase separation; the phosphoric acid side chain contained in the single liquid non-solvent resin The adhesion strength between the anti-corrosive coating film and the steel surface is further enhanced. The single-liquid non-solvent type phosphoric acid-containing side chain radical cross-linking polymer coating system related to the present invention uses a radical-hardening type (including acrylic terminal group) epoxy resin, 8 1290943, which is commercially available. The epoxy resin (such as South Asia Resin Company NPES-904) is used as raw material, and the epoxy equivalent of Acrylic Acid and epoxy resin is about 85 〇. : anti-fine triethylamine (tea) as a dopant, and - the reaction temperature (four) in 11G ~ boots, auxiliary gas or f oxygen correction (mG_ethyl etto - _e, MEHQ) as a free radical inhibitor. The reaction is controlled by the acid value (Add Vaiue), and the reaction can be stopped when the acid value is close to zero; or by FT_jR (Fourier-transfer infrared spectrometer), when the absorption of the epoxy group is completely disappeared in ft_ir, Stop the reaction, the product is a free radical hardening type (including acrylic end group) epoxy resin oligopolymer (hereinafter referred to as UV-EPOXY), the spectrum of which is shown in Figure 1, the reaction scheme is as follows: Preparation of hardened (including acrylic end group) epoxy resin oligopolymer (UV-EPOXY)).

Formula I 〇 -ch2( /\ ·· Δ 0

Acrylic Acid catafyst (TEA) Ο , ch2 丨

OH (_<Q-{-^-〇ch2chch2 o

-och2chch2〇" OH

UV-EPOXY 1290943 A single-liquid non-solvent type phosphoric acid-containing side chain radical cross-linking polymer coating system related to the present invention, which uses a phosphate-containing reactive (double bond) monomer (HEMA_P0H) The acrylate (such as 2-hydroxyethylmethacrylate, 2_HEMA) reacts with • PhosPhorus pentoxide (P205) until the white solid phosphorus pentoxide is reacted to form a liquid phosphate-containing reactive monomer (HEMA-P0H). Precursor, a mixture of acetone and deionized water (volume ratio: 1 〇 / 1) is added to the filtrate, and after fully-mixed, the phosphate-containing reactive monomer precursor is hydrolyzed to a phosphate-containing reactivity. Monomer (HEMA-P0H). The reaction scheme is as follows: (Preparation of a phosphoric acid-containing monomer (ΗΕΜΑ_ΡΟΗ) containing a phosphoric acid group, taking 2-oxime as an example).

1290943 Coating system, using a phosphoric acid radical-hardening epoxy resin oligomer 〇epoxy_poh), a free radical hardening type (including acrylic terminal group) epoxy resin synthesized by the previous formula J (UV-EPOXY) Reaction with phosphorus pentoxide, the steps and conditions are similar to those of the phosphoric acid-reactive (double bond) monomer (HEMA-POH) synthesized in Formula 11. The reaction scheme is as follows: m (preparation of a phosphoric acid-containing ultraviolet-reactive oligopolymer (Ερ〇χγ_ρ〇Η)).

The single-liquid non-solvent type phosphoric acid-containing side chain radical cross-linking polymer coating system of the invention adopts a phosphate-containing radical-hardening epoxy resin oligomer (EP0XY40H) and a phosphate-containing (double bond) monomer. (HEM A -P OH) is the raw material source of the main phosphoric acid-containing coating. More than one reactive diluent (such as trimethylolpropane triacrylate (TMPTA); difunctional group) is selected. 11 1290943 hexanediol diacrylate (HDDA); tripropylene glocol diacrylate (TPGDA); monofunctional methyl acrylate, decyl methacrylate Methyl ^ methacryhte), styrene, etc., adjust the viscosity of the coating system and the cross-linking density of the coating after hardening; use a heating initiator such as benzoyl peroxide (BPO); Diphenylidene phenyl peroxide (to (10) coffee per〇xide, - DCP); azobisisobutyronitrile (azo^^butyrinitriie, aibn), etc., or UV Lulu photoinitiator' such as benzoin Benzoin alkyl Ether), such as Merck 1173, etc., photosensitizers, such as benzophenone (BP) series, etc.; respectively, forming a single liquid non-solvent type phosphoric acid side chain free radical crosslinked polymer coating system, for scraping , spraying, or impregnation, etc., apply the surface of the material, and then use the normal temperature, heating or ultraviolet light to carry out the crosslinking reaction to achieve the purpose of hardening and drying the coating film. The single-liquid non-solvent type containing the phosphoric acid side chain free radical crosslinking polymer (4) related to the present invention, in the slit and Lai Wei fortune, no volatile mechanical solvent, and also appeals to the discharge of residual water 'is environmentally friendly and resource-saving Clean the process. The single-liquid non-solvent type phosphoric acid-containing side chain radical cross-linking polymer coating system (per 1000 g of anti-recording film _ acid content of 0.25 equivalent or more) which is related to the present invention is subjected to adhesion prevention. The strength of the grid test (Japanese Industrial Standard Claw (3) moved) and salt spray accelerated detection (10) 3), confirmed that the coating system can simplify the coating process, so that the steel surface has the practicality of the button. [Embodiment] 12 1290943 The following examples illustrate preferred embodiments of the present invention, but the present invention is not limited thereto. Preparation Example 1: Preparation of Radical Curing Epoxy Resin Oligomer (υν-ΕΡΟΧΥ) ^ Epoxy Resin Oligomer (Ethylene Equivalent EEW=828) 82.8 g dissolved in 100 ml of toluene and transferred In a three-necked reaction flask, slowly heat it to ii〇°c with a heating pack and mechanically stir it; add 8.0 g of acrylic acid to a small amount of triethylamine, mix well and homogenize, and slowly add in an isobaric addition funnel. In the reaction flask; air can be introduced into the reaction or p-methoxyphenol (MEHQ) can be added as a free radical inhibitor to control the temperature in the reaction flask to react between 110 and 140 ° C until the epoxy in the FT-IR spectrum. The reaction is completed when the absorption peak of the radical disappears completely, or when the acid value is approximately equal to 1 Torr or lower. The reaction is controlled by Acid Value. When the acid value is close to zero, the reaction can be stopped; or f1hr (Fourier transform infrared spectrometer) can be used to trace the FT-IR when the absorption of the epoxy group disappears completely. The reaction is stopped, and the product is a free radical hardening type (including an acrylic end group) epoxy resin oligopolymer (hereinafter referred to as UV-Ep0XY), and its spectrum is as shown in Fig. 1 Lulu. Formula I is a schematic diagram of the reaction scheme of a radically curable epoxy oligomer resin (υν-ΕΡ〇χγ). Preparation Example 2: Preparation of a UV-reactive monomer containing a tank acid group (ΗΕΜΑ_ρ〇Η) 0.11 mol of phosphorus pentoxide was placed in a reaction flask, and 0.2 mol of a hydroxyl group was added in an isobaric addition funnel. The acrylate compound (such as 24 ΙΕΜΑ) is slowly added to the reaction bottle. • When the pentoxide powder disappears slowly and the solution gradually turns into a yellowish clear liquid 13 1290943, the pentoxide is formed into a liquid scaly due to the reaction (ΙΕΜΑΙΕΜΑ_Κ )Η)^_,_ ▲" Early body green went to play the five oxidized two scales and collected Lai and deionized her view: _) _ liquid plus people gift, fully mixed, will contain two base anti-ship The bribe flooding is hydrolyzed into a phosphate-containing reactive early body (ΗΕΜΑ·Ρ〇Η), and the county will take C to the solution of the liquid (volume ratio: the ratio is about enough to be added to the human filtrate, fully mixed, then reduced Acetone and water are removed by pressure concentration; this product is a phosphate-containing reactive monomer (HEMA-PGH). Formula II is a schematic diagram of the preparation of a UV-reactive monomer (ΗΕΜΑ-ΡΟΗ) containing a Wei group. The spectrum is shown in Figures 2 to 4. Side 3 · UV reaction with acid groups Preparation of the oligopolymer ❹ ❹ ) 于 制备 制备 制备 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基 自由基The mean Φ Φ is the same as in the second embodiment. Formula 111 is a schematic diagram for the preparation of a phosphoric acid group-containing ultraviolet-reactive oligomer (EPOXY_POH). Its spectrum is shown in Figure 5. Example 1 The scaly acid-based radical-reactive monomer (HEMA_POH) prepared in Preparation Example 2 was different from the phosphate-containing radical-curable epoxy resin (EPOXY-ΡΟΗ) prepared in Example #3. The ratios were uniformly mixed (Table 1), and 1290943 HMOphr (per resin amount per mole) of reactive diluent was added to adjust the viscosity of the coating system to below 500 〇 cps and take 3-8 〇/. The benzammonium peroxide (Bp〇) heated radical initiator is added to the coating system formulation and applied to the surface of the steel by means of knife coating, spraying, or impregnation, respectively, and then heated separately. The cross-linking hardening reaction reaches the coating film and is dried to form a strong and continuous steel protective film. Example 2 #· Employment Example 1 'The unsaturated-containing polyester was used instead of the epoxy-based radical-curable epoxy resin (EPOXY_P〇H) prepared in Preparation Example 3, and the crosslinking hardening reaction was carried out by heating to obtain a coating film. Drying forms a strong and continuous steel protective film. Example 3: The same as the actual supplement h using an acid alcohol resin instead of the _ radical-curable epoxy resin (ΕΡΟΧΥ·Ρ〇Η) prepared in Preparation Example 3, using heat to carry out cross-linking hardening and anti-10 should be coated The film is dried to form a strong and continuous steel protective film. Example 4: The same procedure as in the preparation of the ultraviolet-curing type pu (poly) resin instead of the phosphate-containing radical-hardening type epoxy resin prepared in Preparation Example 3, using heat for crosslinking The hardening reaction forms a firm continuous steel protective film. 15 1290943 Example 5 In the same manner as in Example 1, benzoic acid phenylenediphenyl (DCP) was used instead of benzoic acid benzoate (BPO). The crosslinking hardening reaction was carried out at room temperature to achieve a firm and continuous coating film drying. Steel protective film. Example 6 Φ% The phosphate-containing radical-reactive monomer (HEMA_PQH) prepared in Preparation Example 2 and (iv) Example 3 剌 得 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸Mix uniformly in different proportions (Table 1}, and add 1〇_4_ of reactive diluent to adjust the viscosity of the coating system below 5〇〇〇cps, and take 3-5% Merck 1173 photoinitiator to the coating system. In the formulation, it is applied to the surface of the steel by means of blade coating, spraying, or impregnation, and then m cross-linking hardening reaction is carried out by ultraviolet light irradiation to form a firm and continuous steel protective film. ·· Example 7 _ Same as the method of Example 6 'Select 5-10% benzophenone photosensitizer with a tertiary amine\ as a cocatalyst to replace the photoinitiator, use UV light to carry out cross-linking hardening reaction to reach the coating film Drying to form a strong and continuous steel protective film. Example 8 16 1290943 In the same manner as in Example 6, the ultraviolet-curing type pu resin was used instead of the phosphate-containing radical-hardening type epoxy resin prepared in Example 3 (ΕΡ0ΧΥ-Ρ0Η) ), using ultraviolet light Cross-linking curing reaction, to form a coating film dried solid and continuous protective film of the steel.

Table 1 Proportion of main ingredients of anti-corrosion coatings

Adhesion strength (checker test) ◎ ◎ ◎ ◎ ◎ [Simplified description of the drawings] ·· The figure shows the single-liquid non-solvent type acid-containing side chain radical cross-linking polymer coating of the present invention. FT-IR spectrum of two radical-hardening epoxy resin oligomers (UV-EPOXY). Fig. 2 is a diagram showing the 1H- of the single-liquid non-solvent type acid-containing side bond radical cross-linking polymer coating system of the present invention, which contains a UV-reactive monomer 〇ΚΜΑ_Ρ〇ϋ. NMR spectrum. Figure 3 is a graph showing the 13c_NMR spectrum of a phosphoric acid group-containing ultraviolet-reactive monomer (HEMA-POH) used in the single-liquid non-solvent type hetero-containing side bond radical-free 17 1290943 polymer coating system of the present invention. Figure. • Figure 4 shows the 31P of the phosphoric acid-containing UV-reactive monomer (HEMA_P〇H) used in the single-liquid non-solvent type phosphoric acid-containing side chain radical crosslinking system of the present invention. - NMR spectrum. Figure 5 is a view showing the FT- of the phosphoric acid group-containing ultraviolet-reactive oligomer (EP0XV" P0h) used in the single-liquid non-solvent type phosphoric acid-containing side chain radical crosslinking high-component coating system of the present invention. IR spectrum. [Main component symbol description] 益参· 18

Claims (1)

1290943 X. Patent application scope: 1. A single-liquid non-solvent type phosphoric acid side chain free radical crosslinked polymer coating system, which is a phosphate-containing monomer with free radical reaction type (including double bond) and phosphoric acid The proportion of the radical-reactive oligomer is adjusted to the phosphoric acid content of the polymer coating system to a phosphoric acid content of at least 0.25 to 2.5 eq per 1000 g of the anti-corrosion coating film, and the radical-reactive monomer is blended The reactive diluent adjusts the viscosity of the coating and the crosslinking density of the coating film, and is selected from a thermal decomposition or ultraviolet light-initiating initiator to prepare a single-liquid non-solvent type phosphoric acid side chain free radical crosslinking polymer coating system. 2. The polymer coating system according to claim 1, which is applied to the surface of a steel material and then subjected to radical hardening reaction by heating or ultraviolet light to form a protective coating film for the steel material, and is contained in the coating film polymer. The phosphoric acid side chain and the steel surface produce a crystalline film of iron phosphate, and the phosphate film is treated with an anti-corrosion treatment and a primer treatment on the surface of the steel to simplify the process and provide a double anti-corrosion coating. 3. The polymer coating secret according to claim 1, wherein the single acid system having a pure acid group and having a radical reaction type (including a double bond) contains a thiophene and a pentoxide. Work scale (4) 5) reaction until the white solid pentoxide scale is formed by reaction to form a liquid acid-containing reactive monomer precursor, which is called a mixture of deionized water and added to the liquid mixture. The disc acid-reactive monomer precursor is hydrolyzed to a rock-containing acid-reactive monomer (ΗΕΜΑ-ΡΟΗ). The polymer coating system according to claim 1, wherein the phosphoric acid-containing reactive oligomer is an ultraviolet light curing epoxy resin oligomer and/or is selected from the group consisting of unsaturated polyesters and alkyds. Resin, polyamino phthalate (PU), and other epoxy resin groups ▲ , at least one reactive oligomer reacts with phosphorus pentoxide to synthesize a phosphate-containing radical-curable epoxy resin. The polymer coating system according to claim 1, wherein the radical reaction type single system as a reactive diluent contains a monofunctional (double bond) or a polyfunctional (double bond) press Monomer consisting of trimethylolpropane triacrylate (TMPTA) with trifunctional groups; difunctional hexanediol diacrylate (HDDA), tripropyl propyl diacrylate (TPGDA); monofunctional At least one selected from the group consisting of methyl acrylate, decyl decyl acrylate, and the present ethylene group. The polymer coating system according to claim 4, wherein the acid-containing reactive oligomer is selected from the group consisting of unsaturated polyester, alkyd resin and polyamino phthalate (PU). • At least one or all of the radically reactive oligomers containing phosphoric acid. 7. The polymer coating system according to claim 1, wherein the initiator is selected from the group consisting of bismuth oxide (BPO), benzodiazyl peroxide (DCP), azobis A heating initiator composed of butadiene nitrile (AIBN) or at least one of a benzoin-based radical ultraviolet light initiator and a dimercapone (BP) photosensitizer. 20