Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G10/00—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only
  • C08G10/02—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only of aldehydes
  • C08G10/04—Chemically-modified polycondensates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/62—Alcohols or phenols

Definitions

• the present invention relates to a modified aromatic hydrocarbon formaldehyde resin, an aqueous epoxy resin composition, and a cured product thereof.
• Aromatic hydrocarbon formaldehyde resin as a non-reactive modifier and a reactive modifier, improves various properties such as water resistance, corrosion resistance, and adhesion of resins such as acrylic resin, urethane resin, and epoxy resin. It is widely used for this purpose (Patent Document 1). In recent years, regulations on the use of solvents have become stricter due to the danger of fire and the effects on the human body. Therefore, it is desired to develop an aromatic hydrocarbon formaldehyde resin that can be used in an aqueous system (Patent Document 2).
• JP-A-61-228013 Japanese Unexamined Patent Publication No. 2001-261815
• Aromatic hydrocarbon formaldehyde resins that can be used in water systems are required to have further improvements in water resistance and adhesion. Further, if a commercially available surfactant is added to improve the emulsion stability, the water resistance, corrosion resistance and adhesion may be impaired. In response to this concern, a modified aromatic hydrocarbon formaldehyde resin having emulsifying performance is desired without using a commercially available surfactant.
• the present inventors have found that the above problems can be solved by modifying an aromatic hydrocarbon formaldehyde resin with a polyether monool or a polyether polyol, and have completed the present invention. It was. That is, the present invention is as follows.
• a modified aromatic hydrocarbon formaldehyde resin obtained by reacting an aromatic hydrocarbon formaldehyde resin with a polyether monool or a polyether polyol.
• the polyether monool or the polyether polyol is an ethylene oxide adduct or a trimethylene oxide adduct of a monohydric alcohol or polyol having 1 to 20 carbon atoms. Modified aromatic hydrocarbon formaldehyde resin.
• the polyether monool or the polyether polyol is a polyoxyethylene monomethyl ether, polyethylene glycol, polyoxyethylene glycerol ether, polyoxyethylene trimethylolpropane ether, polyoxyethylene neopentyl glycol ether and polyoxyethylene pentaeri.
• Modified aromatic hydrocarbon formaldehyde resin [9] The modified aromatic hydrocarbon formaldehyde resin according to the above [8], wherein 30 to 900 parts by mass of a polyether monool or a polyether polyol is reacted with 100 parts by mass of the aromatic hydrocarbon formaldehyde resin. [10] The modified aromatic hydrocarbon formaldehyde resin according to any one of the above [1] to [9], wherein the modified aromatic hydrocarbon formaldehyde resin has a weight average molecular weight of 300 to 100,000. [11] An aqueous epoxy resin composition containing the modified aromatic hydrocarbon formaldehyde resin (A), the epoxy resin (B) and the aqueous medium (C) according to any one of the above [1] to [10].
• the present embodiment a mode for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail.
• the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the embodiments.
• the present invention can be appropriately modified and implemented within the scope of the gist thereof.
• the preferred provisions can be arbitrarily adopted, and it can be said that a combination of preferable ones is more preferable.
• the description of "XX to YY" means "XX or more and YY or less”.
• Aromatic hydrocarbons include benzene, toluene, xylene, mesitylene, pseudocumene, ethylbenzene, propylbenzene, decylbenzene, cyclohexylbenzene, biphenyl, methylbiphenyl, naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, anthracene, methylanthracene, dimethyl.
• At least one selected from the group consisting of anthracene, ethylanthracene, and benzene can be mentioned.
• At least one selected from the group consisting of xylene, toluene, mesitylene and pseudocumene from the viewpoint of imparting excellent flexibility, adhesion, water resistance and corrosion resistance to the cured product obtained by curing the aqueous epoxy resin composition containing the resin. More preferably xylene, and even more preferably metaxylene.
• the aromatic hydrocarbon formaldehyde resin is a xylene formaldehyde resin obtained by reacting xylene with formaldehyde, a toluene formaldehyde resin obtained by reacting toluene with formaldehyde, and mesitylene and formaldehyde. It is preferable to contain at least one selected from the mesitylene formaldehyde resin obtained by the reaction, and it is more preferable to contain the xylene formaldehyde resin.
• the aromatic hydrocarbon formaldehyde resin may be a commercially available product or may be prepared by a known method.
• commercially available products include "Nicanor Y-100", “Nicanor Y-300", “Nicanor LLL” and “Nicanor H” as xylene resins manufactured by Fudow Company Limited.
• known methods include a method of condensing aromatic hydrocarbons and formaldehyde in the presence of a catalyst by the method described in Japanese Patent Publication No. 37-5747.
• the weight average molecular weight (Mw) of the aromatic hydrocarbon formaldehyde resin is preferably 200 to 10,000, more preferably 300 to 2,000, still more preferably 350 to 1,500, still more preferably 350 to 1,500 in terms of polystyrene. It is 500 to 1,000. It is preferable that the Mw of the aromatic hydrocarbon formaldehyde resin is in the above range because the compatibility with other resin components in the composition can be sufficiently maintained.
• the weight average molecular weight (Mw) can be measured by the method described in the examples of the present application by the gel filtration chromatography (GPC) method.
• the polyether monool or the polyether polyol is not particularly limited, and examples thereof include an ethylene oxide adduct or a trimethylene oxide adduct of a monohydric alcohol or polyol having 1 to 20 carbon atoms.
• the number of carbon atoms of the ethylene oxide adduct or trimethylene oxide adduct of the monohydric alcohol or polyol is more preferably 1 to 10, and even more preferably 1 to 5.
• monohydric alcohols or polyols having 1 to 20 carbon atoms examples include aliphatic monohydric alcohols or polyols such as methanol, ethanol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, trimethylolpropane, and neopentyl glycol, or phenol.
• Aromatic monohydric alcohols such as cresol, butylphenol and nonylphenol or polyols can be used.
• an aliphatic polyol is preferable.
• the aliphatic polyol is not particularly limited, but is limited to trimethylolpropane, neopentyl glycol, ester glycol, spiroglycol, pentaerythritol, ethylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, and 1,3-butanediol.
• 1,4-Butanediol 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-hexanediol, trimethylolethane, 1,2-octanediol, 1,10 -Decandiol, 3-hexine-2,5-diol, 2,5-dimethyl-3-hexine-2,5-diol, 2,2,4-trimethyl-1,3-pentanediol, polyethylene glycol and polyoxy Examples include propylene glycol and the like.
• At least one selected from the group consisting of ethylene glycol, propylene glycol, glycerin, trimethylolpropane and neopentyl glycol is preferable, ethylene glycol or glycerin is more preferable, and ethylene glycol is further preferable.
• These monohydric alcohols or polyols can be used alone or in combination of two or more.
• the polyether monool or the polyether polyol refers to a compound in which ethylene oxide or trimethylene oxide is added to the monohydric alcohol or polyol, more preferably a compound in which ethylene oxide is added, and is not particularly limited as long as the requirements are satisfied. .. Specific polyether monools or polyether polyols include polyoxyethylene monomethyl ether, polyethylene glycol, polyoxyethylene glycerol ether, polyoxyethylene trimethylolpropane ether, polyoxyethylene neopentyl glycol ether and polyoxyethylene pentaeri. At least one selected from the group consisting of striel ether and the like can be mentioned.
• polyethylene glycol or polyoxyethylene glycerol ether it is more preferable to use polyethylene glycol.
• polyether monools or polyether polyols may be used alone or in combination of two or more.
• the weight average molecular weight (Mw) of the above-mentioned polyether monool or the polyether polyol is preferably in the range of 450 to 50,000 in terms of polystyrene.
• the weight average molecular weight of the polyether monool or the polyether polyol can be measured by the method described in Examples of the present application by the GPC method.
• the weight average molecular weight of the polyether monool or the polyether polyol is in the above range, the composition emulsion containing the aqueous medium, other resins, and the modified aromatic hydrocarbon formaldehyde resin is excellent in static stability.
• the weight average molecular weight of the above-mentioned polyether monool or polyether polyol is more preferably 750 to 25,000, still more preferably 1,100 to 14,000 in terms of polystyrene.
• the modified aromatic hydrocarbon formaldehyde resin of the present embodiment can be obtained by reacting the above-mentioned aromatic hydrocarbon formaldehyde resin (unmodified) with a polyether monool or a polyether polyol. Since the modified aromatic hydrocarbon formaldehyde resin of the present embodiment uses an aromatic hydrocarbon formaldehyde resin whose structure is difficult to identify by analysis as a raw material, the modified aromatic hydrocarbon formaldehyde resin modified with the above additives can also be used. It is difficult to analyze and identify its structure.
• the modified aromatic hydrocarbon formaldehyde resin of the present embodiment is a polyether monool or a polyether polyol modified xylene formaldehyde resin, from the viewpoint of imparting flexibility to a cured product obtained by curing an aqueous epoxy resin composition containing the resin. It is preferable to contain at least one selected from a polyether monool or a polyether polyol modified toluene formaldehyde resin and a polyether monool or a polyether polyol modified mesityrene formaldehyde resin, and a polyether monool or a polyether polyol modified xylene formaldehyde resin is preferably contained. It is more preferable to include it.
• the modified aromatic hydrocarbon formaldehyde resin of the present embodiment can be prepared by adding a polyether monool or a polyether polyol to the aromatic hydrocarbon formaldehyde resin under an acidic catalyst.
• the acidic catalyst is not particularly limited, but paratoluenesulfonic acid, metaxylenesulfonic acid, paratoluenesulfonic acid chloride and the like can be used.
• the reaction temperature of the aromatic hydrocarbon formaldehyde resin and the polyether monool or the polyether polyol can be usually 100 to 190 ° C, preferably 120 to 150 ° C.
• the reaction time is not particularly limited, but is, for example, 0.5 to 30 hours, preferably 0.5 to 15 hours.
• the amount is preferably 10 to 990 parts by mass, more preferably 30 to 900 parts by mass with respect to 100 parts by mass of the aromatic hydrocarbon formaldehyde resin.
• the part of the polyether monool or the polyether polyol is reacted.
• the amount of the polyether monool or the polyether polyol is in the above range, the static stability of the composition emulsion containing the aqueous medium, other resins and the obtained modified aromatic hydrocarbon formaldehyde resin can be kept good. ..
• the weight average molecular weight (Mw) of the modified aromatic hydrocarbon formaldehyde resin of the present embodiment is preferably 300 to 100,000, more preferably 700 to 30,000, still more preferably 700 to 10, in terms of polystyrene. It is 000.
• the weight average molecular weight can be measured by the method described in Examples of the present application by the GPC method.
• the aqueous epoxy resin composition in the present embodiment contains a modified aromatic hydrocarbon formaldehyde resin (A), an epoxy resin (B) and an aqueous medium (C).
• a modified aromatic hydrocarbon formaldehyde resin (A) the above-mentioned modified aromatic hydrocarbon formaldehyde resin is used.
• the epoxy resin (B) is not particularly limited, and any of an epoxy resin derived from alicyclic alcohols, an epoxy resin derived from aromatic alcohols (phenols), or an alicyclic epoxy resin can be used. it can. Specifically, an epoxy resin having a glycidyl ether moiety derived from bisphenol A type, an epoxy resin having a glycidyl ether moiety derived from bisphenol F type, and an alicyclic aliphatic epoxy having an epoxycyclohexyl ring in the molecule. Examples include resin. Among these, an epoxy resin having a glycidyl ether moiety derived from bisphenol A type is particularly preferable from the viewpoint of viscosity and availability.
• the aqueous epoxy resin composition of the present embodiment has a modified aromatic content such that the content of the modified aromatic hydrocarbon formaldehyde resin (A) is 0.01 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin (B). It is preferable to contain the group hydrocarbon formaldehyde resin (A) and the epoxy resin (B). When the amount relationship between the two is within the above range, the aqueous epoxy resin composition can be sufficiently cured, and a cured product having sufficient adhesion and the like can be obtained.
• the content of the modified aromatic hydrocarbon formaldehyde resin (A) in the aqueous epoxy resin composition in the present embodiment is more preferably 1 to 25 parts by mass, still more preferably 1 to 25 parts by mass, based on 100 parts by mass of the epoxy resin (B). Is 9 to 20 parts by mass.
• the aqueous medium (C) is not particularly limited, and known aqueous media such as water and a water-soluble organic solvent can be used.
• water include ion-exchanged water, distilled water, tap water, industrial water and the like.
• water-soluble organic solvent include alcohols having 1 to 3 carbon atoms (methanol, ethanol, isopropanol, etc.), ketones having 3 to 6 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), and ethers having 2 to 6 carbon atoms (dimethyl ether).
• aqueous media water and a mixed solvent of water and a hydrophilic organic solvent are preferable from the viewpoint of safety and the like, and water is more preferable.
• the aqueous epoxy resin composition of the present embodiment contains a filler, a modifying component such as a plasticizer, a reactive or non-reactive diluent, depending on the application, as long as the effects of the embodiment of the present invention are not impaired.
• Flow adjusting components such as rocking modifiers, components such as pigments, and additives such as epoxy inhibitors, spreading agents, defoaming agents, ultraviolet absorbers, and preservatives can be used.
• the cured product of the aqueous epoxy resin composition of the present embodiment can be obtained by various known methods, and may be cured at room temperature or by heating. When curing at room temperature, the curing time may be about 1 to 10 days.
• the heating conditions may be appropriately selected according to the epoxy resin, each component in the composition containing the resin, and the content of the resin and each component, but are preferably 60 to 120 ° C. for 90 minutes to 150. It is selected in the range of minutes, more preferably 70 to 90 ° C. for 100 to 140 minutes.
• the cured product of the aqueous epoxy resin composition of the present embodiment is preferably obtained by adding an epoxy resin curing agent to the above aqueous epoxy resin composition and reacting it.
• the epoxy resin curing agent is not particularly limited, and for example, amine compounds, polyfunctional phenols, acid anhydride compounds, amide compounds and the like are used. Of these, it is preferable to use an amine compound from the viewpoint of improving the water resistance, adhesion and corrosion resistance of the cured product of the aqueous epoxy resin composition.
• the content of the epoxy resin curing agent is preferably 10 to 300 parts by mass with respect to 100 parts by mass of the epoxy resin (B), preferably 50 to 280 parts by mass. It is more preferably contained by mass, and further preferably 100 to 250 parts by mass.
• the content of the epoxy resin curing agent is within the above range, the water resistance, adhesion and corrosion resistance of the cured product of the aqueous epoxy resin composition can be improved.
• the aqueous epoxy resin composition of the present embodiment contains the above-mentioned modified aromatic hydrocarbon formaldehyde resin (A) having an excellent emulsifying action, the obtained cured product is excellent in adhesion, corrosion resistance, flexibility and hardness of the coating film. Has advantages.
• Emulsified phase volume ratio is 90% or more: A Emulsified phase volume ratio less than 90% 80% or more: B Emulsified phase volume ratio less than 80% 70% or more: C Does not become an emulsion: D
• Xylene resin "NIKANOL Y-100" (hydroxyl value: 25 mgKOH / g) manufactured by Fudo Co., Ltd. as an aromatic hydrocarbon formaldehyde resin in a reaction vessel having an internal volume of 500 mL equipped with a stirrer, a thermometer, a steam introduction pipe, and a distillate.
• 234 g (100 parts by mass) of (weight average molecular weight: 350) and 26 g (11 parts by mass) of polyethylene glycol 2000 (manufactured by Kanto Chemical Co., Ltd.) as a polyether polyol were charged, heated to 60 ° C. and stirred.
• Examples 2 to 15 The reaction was carried out in the same manner as in Example 1 except that the type and amount of the aromatic hydrocarbon formaldehyde resin or polyether polyol were changed as shown in Table 1, to obtain a polyether polyol-modified aromatic hydrocarbon formaldehyde resin.
• ⁇ Comparative example 1> Xylene resin "NIKANOL Y-100" (hydroxyl value: 25 mgKOH / g) manufactured by Fudo Co., Ltd. as an aromatic hydrocarbon formaldehyde resin in a reaction vessel with an internal volume of 500 mL equipped with a stirrer, thermometer, steam introduction pipe, and distillate. 130 g (100 parts by mass) of (weight average molecular weight: 350) was charged, 130 g (100 parts by mass) of polyethylene glycol 2000 (manufactured by Kanto Chemical Co., Ltd.) was charged as a polyether polyol, the temperature was raised to 80 ° C., and the mixture was stirred for 30 minutes. After that, it was taken out from the flask to obtain a resin mixture of a polyether polyol and an aromatic hydrocarbon formaldehyde resin.
• NIKANOL Y-100 hydroxyl value: 25 mgKOH / g
• NIKANOL H manufactured by Fudo Co., Ltd.
• Epoxy resin jER1003 ⁇ trade name, manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 700
• MIBK methyl isobutyl ketone
• NIKANOL L5" hydroxyl value: 35, weight average molecular weight: 1200 (polystyrene equivalent) manufactured by Fudow Company Limited.
• An emulsion for evaluation of static stability of Reference Example was obtained in the same manner as described above except that it was changed.
• the static stability evaluation of the above emulsion was carried out. The results are shown in Table 2.
• "NIKANOL L5" is a xylene resin to which ethylene oxide is added, and the average number of moles of the added ethylene oxide added is 12.
• Examples A to J and Comparative Examples A to D > 10 parts by mass of the modified aromatic hydrocarbon formaldehyde resin or resin mixture obtained in the examples or comparative examples shown in Tables 3 and 4 is added to an epoxy resin (an epoxy resin jER828 having a glycidyl ether moiety derived from bisphenol A type].
• an epoxy resin an epoxy resin jER828 having a glycidyl ether moiety derived from bisphenol A type.
• Product name manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 190]
• ion-exchanged water 85 parts by mass of ion-exchanged water was further prepared and added dropwise with stirring.
• the dropping of ion-exchanged water was temporarily stopped, and then stirring was performed for 2 minutes.
• the remaining ion-exchanged water was added and stirred for 5 minutes to obtain each aqueous epoxy resin composition shown in Tables 3 and 4.
• Each of the obtained aqueous epoxy resin compositions, an amine-based epoxy resin curing agent (ARADUR 3896, manufactured by HUNTSMAN) and an aqueous solvent (water, butyl cellosolve) were mixed in parts by mass shown in the table to obtain a curable resin composition.
• the above curable resin composition was applied onto a steel plate (“PB-N144” manufactured by PALTEK Corporation, thickness 0.5 mm, 150 ⁇ 70 mm) using an applicator, and in an atmosphere of 23 ° C. and 50% RH for 7 days. It was cured to obtain a cured coating film having a thickness of about 40 ⁇ m. The above evaluation test was carried out on the obtained cured coating film. The results are shown in Tables 3 and 4.
• Example K 10.6 parts by mass of the modified aromatic hydrocarbon formaldehyde resin obtained in Example 1 was added to T.I. While stirring at 3000 rpm using K HOMO DISPER MODEL 2.5 (a product manufactured by Premix Co., Ltd.), 4.0 parts by mass of ion-exchanged water was added dropwise as an aqueous medium (C) and stirred for 10 minutes. Then, 2.2 parts by mass of ion-exchanged water was added and stirred for 5 minutes, and then this operation was repeated twice to obtain an emulsion of Example K. A total of 10.6 parts by mass of ion-exchanged water was added as the aqueous medium (C).
• K HOMO DISPER MODEL 2.5 a product manufactured by Premix Co., Ltd.
• the obtained emulsion was mixed with 100.0 parts by mass of an aquatic epoxy resin composition (jER WD1155R55, manufactured by Mitsubishi Chemical), 69.2 parts by mass of an amine-based epoxy resin curing agent (jER WD11M60, manufactured by Mitsubishi Chemical), and an aqueous solvent (ion exchange). Water) 63.4 parts by mass was mixed to obtain a curable resin composition of Example K.
• the above curable resin composition was applied onto a steel plate (“PB-N144” manufactured by PALTEK Corporation, thickness 0.5 mm, 150 ⁇ 70 mm) using an applicator, and in an atmosphere of 23 ° C. and 50% RH for 7 days. It was cured to obtain a cured coating film (thickness of about 40 ⁇ m) of Example K.
• Examples L and M The modified aromatic hydrocarbon formaldehyde resin was changed to the modified aromatic hydrocarbon formaldehyde resin obtained in Example 3 or 4, and the modified aromatic hydrocarbon formaldehyde resin and the xylene resin "NIKANOL H" manufactured by Fudo Co., Ltd. were used. Valuation: 33 mgKOH / g, weight average molecular weight: 1000) were mixed at the ratios shown in Table 5 to prepare emulsions, and the emulsions and curable properties of Examples L and M were prepared in the same manner as in Example K. A resin composition and a cured coating film were obtained.
• Comparative example E A curable resin composition and a cured coating film of Comparative Example E were obtained in the same manner as in Example K except that an emulsion was not used.
• Examples KM are superior in mirror glossiness and water resistance as compared with Comparative Example E to which the emulsion obtained by using the modified formaldehyde hydrocarbon resin of the present embodiment is not added. It is confirmed.

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• 2020
  • 2020-08-19 WO PCT/JP2020/031189 patent/WO2021039512A1/ja active Application Filing
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