Scale-preventing composition and scale-preventing agent

Abstract

To provide means that can reduce the number of times a water scale deposition inhibitor is applied.SOLUTION: A composition for inhibiting water scale deposition includes a water scale deposition inhibitor represented by the following formula (1), and a resin.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a scale adhesion prevention composition and a scale adhesion prevention agent.

Background Art

[0002] In places where water is used, such as toilets, washbasins, and bathrooms, scale stains occur. Scale stains are caused by minerals such as magnesium and calcium contained in tap water, and are generated when only the minerals contained in the water droplets remain after the water has evaporated. If left untreated, scale becomes stubborn dirt and is difficult to remove with regular cleaning. For this reason, various detergents for removing scale have been proposed.

[0003] For example, Patent Document 1 discloses a slowly soluble polymer film as a scale adhesion prevention agent with water resistance.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, since the scale adhesion prevention agent described in Patent Document 1 removes the adhered dirt by dissolving the surface layer portion of the film when water flows, it is necessary to apply the scale adhesion prevention agent every time it is washed. Therefore, it is required to reduce the number of applications.

[0006] Therefore, the present invention has been made in view of the above circumstances, and an object thereof is to provide means for reducing the number of applications.

Means for Solving the Problems

[0007] The inventors of this invention conducted diligent research to solve the above problems. As a result, they discovered that the above problems can be solved by using a specific limescale inhibitor, and thus completed the present invention.

[0008] In other words, the above objective is expressed in the following formula (1):

[0009] [ka]

[0010] In the above formula (1), Q is an alkali metal, an alkaline earth metal, or a nitrogen-containing compound. A is a linear or branched alkylene group having 2 to 4 carbon atoms. m represents the average number of moles of AO added, and ranges from 1 to 200. Y is a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms. n is either 0 or 1. R 1 is a hydrogen atom or a methyl group, R 2 This is a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, or a group represented by the following formula (2):

[0011] [ka]

[0012] In equation (2) above, R 3 and R 4 Each of these is independently a hydrogen atom or a methyl group, and * represents a linking point. l is 1 to 3, p is Q + It represents the valence, which is 1 or 2. This is achieved by a limescale prevention composition comprising a limescale prevention agent and a resin, as indicated by [the relevant symbol].

[0013] Moreover, the above object is achieved by the scale adhesion inhibitor represented by the above formula (1).

Advantages of the Invention

[0014] According to the present invention, the number of coating times can be reduced.

Embodiments for Carrying Out the Invention

[0015] The present invention provides the following formula (1):

[0016]

Chemical Formula

[0017] In the above formula (1), Q is an alkali metal, an alkaline earth metal, or a nitrogen-containing compound, A is a linear or branched alkylene group having 2 to 4 carbon atoms, m represents the average number of moles of AO added, and is 1 to 200, Y is a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms, n is 0 or 1, R 1 is a hydrogen atom or a methyl group, R 2 is a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, or a group represented by the following formula (2),

[0018]

Chemical Formula

[0019] In the above formula (2), R 3 and R 4 are each independently a hydrogen atom or a methyl group, * represents a connection point, l is 1 to 3, p represents the valence of Q + and is 1 or 2, A limescale-preventing composition (first embodiment) is provided, comprising a limescale-preventing agent and a resin as shown in [the relevant diagram].

[0020] Furthermore, the present invention provides a limescale inhibitor represented by the above formula (1) (second embodiment).

[0021] According to the present invention, the number of applications can be reduced (the limescale prevention effect can be maintained for a long period of time).

[0022] The embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments described below.

[0023] Furthermore, in this specification, the range "X~Y" includes X and Y, meaning "X or greater and Y or less." Also, in this specification, "and / or" is used to mean including at least one of the components listed before or after it. For example, "A and / or B" includes A only, B only, and a combination of A and B. Unless otherwise specified, operations and measurements of physical properties, etc., are performed under conditions of room temperature (20~25°C) / relative humidity 40~50%RH.

[0024] (Water stain prevention agent) The limescale-preventing composition according to this disclosure comprises a limescale-preventing agent of the following formula (1). The limescale-preventing agent according to this disclosure is represented by the following formula (1). The limescale-preventing composition may contain one limescale-preventing agent of the following formula (1) alone, or it may contain two or more limescale-preventing agents of the following formula (1). Similarly, the limescale-preventing agent may consist of one limescale-preventing agent of the following formula (1) alone, or it may consist of two or more limescale-preventing agents of the following formula (1).

[0025] [ka]

[0026] In the above formula (1), Q is an alkali metal, an alkaline earth metal, or a nitrogen-containing compound. Here, Q +As an alkali metal cation, lithium ions (Li + ), sodium ions (Na + ), potassium ions (K + ), rubidium ion (Rb + ), cesium ions (Cs + ) is also available. + As an alkaline earth metal cation, magnesium ion (Mg 2+ ), calcium ions (Ca 2+ ), strontium ions (Sr 2+ ), barium ions (Ba 2+ ) exists. Q + As for nitrogen-containing compound cations (unsubstituted form), there is ammonium ion (ammonium cation) (NH4 + ), there are imidazolium ions, pyridinium ions, pyrrolidinium ions, pyrrolidinium ions, piperidinium ions, pyrazinium ions, pyrimidinium ions, triazolium ions, triazinium ions, quinolinium ions, isoquinolinium ions, indolinium ions, quinoxalinium ions, piperadinium ions, oxazolinium ions, thiazolinium ions, and morpholinium ions. See above Q + The example ions may exist individually or in combination of two or more. + The nitrogen-containing compound constituting the exemplary ion may be in the form described above (unsubstituted form), or it may have at least one selected from the group consisting of alkyl groups, ethylenically unsaturated bonding groups, and alkylene groups. Here, "the nitrogen-containing compound has at least one selected from the group consisting of alkyl groups, ethylenically unsaturated bonding groups, and alkylene groups" refers to the above Q + The exemplary ions are in which the hydrogen atoms of nitrogen-containing compounds are substituted with alkyl groups or ethylenically unsaturated bonding groups, and the above Q +The nitrogen atom of the nitrogen-containing compound constituting the exemplary ion is linked to an alkyl group or an ethylenically unsaturated bond group via an alkylene group. It may satisfy only one of these forms, or both. Alkyl groups include linear, branched, or cyclic alkyl groups having 1 to 25 carbon atoms. Specifically, these include methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, tert-butyl, i-butyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, i-pentyl, neopentyl, tert-pentyl (t-pentyl), cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n -Hexyl group, 1-methylhexyl group, 2-ethylhexyl group, 2-butylhexyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-tert-butylcyclohexyl group (4-t-butylcyclohexyl group), n-heptyl group, 1-methylpeptyl group, 2,2-dimethylheptyl group, 2-ethylheptyl group, 2-butylheptyl group, n-octyl group, tert-octyl group (t-octyl group), 2-ethyl Octyl group, 2-butyloctyl group, 2-hexyloctyl group, 3,7-dimethyloctyl group, cyclooctyl group, n-nonyl group, n-decyl group, adamantyl group, 2-ethyldecyl group, 2-butyldecyl group, 2-hexyldecyl group, 2-octyldecyl group, n-undecyl group, n-dodecyl group, 2-ethyldodecyl group, 2-butyldodecyl group, 2-hexyldodecyl group, 2-octyldecyl group, n-tridecyl group, Linear or branched alkyl groups such as n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, 2-ethylhexadecyl group, 2-butylhexadecyl group, 2-hexylhexadecyl group, 2-octylhexadecyl group, n-heptadecyl group, and n-octadecyl group; for example, cycloalkyl groups include cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. Of these, linear or branched alkyl groups having 1 to 8 carbon atoms are preferred, linear or branched alkyl groups having 1 to 3 carbon atoms are more preferred, and methyl or ethyl groups are particularly preferred.Examples of ethylenically unsaturated bonding groups include acryloyl group (H2C=CH-C(=O)-), methacryloyl group (H2C=C(CH3)-C(=O)-), acryloyloxy group (H2C=CH-C(=O)-O-), methacryloyloxy group (H2C=C(CH3)-C(=O)-O-), acrylamide group (H2C=CH-C(=O)-NH-), methacrylamide group (H2C=C(CH3)-C(=O)-NH-), vinyl group (H2C=CH-), and allyl group (H2C=CHCH2-). Alkylene groups can exist, for example, between the above nitrogen-containing compound ions and alkyl groups or ethylenically unsaturated bonding groups. Preferably, alkylene groups exist between the above nitrogen-containing compound ions and ethylenically unsaturated bonding groups. Alkylene groups include linear or branched alkylene groups having 1 to 4 carbon atoms. Specifically, these include methylene, ethylene, trimethylene, propylene, and tetramethylene groups. Of these, ethylene, trimethylene, and propylene groups are preferred, with ethylene being more preferred. Alkylene oxide groups include groups represented by the formula -A'O-, where A' is a linear or branched alkylene group having 1 to 4 carbon atoms. Specifically, these include methylene, ethylene, trimethylene, propylene, and tetramethylene groups. Of these, ethylene, trimethylene, and propylene groups are preferred, with ethylene being more preferred.

[0027] The above Q + The nitrogen-containing compounds constituting the exemplary ions preferably have an alkyl group, and more preferably have an alkyl group and an ethylenically unsaturated bonding group.

[0028] Specific examples of nitrogen-containing compound cations include, for example, the ammonium ion (NH4). +), monovinylammonium ion, divinylammonium ion, trivinylammonium ion, monopropenylammonium ion, dipropenylammonium ion, trippropenylammonium ion, monobutenylammonium ion, dibutenylammonium ion, triphenylammonium ion, monopentenylammonium ion, dipentenylammonium ion, tripentenylammonium ion, monohexenylammonium ion, dihexenylammonium ion, monoheptenylammonium ion, diheptenylammonium ion, monooctenylammonium ion, dioctenylammonium ion, monononenylammonium ion, monodecenylammonium ion, monoundecenylammonium ion, monododecenylammonium ion, monotridecenylammonium ion, monotetradecenylammonium ion, monopentadecenylammonium ion, monohexadecenylammonium ion, monoheptadecenylammonium ion, monooctadecenylammonium ion, monononadecenylammonium ion, monoikose Nylammonium ion, monohenicocenylammonium ion, monodococenylammonium ion, monotricocenylammonium ion, dimethyl(vinyl)ammonium ion, dimethyl(propenyl)ammonium ion, dimethyl(butenyl)ammonium ion, dimethyl(pentenyl)ammonium ion, dimethyl(hexenyl)ammonium ion, dimethyl(heptenyl)ammonium ion, dimethyl(octenyl)ammonium ion, dimethyl(nonenyl)ammonium ion, dimethyl(decenyl)ammonium ion, dimethyl(undecenyl)ammonium ion, dimethyl(dodecenyl)ammonium ion, dimethyl(tridecenyl)ammonium ion, dimethyl(tetradecenyl)ammonium ion, dimethyl(pentadecenyl)ammonium ion, dimethyl(hexadecenyl)ammonium ion, dimethyl(heptadecenyl)ammonium ion, dimethyl(octadecenyl)ammonium ion, dimethyl(nonadecenyl)ammonium ion, dimethyl(icocenyl)ammonium ion, dimethyl(henicocenyl)ammonium ion,Dimethyl(tricocenyl)ammonium ion, dimethylmonoacrylate ethylammonium ion, dimethylmonomethacrylate ethylammonium ion, diethylmonoacrylate ethylammonium ion, diethylmonomethacrylate ethylammonium ion, 2-vinylpyridinium ion, 4-vinylpyridinium ion, 1,2,2,6,6-pentamethyl-4-acrylate piperidinium ion, 1,2,2,6,6-pentamethyl-4-methacrylate piperidinium ion, 1,3,5-triacryloylhexahydro-1,3,5-triazinium ion, 2,4,6-tris(allyloxy)-1,3,5-triazinium ion, 2,4,6-tris(allyloxy)-1,3,5-triazinium ion, 1-allylpiperazinium ion, 1-(2-methylallyl)piperazinium ion, N-(meth)acryloylmorpholinium ion, ethylethanolammonium ion (NH2, + Examples include (C2H5)(C2H4OH), 1-(acrylamideethyl)trimethylammonium ion, 1-(methacrylamideethyl)trimethylammonium ion, 1-(acrylamidepropyl)trimethylammonium ion, 1-(methacrylamidepropyl)trimethylammonium ion, 1-(acrylamideethyl)dimethylammonium ion, 1-(methacrylamideethyl)dimethylammonium ion, 1-(acrylamidepropyl)dimethylammonium ion, 1-(methacrylamidepropyl)dimethylammonium ion, diethylmono(2-isocyanoethyl)ammonium ion, diethylmono(2-cyanopropyl)ammonium ion, and diethylmono(1,2-epoxypropane)ammonium ion. Among these, ammonium ions (NH4 +), dimethylmonoacrylate ethylammonium ion, dimethylmonomethacrylate ethylammonium ion, diethylmonoacrylate ethylammonium ion, diethylmonomethacrylate ethylammonium ion, 1,2,2,6,6-pentamethyl-4-acrylate piperidinium ion, 1,2,2,6,6-pentamethyl-4-methacrylate piperidinium ion, and ethylethanolammonium ion are preferred. Ammonium ion (NH4 + More preferably, dimethylmonoacrylate ethylammonium ion, dimethylmonomethacrylate ethylammonium ion, 1,2,2,6,6-pentamethyl-4-methacrylate piperidinium ion, and ethylethanolammonium ion are used.

[0029] Of these, from the viewpoint of further improving the effects according to the present invention, Q + These are alkali metal cations (Q = alkali metal) and ammonium cations (NH4 + ) or a nitrogen-containing compound cation having an alkyl group is preferable. + These are alkali metal cations (Q = alkali metal) and ammonium cations (NH4 + ) or a nitrogen-containing compound cation having an alkyl group and an ethylenically unsaturated bonding group. More preferably Q + These are sodium ions, potassium ions, and ammonium cations (NH4 + ), N,N-dimethylmonoacrylate ethylammonium ion, N,N-dimethylmonomethacrylate ethylammonium ion, diethylmonoacrylate ethylammonium ion, diethylmonomethacrylate ethylammonium ion, 1,2,2,6,6-pentamethyl-4-acrylate piperidinium ion, 1,2,2,6,6-pentamethyl-4-methacrylate piperidinium ion, ethylethanolammonium ion. Particularly preferred is Q + These are sodium ions and ammonium cations (NH4 +These are N,N-dimethylmonoacrylate ethylammonium ion, N,N-dimethylmonomethacrylate ethylammonium ion, 1,2,2,6,6-pentamethyl-4-methacrylate piperidinium ion, and ethylethanolammonium ion.

[0030] In formula (1) above, A is a linear or branched alkylene group having 2 to 4 carbon atoms. Examples of linear or branched alkylenes having 2 to 4 carbon atoms include ethylene, trimethylene, propylene, tetramethylene, and butylene groups. Of these, from the viewpoint of further improving the effects of the present invention, A is preferably an ethylene group, trimethylene group, or propylene group, and more preferably an ethylene group.

[0031] In formula (1) above, m represents the average number of moles of AO added and is between 1 and 200. From the viewpoint of further improving the effects of the present invention, m is preferably between 1 and 150, more preferably between 2 and 100, even more preferably between 5 and 50, and particularly preferably between 8 and 15.

[0032] In formula (1) above, Y is a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms. Examples of linear or branched alkylene groups having 1 to 5 carbon atoms include methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, and butylene groups. Of these, from the viewpoint of further improving the effects of the present invention, Y is preferably a single bond or a methylene group, and more preferably a single bond.

[0033] In the above formula (1), n ​​is either 0 or 1, and is preferably 1.

[0034] In the above equation (1), R 1 This is either a hydrogen atom or a methyl group, and a methyl group is preferred.

[0035] In equation (1) above, p is Q +This represents the valence of the atom, which is 1 or 2, preferably 1.

[0036] In the above equation (1), R 2 R is a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, or a group represented by the following formula (2). Here, R 2 If there are multiple instances (where l is 2 or 3), then each R 2 These may be the same or different. 1 and R 2 Preferably, at least one of them is an atom other than a hydrogen atom.

[0037] [ka]

[0038] A linear, branched, or cyclic alkyl group (R) having 1 to 25 carbon atoms. 2Examples of substituents include alkyl groups similar to those described above. Alkyl groups may be substituted. When alkyl groups are substituted, examples of substituents include halogen atoms such as fluorine, chlorine, bromine, and iodine; aryl groups such as phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthuryl, and phenanthryl groups; alkoxy groups such as methoxy, ethoxy, and tert-butoxy groups; aryloxy groups such as phenoxy and p-tolyloxy groups; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, 2-ethylhexyloxycarbonyl, and phenoxycarbonyl groups; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy groups; acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, and methoxali groups. Examples of aryl groups include acyl groups such as the 'l' group, alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group, arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group, alkylamino groups such as methylamino group and cyclohexylamino group, dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, as well as hydroxyl group, carboxyl group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, and phosphono group.

[0039] In equation (2) above, R 3 and R 4 Each of these is independently either a hydrogen atom or a methyl group. Here, R 3 and R 4 These may be the same or different. Also, * represents a connection point. From the viewpoint of further improving the effects of the present invention, R 3 and R 4 Preferably, one of the atoms is a hydrogen atom and the other is a methyl group.

[0040] From the viewpoint of further improving the effects according to the present invention, R2 It is preferably a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms, or a group represented by the above formula (2), and is an unsubstituted linear or branched alkyl group having 2 to 5 carbon atoms, R 3 and R 4 It is more preferable that the group is represented by the above formula (2) in which at least one of the groups is a methyl group, and is an unsubstituted isopropyl group, R 3 and R 4 It is particularly preferable that the group is represented by formula (2) above, where one of the atoms is a hydrogen atom and the other is a methyl group.

[0041] In formula (1) above, l is 1 to 3. The limescale inhibitor (ionic salt) shown in formula (1) above may exist as a single compound, or as a mixture of two or more compounds, such as a compound with l = 1 (1 molar adduct), a compound with l = 2 (2 molar adduct), and a compound with l = 3 (3 molar adduct). For example, in the case of the manufacturing method described below, the limescale inhibitor (ionic salt) shown in formula (2) above usually exists as a mixture of 1 molar adducts, 2 molar adducts, and 3 molar adducts. If the limescale inhibitor of formula (1) is a single compound, then l is R 2 This indicates the number of moles added to the benzene ring. On the other hand, if the limescale inhibitor of formula (1) is a mixture, then l is R 2 This represents the average number of moles added to the benzene ring. Note that "l" is the formula used when manufacturing the limescale inhibitor of formula (1): R 1 R in relation to the amount (moles) of a raw material (e.g., cresol) having -Ph-YO- (Ph = group derived from a benzene ring) 2 This is substantially equivalent to the proportion of the amount (moles) of the constituent raw materials (e.g., styrene, methylstyrene) charged. Here, the presence of 1-mol adducts, 2-mol adducts, and 3-mol adducts in the limescale inhibitor (ionic salt), as well as the ratio (molar ratio) of 1-mol adduct / 2-mol adduct / 3-mol adduct, can be confirmed and measured by gas chromatography (GC) analysis under the following conditions.

[0042] (Method for confirming the presence of each adduct and method for measuring the proportion (molar ratio) of each adduct) Measurement conditions GC:GC-14B (manufactured by Shimadzu Corporation) Column: SE-30 Column temperature: 100°C → (20°C / min) → 300°C INJ, DET: 320℃ Sample volume: 0.4 μl (50% methanol solution).

[0043] A specific example of a limescale inhibitor as described above is a compound having the following structure. Note that the combination of the anionic and cationic parts in the following structure is not limited to the combinations shown below, and may be combined as appropriate. Furthermore, the following compound encompasses both (a) existing as a single 1-mol adduct, 2-mol adduct, or 3-mol adduct; and (b) existing as a mixture of two or more 1-mol adducts, 2-mol adducts, and 3-mol adducts.

[0044] [ka]

[0045] [ka]

[0046] The limescale inhibitor according to this disclosure is an ionic salt as shown in formula (1) above. The limescale inhibitor composition according to this disclosure may contain ionic salts other than the ionic salt shown in formula (1) above, but it is preferable that it is substantially composed of the ionic salt shown in formula (1) above. Here, "the limescale inhibitor composition is substantially composed of the ionic salt shown in formula (1) above" means that the proportion of the ionic salt shown in formula (1) above in the total ionic salts exceeds 95% by mass (upper limit: 100% by mass), and is preferably exceeds 98% by mass (upper limit: 100% by mass).

[0047] The limescale inhibitors relating to this disclosure can be manufactured by known methods. Specifically, the method described in Japanese Patent Application Publication No. 2016-69523 and the method described in the following examples can be used as is or with appropriate modifications. For example, a compound of formula (3) below can be reacted with styrene or methylstyrene according to a conventional method to obtain a styrene alkylphenol derivative, which can then be used as a starting material to manufacture the product according to known methods. Specifically, first, an alkylene oxide is added in a desired number of moles to the phenolic hydroxyl group of the styrene alkylphenol derivative obtained by the above method in the presence of a base catalyst such as sodium hydroxide or potassium hydroxide. Next, the product is sulfated using a sulfurizing agent such as sulfuric anhydride, chlorosulfonic acid, sulfamic acid, or sulfuric acid, and this sulfated product is neutralized with a base to form a cation (Q + By converting it to a salt with (1), a limescale inhibitor (ionic bonded salt) of formula (1) can be obtained.

[0048] [ka]

[0049] The content of the limescale inhibitor according to this disclosure is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, and particularly preferably 5 to 15 parts by mass, per 100 parts by mass of the resin constituting the composition. With such a ratio, the limescale inhibitor can exert a sufficient limescale prevention effect. Furthermore, with such a ratio, the appearance and surface condition after molding (e.g., transparency, suppression of tack and whitening) can be made to a good state.

[0050] (resin) The limescale-preventing composition relating to this disclosure includes a resin in addition to the limescale-preventing agent of formula (1) described above.

[0051] In one embodiment of the present invention, the resin is a thermosetting resin. In one embodiment of the present invention, the resin is a thermoplastic resin.

[0052] Specific examples of the above resins include, for example, (meth)acrylic resins, urethane resins, styrene resins, olefin resins (including cyclic olefin resins), polyester resins, polycarbonate resins, polyamide resins, polyphenylene ether resins, polyphenylene sulfide resins, halogen-containing resins (polyvinyl chloride, polyvinylidene chloride, fluororesins, etc.), polysulfone resins (polyethersulfone, polysulfone, etc.), cellulose derivatives (cellulose esters, cellulose carbamates, cellulose ethers, etc.), silicone resins (polydimethylsiloxane, polymethylphenylsiloxane, etc.), polyvinyl acetate, etc. Examples of resins include vinyl ester resins, polyvinyl alcohol resins and their derivative resins, rubber or elastomers (diene rubbers such as polybutadiene and polyisoprene, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, acrylic rubber, urethane rubber, silicone rubber, etc.), melamine resins, phenolic resins, urea resins, epoxy resins, acrylonitrile-butadiene-styrene resins (ABS resins), acrylonitrile-styrene resins (AS resins), polyethylene glycol (PEG) resins, polyethylene oxide resins, polypropylene oxide resins, polysaccharide resins, and other photopolymerizable resins. The above resins can be used individually or in combination of two or more. Of these, it is preferable to use urethane resins and polyester resins (more preferably unsaturated polyester resins) as thermosetting resins. It is also preferable to use (meth)acrylic resins as thermoplastic resins. That is, in a preferred embodiment of the present invention, the resin is a thermosetting resin, and the thermosetting resin is at least one selected from the group consisting of urethane resins and polyester resins. In a more preferred embodiment of the present invention, the resin is a thermosetting resin, and the thermosetting resin is an unsaturated polyester resin. In another preferred embodiment of the present invention, the resin is a thermoplastic resin, and the thermoplastic resin is a (meth)acrylic resin.

[0053] Examples of (meth)acrylic resins include (meth)acrylic acid, (meth)acrylic acid esters [(meth)acrylic acid alkyl esters having C1-C10 alkyl groups such as (meth)acrylic acid, (meth)acrylic acid, (meth)acrylic acid, (meth)acrylic acid, (meth)acrylic acid propyl propyl butyl meth)acrylic acid, (meth)acrylic acid 2-ethylhexyl meth)acrylic acid; (meth)acrylic acid hydroxyalkyl esters such as (meth)acrylic acid hydroxyethyl

[0054] Specific examples of the homopolymer or copolymer of the (meth)acrylic monomer include, for example, poly(meth)acrylic acid ester, acrylic acid ester-methacrylic acid ester copolymer, and polyacrylonitrile. Specific examples of copolymers of the (meth)acrylic monomer with other monomers include, for example, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid ester-styrene copolymer, (meth)acrylic acid ester-(meth)acrylic acid-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-(meth)acrylic acid ester copolymer, acrylonitrile-acrylic acid ester-styrene copolymer (AAS resin), and methyl methacrylate-butadiene-styrene copolymer (MBS resin).

[0055] Urethane resin is a resin formed via urethane bonds. Examples of urethane resins that can be used include (meth)acrylic urethane resin, polyester-based urethane resin, polyether-based urethane resin, and polycarbonate-based urethane resin. For example, (meth)acrylic urethane resin can be obtained by curing the above-mentioned (meth)acrylic resin with isocyanate.

[0056] Examples of styrene resins include polystyrene, poly-α-methylstyrene, α-methylstyrene-acrylonitrile copolymer, styrene-N-phenylmaleimide copolymer, styrene-N-phenylmaleimide-acrylonitrile copolymer, and rubber-reinforced polystyrene resin (HIPS resin).

[0057] Olefin resins include not only homopolymers of olefin monomers, but also copolymers of olefin monomers and copolymers of olefin monomers with other copolymerizable monomers. Specific examples of olefin monomers include, for example, chain olefins [such as ethylene, propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene, which are α-olefins with 2 to 20 carbon atoms], and cyclic olefins [such as cycloalkenes with 4 to 10 carbon atoms, such as cyclopentene; cycloalkadienes with 4 to 10 carbon atoms, such as cyclopentadiene; bicycloalkenes with 7 to 20 carbon atoms, such as norbornene and norbornadiene; and tricycloalkenes or tricycloalkadienes with 10 to 25 carbon atoms, such as dihydrodicyclopentadiene and dicyclopentadiene]. These olefin monomers can be used individually or in combination of two or more. Among the above olefin monomers, chain-like olefins such as ethylene, propylene, and α-olefins having 2 to 4 carbon atoms, such as 1-butene, are preferred.

[0058] Specific examples of other copolymerizable monomers that can copolymerize with the aforementioned olefin monomers include, for example, vinyl fatty acid esters such as vinyl acetate and vinyl propionate; (meth)acrylic monomers such as (meth)acrylic acid, alkyl (meth)acrylate, and glycidyl (meth)acrylate; unsaturated dicarboxylic acids or their anhydrides such as maleic acid, fumaric acid, and maleic anhydride; vinyl esters of carboxylic acids (e.g., vinyl acetate, vinyl propionate, etc.); cyclic olefins such as norbornene and cyclopentadiene; and dienes such as butadiene and isoprene. These copolymerizable monomers can be used individually or in combination of two or more.

[0059] More specific examples of the olefin resins mentioned above include, for example, polyethylene (low-density polyethylene, medium-density polyethylene, high-density polyethylene, or linear low-density polyethylene, etc.), polypropylene (homopolypropylene, block polypropylene, random polypropylene, etc.), ethylene-propylene copolymers, ethylene-propylene-butene ternary copolymers, and (co)polymers of chain-like olefins (especially α-olefins having 2 to 4 carbon atoms). Specific examples of copolymers of olefin monomers with other copolymerizable monomers include, for example, copolymers of chain-like olefins (especially α-olefins having 2 to 4 carbon atoms such as ethylene and propylene) with fatty acid vinyl ester monomers (e.g., ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, etc.); copolymers of chain-like olefins with (meth)acrylic monomers [copolymers of chain-like olefins (especially α-olefins having 2 to 4 carbon atoms) with (meth)acrylic acid (e.g., ethylene-(meth)acrylic acid copolymer, propylene-(meth)acrylic acid copolymer, ionomer, etc.); and copolymers of chain-like olefins (especially α-olefins having 2 to 4 carbon atoms) with alkyl (meth)acrylic acid. Examples include copolymers with acrylates (e.g., ethylene-alkyl(meth)acrylate copolymer); etc.; copolymers of chain olefins (especially α-olefins with 2 to 4 carbon atoms) and dienes (e.g., ethylene-butadiene copolymer); modified polyolefins such as epoxy-modified polyolefins (e.g., ethylene-glycidyl(meth)acrylate copolymer), carboxy-modified polyolefins (e.g., ethylene-maleic anhydride copolymer), and epoxy and carboxy-modified polyolefins (e.g., ethylene-maleic anhydride-glycidyl(meth)acrylate copolymer); and olefin elastomers (e.g., ethylene-propylene rubber).

[0060] Specific examples of polyester resins include polymers or copolymers obtained by polycondensation of at least one selected from the group consisting of (a) dicarboxylic acids or their derivatives and diols or their derivatives, (b) hydroxycarboxylic acids or their derivatives, and (c) lactones.

[0061] Examples of the above-mentioned dicarboxylic acids or their derivatives include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4,4'-diphenyl etherdicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, and 5-sodium sulfisoisophthalic acid; aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedionic acid, malonic acid, glutaric acid, and dimer acid; and 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Examples of the above-mentioned diols or derivatives include aliphatic glycols having 2 to 20 carbon atoms, namely ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimergol, etc., or long-chain glycols with molecular weights of 200 to 100,000, namely polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc., aromatic dioxy compounds, namely 4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F, etc., and derivatives thereof. Examples of the above-mentioned hydroxycarboxylic acids include glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and derivatives thereof. Examples of the lactones mentioned above include caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. The polyester resin also includes polyester elastomers.

[0062] Furthermore, an unsaturated polyester resin may be used as the polyester resin. Examples of unsaturated polyester resins include those obtained from dibasic acids such as maleic acid, fumaric acid, phthalic acid, and isophthalic acid, and dihydric alcohols such as ethylene glycol, propylene glycol, bisphenol A ethylene oxide adduct, and bisphenol A propylene oxide adduct. As the unsaturated polyester resin, an unsaturated polyester resin using a bisphenol A adduct as the dihydric alcohol (bisphenol A type unsaturated polyester resin) is preferred. Examples of epoxy acrylate resins include polyfunctional epoxy resins such as bisphenol A type, bisphenol F type, polyphenol type, halogenated bisphenol type, and polyvalent glycidyl ester type, which are modified with acrylic acid, methacrylic acid, acrylic acid-maleic anhydride, methacrylic acid-maleic anhydride, etc. Examples of polyester acrylate resins include those obtained by polycondensing a polyester resin, which is produced by polycondensing an α,β-unsaturated dicarboxylic acid such as maleic anhydride or fumaric acid with a polyhydric alcohol such as bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, or 2,2'-di(hydroxypropoxyphenyl)propane, and then modifying that polyester resin with acrylic acid, methacrylic acid, etc. The α,β-unsaturated dicarboxylic acid may optionally include dicarboxylic acids such as phthalic anhydride, isophthalic acid, or terephthalic acid. Among the above polyester acrylate resins, bisphenol A type polyester acrylate resins, which are obtained by polycondensing a bisphenol A adduct and other polyhydric alcohols with unsaturated dicarboxylic acids and dicarboxylic acids, and then modifying those bisphenol A type polyester resins with acrylic acid, methacrylic acid, etc., are preferred.

[0063] Specific examples of polycarbonate resins include thermoplastic resins obtained by reacting a divalent or higher phenol compound with a diester carbonate compound such as phosgene or diphenyl carbonate.

[0064] Examples of the divalent or higher phenol compounds include 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4-hydroxyphenyl)-(4-isopropylphenyl)methane, bis(3,5-dichloro-4-hydroxyphenyl)methane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, and 1-naphthyl-1,1- Bis(4-hydroxyphenyl)ethane, 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 2-methyl-1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1-ethyl-1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3-chloro-4-hydroxyphenyl) bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-fluoro-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane, 1,4-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 4-methyl-2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)hexane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis( Dihydroxydiarylalkanes such as 4-hydroxyphenyl)nonane, 1,10-bis(4-hydroxyphenyl)decane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dichloro-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclodecane, and other dihydroxydiarylcycloalkanes. Examples include dihydroxydiarylsulfones such as bis(4-hydroxyphenyl)sulfone, bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, and bis(3-chloro-4-hydroxyphenyl)sulfone; dihydroxyaryl ethers such as bis(4-hydroxyphenyl) ether and bis(3,5-dimethyl-4-hydroxyphenyl) ether; dihydroxydiarylketones such as 4,4'-dihydroxybenzophenone and 3,3',5,5'-tetramethyl-4,4'-dihydroxybenzophenone; dihydroxydiarylsulfides such as bis(4-hydroxyphenyl)sulfide, bis(3-methyl-4-hydroxyphenyl)sulfide, and bis(3,5-dimethyl-4-hydroxyphenyl)sulfide; dihydroxydiarylsulfoxides such as bis(4-hydroxyphenyl)sulfoxide; dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl; and dihydroxyarylfluorenes such as 9,9-bis(4-hydroxyphenyl)fluorene. In addition to the divalent phenol compounds mentioned above, other divalent phenol compounds that can be used include dihydroxybenzenes such as hydroquinone, resorcinol, and methylhydroquinone, and dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene.

[0065] These divalent or higher phenol compounds may be used individually or in combination of two or more. Linear aliphatic divalent carboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid may also be used as copolymerization components.

[0066] Specific examples of polyamide resins include, for example, aliphatic polyamides such as polyamide 46, polyamide 5, polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 11, polyamide 12, polyamide 6 / 66, and polyamide 6 / 11; alicyclic polyamides such as poly-1,4-norbornene terephthalamide, poly-1,4-cyclohexane terephthalamide, and poly-1,4-cyclohexane-1,4-cyclohexaneamide; aromatic polyamides such as polyamide 6T, polyamide 9T, and polyamide MXD; and copolyamides formed from at least two different polyamide-forming components from among these polyamides. Polyamide elastomers are also included in the polyamide resins.

[0067] Specific examples of polyphenylene ether resins include, for example, homopolymers such as poly(2,5-dimethyl-1,4-phenylene ether), poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-di-n-propyl-1,4-phenylene ether), and poly(2-methyl-6-chloroethyl-1,4-phenylene ether); modified polyphenylene ether copolymers constructed based on these homopolymers; and modified graft copolymers in which a styrene polymer is grafted onto a polyphenylene ether homopolymer or copolymer.

[0068] Specific examples of polyphenylene sulfide resins include, for example, polyphenylene sulfide, polyphenylene sulfide ketone, polybiphenylene sulfide, and polyphenylene sulfide sulfone.

[0069] Furthermore, if the above resin is a copolymer, the copolymer may take any of the following forms: block copolymer, random copolymer, graft copolymer, or alternating copolymer.

[0070] The resin may be a synthetic product or a commercially available product. The polymerization method for synthesizing the resin is not particularly limited, and known methods can be used. Examples include high-pressure radical polymerization, medium- and low-pressure polymerization, solution polymerization, slurry polymerization, bulk polymerization, emulsion polymerization, gas-phase polymerization, radical polymerization, living radical polymerization, anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, addition polymerization, condensation polymerization, ring-opening polymerization, etc. Furthermore, the catalyst used for polymerization is not particularly limited, and examples include peroxide catalysts, azo catalysts, Ziegler-Natta catalysts, metallocene catalysts, etc. When synthesizing the resin, after synthesizing the resin, the limescale inhibitor according to this disclosure may be mixed to produce the limescale inhibitor composition according to this disclosure. Alternatively, the monomer constituting the resin, a polymerization initiator, and the limescale inhibitor according to this disclosure may be mixed to produce the limescale inhibitor composition according to this disclosure.

[0071] Other commercially available products include, but are not limited to, unsaturated polyester resin-based materials such as gel coat (manufactured by TOMATEC Corporation, e.g., "3Z-0006PI") and top coat (manufactured by TOMATEC Corporation).

[0072] Of these, (meth)acrylic resin, urethane resin, and polyester resin are preferred from the viewpoint of versatility, further improvement of the effects of the present invention, compatibility with limescale inhibitors, and stability during heat processing, (meth)acrylic resin, (meth)acrylic urethane resin, and bisphenol A type polyester resin are more preferred, bisphenol A type polyester resin is even more preferred, and bisphenol A type unsaturated polyester resin is particularly preferred. That is, in a preferred embodiment of the present invention, the resin is at least one selected from the group consisting of (meth)acrylic resin, urethane resin, and polyester resin. In a more preferred embodiment of the present invention, the resin is at least one selected from the group consisting of (meth)acrylic resin, (meth)acrylic urethane resin, and bisphenol A type polyester resin. In an even more preferred embodiment of the present invention, the resin is bisphenol A type polyester resin. In a particularly preferred embodiment of the present invention, the resin is bisphenol A type unsaturated polyester resin.

[0073] (Other additives) The limescale-preventing composition according to this disclosure may consist of the limescale-preventing agent of formula (1) and a resin, but may also contain other additives. Examples of other additives include curing agents, crosslinking agents, solvents, antioxidants, fillers, lubricants, dyes, organic pigments, inorganic pigments, plasticizers, processing aids, ultraviolet absorbers, light stabilizers, foaming agents, waxes, crystal nucleating agents, mold release agents, hydrolysis inhibitors, matting agents, polishing agents, antiblocking agents, antistatic agents, anti-repellent agents, radical scavengers, anti-fogging agents, anti-stain agents, ion trapping agents, flame retardants, flame retardant aids, curing accelerators, curing catalysts, scratch inhibitors, defoaming agents, viscosity modifiers, surface modifiers, plasticizers, pH adjusters, color inhibitors, deodorants, weathering agents, thread friction reducers, slip agents, etc. When the limescale-preventing composition according to this disclosure contains other additives, the amount of other additives should not impair the purpose of the present invention, and amounts similar to those normally used can be used. Alternatively, the limescale-preventing composition relating to this disclosure may contain known limescale-preventing agents other than the limescale-preventing agent of formula (1) described above. Examples of known limescale-preventing agents include hydrophilic agents and hydrophobic agents. Furthermore, the content of known limescale-preventing agents is not particularly limited and can be appropriately selected according to the desired effect.

[0074] The solvent is not particularly limited as long as it can uniformly dissolve or disperse the limescale inhibitor and the resin. For example, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acetate, toluene, methylpropylene glycol, etc. can be used. Of these, it is preferable that both the limescale inhibitor and the solvent have polymerizable groups. In such cases, the solvent itself copolymerizes with the resin (substrate), so the amount of residual solvent in the molded article during the drying process after molding can be reduced. Therefore, deterioration of the molded article (especially the resin) can be suppressed and prevented. Thus, the effect of the limescale inhibitor according to this disclosure can be exerted more effectively. Therefore, the limescale inhibitory effect can be exerted for an even longer period of time.

[0075] In other words, in a preferred embodiment of the present invention, the limescale inhibitor is Q +The compound is represented by formula (1) above, where is a nitrogen-containing compound cation having an ethylenically unsaturated bonding group, and the solvent has an ethylenically unsaturated bonding group. Here, the ethylenically unsaturated bonding group is an acryloyl group (H2C=CH-C(=O)-), a methacryloyl group (H2C=CH-C(=O)-), an acryloyloxy group (H2C=CH-C(=O)-O-), a methacryloyloxy group (H2C=C(CH3)-C(=O)-O-), a vinyl group (H2C=CH-), or an allyl group (H2C=CHCH2-). Therefore, in a more preferred embodiment of the present invention, the limescale inhibitor is Q + The compound is represented by formula (1) above, wherein is dimethylmonoacrylate ethylammonium ion, diethylmonoacrylate ethylammonium ion, methylethylmonoacrylate ethylammonium ion, dimethylmonomethacrylate ethylammonium ion, diethylmonomethacrylate ethylammonium ion, methylethylmonomethacrylate ethylammonium ion, 1,2,2,6,6-pentamethyl-4-acrylate piperidinium ion, or 1,2,2,6,6-pentamethyl-4-methacrylate piperidinium ion, and the solvent is methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, or butyl acrylate.

[0076] The limescale-preventing composition according to this disclosure can reduce the number of applications. The limescale-preventing composition and limescale-preventing agent according to this disclosure may be applied to a substrate by spraying (may be used as a coating agent). Alternatively, since the limescale-preventing composition according to this disclosure contains a limescale-preventing agent and a resin, it can be molded into a predetermined shape (e.g., a bathtub, toilet, washbasin, kitchen sink). A molded article using the limescale-preventing composition according to this disclosure exhibits a limescale-preventing effect itself and can maintain that limescale-preventing effect (can provide a limescale-preventing effect for a long period of time). The reason for this is unknown, but it is presumed to be as follows. Note that the following mechanism is a presumption and does not limit the technical scope of the present invention. The anionic structure of the limescale-preventing agent according to this disclosure (the left-hand part in formula (1)) acts as a dispersant. Due to this dispersant effect, the aggregation of limescale on the material surface is suppressed and prevented, thereby suppressing and preventing limescale adhesion (it is less likely to aggregate and form large clumps). Furthermore, when molding using the limescale-preventing composition according to this disclosure, the limescale-preventing agent segregates on the surface of the molded body. Therefore, due to the dispersant effect of the limescale-preventing agent, the aggregation of limescale and, consequently, the adhesion of limescale to the molded body can be suppressed and prevented. Since the limescale-preventing agent is positioned within the molded body (resin), it does not detach from the molded body (resin) even after long-term use, or detaches only slightly, or all of the limescale-preventing agent does not detach from the molded body even after long-term use. Therefore, a molded body using the limescale-preventing composition according to this disclosure exhibits a long-lasting limescale-preventing effect, and there is little or no need to apply the limescale-preventing agent separately after cleaning (the number of applications can be reduced). Conventionally, limescale adhesion has generally been prevented by making the surface of the substrate (molded body) hydrophilic or hydrophobic. In contrast, due to the mechanism described above, the limescale-preventing composition or limescale-preventing agent according to this disclosure can exhibit a limescale-preventing effect or limescale removal ability regardless of the hydrophilicity / hydrophobicity of the substrate surface. Furthermore, since the molded body itself contains a limescale inhibitor, there is no need to apply it separately by spraying or other means.

[0077] Therefore, the present invention also provides a molded article formed using the limescale-preventing composition according to the present disclosure. Furthermore, the present invention also provides a method for producing a molded article, comprising preparing a mixture (or mixed liquid) containing the limescale-preventing composition and a solvent according to the present disclosure, and molding the mixture (or mixed liquid).

[0078] (Method of manufacturing a molded product) The present invention relates to a method for manufacturing a molded article (third aspect), comprising preparing a mixture (or liquid mixture) containing the limescale-preventing composition and solvent according to the present disclosure, and molding the mixture (or liquid mixture) (process). The present invention also relates to a molded article containing the limescale-preventing composition according to the present disclosure (fourth aspect).

[0079] In one embodiment of the above-described process, a limescale-preventing composition and a solvent are mixed to prepare a mixture (or mixed liquid) (mixing step); and the mixture (or mixed liquid) is molded to produce a molded body (molding step). This will be described in detail below.

[0080] (Mixing process) In this step, a mixture (or liquid mixture) is prepared by mixing the limescale inhibitor and the resin. Here, the definitions of the limescale inhibitor and the resin are the same as those given above for (liquid scale inhibitor) and (resin), so their explanation is omitted here. The limescale inhibitor or the resin may be used in the form of a mixture with a solvent.

[0081] Furthermore, a curing agent may be further mixed in for the purpose of curing the resin. In this case, the same resins as those described in the (Resin) section above can be used. Preferably, thermosetting resins such as polyester resin (especially unsaturated polyester resin), vinyl ester resin, acrylic resin, and urethane resin can be used. The above resins may be used alone or in combination of two or more. In addition, commercially available resins may be used, for example, unsaturated polyester resin-based materials such as gel coat (manufactured by TOMATEC Corporation, e.g., "3Z-0006PI") and top coat (manufactured by TOMATEC Corporation) (manufactured by TOMATEC Corporation), but are not limited to these. In addition, the curing agent can be appropriately selected depending on the type of resin used. For example, peroxides such as benzoyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, dicumyl peroxide, lauryl peroxide, cyclohexanone peroxide, and t-butyl perbenzoate can be used. Preferably, methyl ethyl ketone peroxide is used. The amount of curing agent used can be the same as usual, for example, 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of resin.

[0082] Alternatively, or in addition to the above, a crosslinking agent may be further mixed in for the purpose of crosslinking (curing) the resin. Suitable resins include amino-curable resins, isocyanate-curable resins (e.g., isocyanate-curable acrylic resins), acid-epoxy-curable resins, hydrolyzable silane-curable resins, hydroxyl-epoxy-curable resins, hydrazine-curable resins, oxidative polymerization-curable resins, photo(thermal) radical polymerization-type resins, and photo(thermal) cationic polymerization-type resins. These resins may be used individually or in combination of two or more. Commercially available resins may also be used, such as the Acrydic series (manufactured by DIC Corporation) and the Yupika Coat series (manufactured by Nippon Yupika Co., Ltd.). The crosslinking agent (curing agent) can be appropriately selected depending on the type of resin used. For example, (blocked) polyisocyanate compounds can be used. The polyisocyanate compound may be a free isocyanate compound or a blocked isocyanate compound. Examples of polyisocyanate compounds having free isocyanate groups include organic diisocyanates themselves, such as aliphatic diisocyanates like hexamethylene diisocyanate or trimethylhexamethylene diisocyanate, cyclic aliphatic diisocyanates like xylene diisocyanate or isophorone diisocyanate, aromatic diisocyanates like tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate, or adducts of these organic diisocyanates with an excess amount of a polyhydric alcohol, a low molecular weight polyester resin, or water, or polymers of the above organic diisocyanates, as well as isocyanate billets. Commercially available crosslinking agents may be used, such as the Barnock series (manufactured by DIC Corporation), the Dismodule series (manufactured by Bayer AG), the Takenate series (manufactured by Mitsui Chemicals, Inc.), the Coronate series (manufactured by Nippon Polyurethane Industries Co., Ltd.), and the Duranate series (manufactured by Asahi Kasei Corporation).Examples of polyisocyanate compounds having blocked isocyanate groups include polyisocyanate compounds having free isocyanate groups that have been blocked with known blocking agents such as oximes, phenols, alcohols, lactams, malonic acid esters, and mercaptans. Commercially available crosslinking agents may be used, such as the Barnock series (manufactured by DIC Corporation), Takenate series (manufactured by Takeda Pharmaceutical Company Limited), Aditol series (manufactured by Hoechst), Coronate series (manufactured by Nippon Polyurethane Industries Co., Ltd.), and Duranate series (manufactured by Asahi Kasei Corporation). The crosslinking agents may be used alone or in combination of two or more. The mixing ratio of the crosslinking agents should be such that the coating film hardens and has sufficient performance. For example, the mixing ratio of resin to crosslinking agent (resin:crosslinking agent (mass ratio)) is about 80:20 to 50:50. If necessary, a catalyst (e.g., dibutyltin dilaurate) may be added.

[0083] (molding process) In this process, the mixture (or liquid mixture) prepared above is molded to produce a molded body.

[0084] The method for molding the mixture (or liquid mixture) is not particularly limited and can be appropriately selected according to the desired shape. In one embodiment of the present invention, a method can be used in which the mixture (or liquid mixture) is poured into a predetermined mold and then dried or pressure molded. According to this method, the final product shape can be easily formed. The limescale inhibitor according to this disclosure is selectively arranged (unevenly distributed) on the surface of the resulting molded article. Furthermore, the limescale inhibitor is present in the molded article (resin) and does not easily detach even when rubbed. Therefore, the molded article can exhibit an excellent limescale inhibitory effect for a long period of time.

[0085] Alternatively, in one embodiment of the present invention, methods for producing a molded article by forming a coating layer on a substrate using analog printing methods such as silk screen printing, offset printing, and gravure printing; digital printing methods such as electrophotographic printing; and coating methods such as roll coating, rod coating, kiss coating, knife coating, air knife coating, die coating, lip coating, flow coating, dip coating, spin coating, reverse coating, brush coating, sponge coating, bar coating, and spray coating can be used. The thickness of the coating layer (wet film thickness) is, for example, 10 to 750 μm, preferably 50 to 500 μm, but is not limited to these values. Here, the limescale inhibitor according to this disclosure is selectively arranged (unevenly distributed) on the surface of the coating layer. Furthermore, the limescale inhibitor is present within the coating layer (resin) and does not easily detach even when rubbed. Therefore, the molded product can exhibit excellent limescale prevention for a long period of time. The above coating process may be performed once or repeatedly.

[0086] After molding in this manner, the desired molded product may be obtained by drying. In this case, the drying conditions can be appropriately selected according to the size of the molded product, etc. For example, the drying temperature is, for example, 20 to 160°C, preferably 40 to 130°C, more preferably 60 to 110°C, but is not limited to these. The drying time is, for example, 1 minute to 12 hours, preferably 5 minutes to 6 hours, more preferably 10 to 120 minutes, but is not limited to these. The above drying process may be performed once or repeatedly. [Examples]

[0087] The effects of the present invention will be explained using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples. In the following examples, unless otherwise specified, the operations were carried out at room temperature (25°C). Unless otherwise specified, "%" and "parts" mean "mass%" and "parts by mass," respectively.

[0088] Synthesis Example 1 M,p-cresol was used as a raw material, and styrene was added to it in an amount of 2 moles of styrene per 1 mole of m,p-cresol and reacted to obtain a styrene-cresol derivative. Next, 12 moles (average) of ethylene oxide were added to the phenolic hydroxyl group of the obtained styrene-cresol derivative in the presence of sodium hydroxide as a base catalyst. Then, sulfamic acid was used as a sulfation agent to perform sulfation esterification, and the obtained sulfated ester was subjected to cation exchange with N,N-dimethylaminoethyl acrylate to obtain polyoxyethylene (12)[distylenized (methylphenyl ether)] sulfate N,N-dimethylaminoethyl acrylate salt, which is compound 1 (scale inhibitor 1) having the structure shown below. The compound obtained in this example is also called "compound 1" or "scale inhibitor 1". Note that compound 1 (scale inhibitor 1) is a mixture of 1-mol adduct, 2-mol adduct, and 3-mol adduct (l=1~3 in the structure shown below).

[0089] [ka]

[0090] Synthesis Example 2 m,p-cresol was used as a raw material, and styrene was added to it in an amount of 2 moles of styrene per 1 mole of m,p-cresol and reacted to obtain a styrene-cresol derivative. Next, 12 moles (average) of ethylene oxide were added to the phenolic hydroxyl group of the obtained styrene-cresol derivative in the presence of sodium hydroxide as a base catalyst. Then, sulfamic acid was used as a sulfation agent to perform sulfation esterification, and the obtained sulfated ester was subjected to cation exchange using N,N-dimethylaminoethyl methacrylate to obtain compound 2 (scale inhibitor 2) having the structure shown below. The compound obtained in this example is also called "compound 2" or "scale inhibitor 2". Note that compound 2 (scale inhibitor 2) is a mixture of 1-mol adduct, 2-mol adduct, and 3-mol adduct (l=1~3 in the structure below).

[0091] [ka]

[0092] Synthesis Example 3 M,p-cresol was used as a raw material, and styrene was added to it in an amount of 2 moles of styrene per 1 mole of m,p-cresol and reacted to obtain a styrene-cresol derivative. Next, 12 moles (average) of ethylene oxide were added to the phenolic hydroxyl group of the obtained styrene-cresol derivative in the presence of sodium hydroxide as a base catalyst. Then, sulfamic acid was used as a sulfation agent to perform sulfation esterification, and the obtained sulfated ester was subjected to cation exchange using 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate to obtain compound 3 (scale inhibitor 3) having the structure shown below. The compound obtained in this example is also called "compound 3" or "scale inhibitor 3". Note that compound 3 (scale inhibitor 3) is a mixture of 1-mol adduct, 2-mol adduct, and 3-mol adduct (l=1~3 in the structure below).

[0093] [ka]

[0094] Synthesis Example 4 M,p-cresol was used as a raw material, and styrene was added to it in an amount of 2 moles of styrene per 1 mole of m,p-cresol and reacted to obtain a styrene-cresol derivative. Next, 12 moles (average) of ethylene oxide were added to the phenolic hydroxyl group of the obtained styrene-cresol derivative in the presence of sodium hydroxide as a base catalyst. Then, sulfamic acid was used as a sulfation agent to perform sulfuric esterification, and the obtained sulfurized ester was subjected to cation exchange using caustic soda (sodium hydroxide) to obtain compound 4 (scale inhibitor 4) having the structure shown below. The compound obtained in this example is also called "compound 4" or "scale inhibitor 4". Note that compound 4 (scale inhibitor 4) is a mixture of 1-mol adduct, 2-mol adduct, and 3-mol adduct (l=1~3 in the structure below).

[0095] [ka]

[0096] Synthesis Example 5 Compound 5 (scale inhibitor 5) having the following structure was obtained by neutralizing the raw material, cumenesulfonic acid, with ethylethanolamine. The compound obtained in this example is also referred to as "Compound 5" or "Scale Inhibitor 5".

[0097] [ka]

[0098] Synthesis Example 6 Phenol was used as a raw material, and styrene was added to it in an amount of 3 moles of styrene per 1 mole of phenol, and the mixture was reacted to obtain a styrene-containing phenol derivative. Next, 12 moles (on average) of ethylene oxide were added to the phenolic hydroxyl group of the obtained styrene-containing phenol derivative in the presence of sodium hydroxide as a base catalyst. Then, sulfamic acid was used as a sulfating agent to perform sulfuric esterification, and the resulting sulfurized ester was subjected to cation exchange using ammonia to obtain compound 6 (scale inhibitor 6) having the structure shown below. The compound obtained in this example is also called "compound 6" or "scale inhibitor 6". Note that compound 6 (scale inhibitor 6) is a mixture of 1-mol adduct, 2-mol adduct, and 3-mol adduct (l=1~3 in the structure below).

[0099] [ka]

[0100] Synthesis Example 7 M,p-cresol was used as a raw material, and styrene was added to it in an amount of 2 moles of styrene per 1 mole of m,p-cresol and reacted to obtain a styrene-cresol derivative. Next, 12 moles (average) of ethylene oxide were added to the phenolic hydroxyl group of the obtained styrene-cresol derivative in the presence of sodium hydroxide as a base catalyst. Then, sulfamic acid was used as a sulfating agent to perform sulfuric esterification, and the obtained sulfurized ester was subjected to cation exchange with ammonia to obtain compound 7 (scale inhibitor 7) having the structure shown below. The compound obtained in this example is also called "compound 7" or "scale inhibitor 7". Note that compound 7 (scale inhibitor 7) is a mixture of 1-mol adduct, 2-mol adduct, and 3-mol adduct (l=1~3 in the structure shown below).

[0101] [ka]

[0102] Synthesis Example 8 To the starting material, isotridecanol, 3 moles (average) of butylene oxide and then 5 moles (average) of ethylene oxide were added in the presence of sodium hydroxide as a base catalyst. Then, sulfamic acid was used as a sulfation agent to perform sulfation esterification, and the resulting sulfated ester was subjected to cation exchange using N,N-dimethylaminoethyl acrylate to obtain compound A having the structure shown below. The compound obtained in this example is also referred to as "compound A".

[0103] [ka]

[0104] Example 1-1 A compound for artificial marble layers was prepared by adding 100 parts by mass of unsaturated polyester resin for artificial marble (Yupika 6424, manufactured by Nippon Yupika Co., Ltd.), 1 part by mass of bis(4-tert-butylcyclohexyl) peroxydicarbonate (Perloyl TCP, manufactured by NOF Corporation) as a curing agent, and 200 parts by mass of glass filler (M-80-S, manufactured by TOMATEC Corporation).

[0105] Separately, compound 1 (scale inhibitor) obtained in the above synthesis example 1 was added to methyl methacrylate to a concentration of 50% by mass to prepare scale inhibitor solution 1-1.

[0106] Coating solution 1-1 was prepared by adding and mixing 95 parts by mass of bisphenol A-based unsaturated polyester resin gel coat (manufactured by TOMATEC Corporation, "3Z-0006PI") with 1 part by mass of methyl ethyl ketone peroxide (manufactured by NOF Corporation, "PERMEC N") as a curing agent and 2.5 parts by mass of compound 1 (1 part of compound = approximately 2.6 parts by mass per 100 parts by mass of polyester resin gel coat).

[0107] The obtained coating solution 1-1 was spray-applied to a mold-released glass plate to form a coating film of 0.3-0.4 mm. Then, the glass plate with this coating film was placed in a 60°C drying oven and heated for 1 hour to harden the coating film and form a coating layer on the glass plate.

[0108] Next, a silicone rubber mold was attached to this coating layer, and the artificial marble layer compound prepared above was vacuum-degassed and poured into the mold. After being left at room temperature for 30 minutes, it was heated at 60°C for 2 hours to cure the artificial marble layer. This formed a coating layer containing a limescale inhibitor and resin on the artificial marble layer (coating material 1-1).

[0109] Examples 1-2 In Example 1-1, a coating material was obtained in the same manner as in Example 1-1, except that the amount of bisphenol A-based unsaturated polyester resin gel coat was changed to 90 parts by mass, and the amount of compound 1 added was changed to 5 parts by mass (amount of compound 1 = approximately 5.5 parts by mass per 100 parts by mass of polyester resin gel coat). (Coating material 1-2)

[0110] Examples 1-3 A compound for the artificial marble layer was prepared in the same manner as in Example 1-1.

[0111] Coating solutions 1-3 were prepared by adding and mixing 90 parts by mass of bisphenol A-based unsaturated polyester resin gel coat (manufactured by TOMATEC Corporation, "3Z-0006PI") with 1 part by mass of methyl ethyl ketone peroxide as a curing agent (manufactured by NOF Corporation, "PERMEC N"), 2.5 parts by mass of the above-mentioned limescale inhibitor 2 (amount of compound 2 = approximately 2.8 parts by mass per 100 parts by mass of polyester resin gel coat) and 2.5 parts by mass of compound A (amount of compound A = approximately 2.8 parts by mass per 100 parts by mass of polyester resin gel coat).

[0112] The obtained coating solutions 1-3 were spray-applied to a mold-released glass plate to form a coating film of 0.3-0.4 mm. Then, the glass plate with this coating film was placed in a 60°C drying oven and heated for 1 hour to harden the coating film and form a coating layer on the glass plate.

[0113] Next, a silicone rubber mold was attached to this coating layer, and the artificial marble layer compound prepared above was vacuum-degassed and poured into the mold. After being left at room temperature for 30 minutes, it was heated at 60°C for 2 hours to cure the artificial marble layer. This formed a coating layer containing a limescale inhibitor and resin on the artificial marble layer (coating material 1-3).

[0114] Comparative Example 1-1 A compound for the artificial marble layer was prepared in the same manner as in Example 1-1.

[0115] Coating solutions 1-4 were prepared by adding and mixing 99 parts by mass of bisphenol A-based unsaturated polyester resin gel coat (manufactured by TOMATEC Corporation, "3Z-0006PI") with 1 part by mass of methyl ethyl ketone peroxide (manufactured by NOF Corporation, "PERMEC N") as a curing agent.

[0116] The obtained coating liquid 1-4 was spray-applied to a release-treated glass plate to form a coating film of 0.3-0.4 mm. Then, the glass plate with this coating film was placed in a 60°C drying oven and heated for 1 hour to harden the coating film, forming a coating layer on the glass plate. Next, a silicone rubber mold was attached to this coating layer, and the artificial marble layer compound prepared above was vacuum-degassed and poured into the mold. After being left at room temperature for 30 minutes, it was heated at 60°C for 2 hours to harden the artificial marble layer. This formed an artificial marble layer on the glass plate (comparative coating material 1-1).

[0117] Comparative Example 1-2 A compound for the artificial marble layer was prepared in the same manner as in Example 1-1.

[0118] Comparative coating solutions 1-2 were prepared by adding and mixing 98 parts by mass of bisphenol A-based unsaturated polyester resin gel coat (manufactured by TOMATEC Corporation, "3Z-0006PI") with 1 part by mass of methyl ethyl ketone peroxide as a curing agent (manufactured by NOF Corporation, "PERMEC N") and 1 part by mass of compound A (amount of compound A = approximately 1.0 part by mass per 100 parts by mass of polyester resin gel coat).

[0119] The obtained comparative coatings 1-2 were spray-applied to a mold-released glass plate to form a coating film of 0.3-0.4 mm. Then, the glass plate with this coating film was placed in a 60°C drying oven and heated for 1 hour to cure the coating film and form a coating layer on the glass plate.

[0120] Next, a silicone rubber mold was attached to this coating layer, and the artificial marble layer compound prepared above was vacuum-degassed and poured into the mold. After being left at room temperature for 30 minutes, it was heated at 60°C for 2 hours to cure the artificial marble layer. This formed a coating layer containing a limescale inhibitor and resin on the artificial marble layer (comparative coating material 1-2).

[0121] Comparative Examples 1-3 A compound for the artificial marble layer was prepared in the same manner as in Example 1-1.

[0122] Comparative coating solutions 1-3 were prepared by adding and mixing 95 parts by mass of bisphenol A-based unsaturated polyester resin gel coat (manufactured by TOMATEC Corporation, "3Z-0006PI") with 1 part by mass of methyl ethyl ketone peroxide as a curing agent (manufactured by NOF Corporation, "PERMEC N") and 2.5 parts by mass of compound A (amount of compound A = approximately 2.6 parts by mass per 100 parts by mass of polyester resin gel coat).

[0123] The obtained comparative coatings 1-3 were spray-applied to a mold-released glass plate to form a coating film of 0.3-0.4 mm. Then, the glass plate with this coating film was placed in a 60°C drying oven and heated for 1 hour to cure the coating film and form a coating layer on the glass plate.

[0124] Next, a silicone rubber mold was attached to this coating layer, and the artificial marble layer compound prepared above was vacuum-degassed and poured into the mold. After being left at room temperature for 30 minutes, it was heated at 60°C for 2 hours to cure the artificial marble layer. This formed a coating layer containing a limescale inhibitor and resin on the artificial marble layer (comparative coating material 1-3).

[0125] <Performance Evaluation 1> The coating materials 1-1 to 1-3 of Examples 1-1 to 1-3 and the comparative coating material 1-1 to 1-3 of Comparative Examples 1-1 to 1-3 were evaluated for their limescale adhesion prevention (limescale removal), appearance, hydrophilicity, and heat water resistance using the method described below. The results are shown in Table 1 below.

[0126] [Water scale buildup prevention (water scale removal)] Drop a single drop of tap water onto the coated surface of each coating material and allow it to dry. After drying, drop another drop of water onto the same surface and allow it to dry. Repeat this process for one week to allow limescale to accumulate on the surface of the coating material. Wipe off the limescale with a paper towel, visually check the degree of limescale buildup, and evaluate it according to the following criteria.

[0127] ×: Similar limescale remains on the surface as with comparative coating material 1-1. ○: Less limescale remains on the surface compared to comparative coating material 1-1. ◎: The limescale has been completely removed.

[0128] [exterior] The surface condition of the coating layer (immediately after coating) of each coating material will be visually inspected and evaluated according to the following criteria.

[0129] (Appearance evaluation criteria) ×: At least one of the following phenomena is observed: compound bleed-out, pinching, crocodile skin, and whitening. ○: The above phenomena were not observed, and the surface was smooth and transparent.

[0130] [Hydrophilicity] Visually observe how a single drop of tap water spreads when it is placed on the coated surface of each coating material.

[0131] [Hot water resistance] After exposing the coated surface of the coating material to 90°C hot water, the color change and surface condition change are visually inspected and evaluated according to the following criteria.

[0132] (Heat water resistance evaluation criteria) ×: Blister is observed ○: No blistering is observed, but bleaching is observed. ◎: No blistering observed, only slight whitening observed, or no whitening observed.

[0133] [Table 1]

[0134] The results in Table 1 show that the coating materials 1-1 to 1-3 in the examples exhibit significantly superior limescale prevention (limescale removal) compared to the comparative coating materials 1-1 to 1-3.

[0135] Example 2-1 In a four-necked flask equipped with a condenser, nitrogen inlet tube, thermometer, and Teflon® crescent-shaped stirring blade, 100 parts by mass of toluene, 35 parts by mass of n-butyl acrylate, and 65 parts by mass of methyl methacrylate were charged. 1 part by mass of azobisisobutyronitrile (AIBN) was added as a polymerization catalyst, and polymerization was carried out at 90°C for 3 hours to obtain a toluene solution of (meth)acrylic resin with a solid content of 50% by mass.

[0136] To obtain coating solution 2-1, 200 parts by mass of the (meth)acrylic resin solution prepared above was mixed with 5 parts by mass of compound 4 (scale inhibitor) obtained in synthesis example 4 above.

[0137] The obtained coating solution 2-1 was applied to a glass plate using a bar coater to a wet film thickness of 75 μm, and then dried in a 110°C dryer for 10 minutes to form a coating layer containing a limescale inhibitor and resin on the glass plate (coating material 2-1).

[0138] Examples 2-2 to 2-5 In Example 2-1, a coating layer containing a limescale inhibitor and resin was formed on a glass plate in the same manner as in Example 2-1, except that compound 1 obtained in Synthesis Example 1 (Example 2-2), compound 3 obtained in Synthesis Example 3 (Example 2-3), compound 5 obtained in Synthesis Example 5 (Example 2-4), and compound 6 obtained in Synthesis Example 6 (Example 2-5) were used instead of compound 4 (coating materials 2-2 to 2-5).

[0139] Comparative Example 2-1 A toluene solution of (meth)acrylic resin with a solid content of 50% by mass was obtained in the same manner as in Example 2-1.

[0140] 200 parts by mass of this (meth)acrylic resin toluene solution was applied to a glass plate using a bar coater to a wet film thickness of 75 μm, and then dried in a 110°C dryer for 10 minutes to form a coating layer containing only resin on the glass plate (comparative coating material 2-1).

[0141] Comparative Examples 2-2 to 2-5 In Example 2-1, a coating layer was formed on a glass plate in the same manner as in Example 2-1, except that compound A (Comparative Example 2-2), compound 9 (Comparative Example 2-3), compound 10 (Comparative Example 2-4), and compound 11 (Comparative Example 2-5) obtained in Synthesis Example 8 were used instead of compound 4 (comparative coating materials 2-2 to 2-5). Hereafter, compounds 9, 10, and 11 will simply be referred to as "compound 9," "compound 10," and "compound 11," respectively. Compound 10 is a mixture of 1-mol adduct, 2-mol adduct, and 3-mol adduct (l=1 to 3 in the structure below), and has a structure in which 12 moles (average) of ethylene oxide are added.

[0142] [ka]

[0143] Comparative Example 2-6 A toluene solution of (meth)acrylic resin with a solid content of 50% by mass was obtained in the same manner as in Example 2-1.

[0144] To obtain comparative coating solution 2-6, 10 parts by mass of compound 9 was mixed with 200 parts by mass of the (meth)acrylic resin solution prepared above.

[0145] The obtained comparative coating solution 2-6 was applied to a glass plate using a bar coater to a wet film thickness of 75 μm, and then dried in a 110°C dryer for 10 minutes to form a coating layer containing a limescale inhibitor and resin on the glass plate (comparative coating material 2-6).

[0146] Example 3-1 Mix 122 parts by mass of isocyanate-curable acrylic resin (Acridic WFU-580, manufactured by DIC Corporation), 60 parts by mass of toluene, and 5 parts by mass of compound 7 (water stain inhibitor) obtained in the above synthesis example 7. Immediately before coating, apply isocyanurate (Duranate, manufactured by Asahi Kasei Corporation) TM 21 parts by mass of TPA-100 and 2 parts by mass of dibutyltin dilaurate (DBTL) were added and mixed again to obtain coating solution 3-1.

[0147] The obtained coating solution 3-1 was applied to an acrylic plate using a bar coater to a wet film thickness of 75 μm, and then dried in an 80°C dryer for 30 minutes to form a coating layer on the acrylic plate containing a water stain inhibitor and urethane resin (acrylic urethane resin) (coating material 3-1).

[0148] Examples 3-2 to 3-6 In Example 3-1, a coating layer containing a limescale inhibitor and a urethane resin (acrylic urethane resin) was formed on an acrylic plate in the same manner as in Example 3-1, except that compound 4 obtained in Synthesis Example 4 (Example 3-2), compound 1 obtained in Synthesis Example 1 (Example 3-3), compound 3 obtained in Synthesis Example 3 (Example 3-4), compound 5 obtained in Synthesis Example 5 (Example 3-5), and compound 6 obtained in Synthesis Example 6 (Example 3-6) were used instead of compound 7.

[0149] Comparative Example 3-1 Mix 122 parts by mass of Acrydic WFU-580 (manufactured by DIC Corporation) and 60 parts by mass of toluene. Immediately before coating, add 21 parts by mass of Duranate TPA-100 (manufactured by Asahi Kasei Corporation) and 2 parts by mass of dibutyltin dilaurate (DBTL), mix again, and obtain comparative coating solution 3-1.

[0150] The obtained comparative coating solution 3-1 was applied to an acrylic plate using a bar coater to a wet film thickness of 75 μm, and then dried in an 80°C dryer for 30 minutes to form a coating layer containing only resin on the acrylic plate (comparative coating material 3-1).

[0151] Comparative Examples 3-2 to 3-5 In Example 3-1, the coating layer was formed on an acrylic plate in the same manner as in Example 3-1, except that compound A (Comparative Example 3-2), compound 9 (Comparative Example 3-3), compound 10 (Comparative Example 3-4), and compound 11 (Comparative Example 3-5), obtained in Synthesis Example 8, were used instead of compound 7 (comparative coating materials 2-2 to 2-5).

[0152] Comparative Example 3-6 Mix 122 parts by mass of Acrydic WFU-580 (manufactured by DIC Corporation), 60 parts by mass of toluene, and 10 parts by mass of compound 9. Immediately before coating, add 21 parts by mass of Duranate TPA-100 (manufactured by Asahi Kasei Corporation) and 2 parts by mass of dibutyltin dilaurate (DBTL), and mix again to obtain comparative coating solution 3-6.

[0153] The obtained comparative coating solution 3-6 was applied to an acrylic plate using a bar coater to a wet film thickness of 75 μm, and then dried in an 80°C dryer for 30 minutes to form a coating layer containing a limescale inhibitor and resin on the acrylic plate (comparative coating material 3-6).

[0154] <Performance Evaluation 2> The coating materials 2-1 to 2-5 of Examples 2-1 to 2-5 and the comparative coating material 2-1 to 2-6 of Comparative Examples 2-1 to 2-6 were evaluated for their limescale adhesion prevention (limescale removal), water contact angle, and surface condition using the method described below. The results are shown in Table 2 below.

[0155] Furthermore, the coating materials 3-1 to 3-6 of Examples 3-1 to 3-6 and the comparative coating material 3-1 to 3-6 of Comparative Examples 3-1 to 3-6 were evaluated for their limescale adhesion prevention (limescale removal), water contact angle, and surface condition using the method described below. The results are shown in Table 3 below.

[0156] [Water scale buildup prevention (water scale removal)] Drop one drop of tap water onto the coated surface of each coating material and allow it to dry. After drying, drop another drop of water onto the surface where the first drop was placed and allow it to dry. Repeat this process until 0.5g of limescale has accumulated. Wipe off the accumulated limescale with a paper towel, making two passes back and forth, and visually check the degree of limescale accumulation. Evaluate the results according to the following criteria.

[0157] (Evaluation criteria for limescale removal performance) ×: A considerable amount of limescale remains on the surface. ○: Some limescale remains on the surface. ◎: Limescale has been completely removed. [Hydrophilicity] In a dry state (25°C / 50%RH), a droplet of approximately 2 μL is created on the tip of a needle using pure water, and this droplet is brought into contact with the surface of the coating layer of each coating material to create a droplet on the coating layer. The angle between the tangent to the droplet surface and the coating film surface at the point where the coating layer and the droplet meet is measured using a contact angle meter (Kyowa Interface Science Co., Ltd., model number: CA-XP), and this angle is defined as the contact angle. If the contact angle is 50° or less, it is evaluated as hydrophilic ("Yes" in the table below), and if the contact angle exceeds 50°, it is evaluated as not hydrophilic ("No" in the table below).

[0158] [Surface condition] Visually inspect the transparency and presence or absence of tack on the surface of the coating layer of each coating material.

[0159] [Table 2]

[0160] [Table 3]

[0161] The results in Tables 2 and 3 show that the coating materials in the examples exhibit significantly superior limescale prevention (limescale removal) compared to the comparative coating materials. Although the evaluation methods for limescale prevention differ between Table 1 and Tables 2 and 3, the coating materials in the examples in Table 1 and Tables 2 and 3 are considered to exhibit equivalent limescale prevention.

Claims

1. The following formula (1): 【Chemistry 1】 In the above formula (1), Q is an alkali metal, an alkaline earth metal, or a nitrogen-containing compound. A is a linear or branched alkylene group having 2 to 4 carbon atoms. m represents the average number of moles of AO added, and is between 1 and 200. Y is a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms. n is either 0 or 1, R １ is a hydrogen atom or a methyl group, R ２ This is a group represented by the following formula (2), 【Chemistry 2】 In the above formula (2), R ３ and R ４ Each of these is independently a hydrogen atom or a methyl group, and * represents a linking point. l is 1 to 3, p is Q ＋ It represents the valence, which is 1 or 2. The limescale inhibitor and resin shown are included, A limescale-preventing composition for use in manufacturing molded articles by mixing it with a solvent, applying it to a substrate, and curing the resulting coating film.

2. Compound 5 below: 【Transformation 3】 The limescale inhibitor and resin shown are included, A limescale-preventing composition for use in manufacturing molded articles by mixing it with a solvent, applying it to a substrate, and curing the resulting coating film.

3. In the above formula (1), Q ＋ These are alkali metal cations, ammonium cations (NH ４ ＋ The limescale-preventing composition according to claim 1, wherein the cation is a nitrogen-containing compound cation having an alkyl group.

4. The limescale-preventing composition according to any one of claims 1 to 3, wherein the resin is a thermosetting resin.

5. The limescale-preventing composition according to claim 4, wherein the thermosetting resin is at least one selected from the group consisting of urethane resins and polyester resins.

6. The limescale-preventing composition according to claim 4, wherein the thermosetting resin is an unsaturated polyester resin.

7. The limescale-preventing composition according to any one of claims 1 to 3, wherein the resin is a thermoplastic resin.

8. The limescale-preventing composition according to claim 7, wherein the thermoplastic resin is a (meth)acrylic resin.

9. A limescale-preventing composition according to any one of claims 1 to 8, wherein the proportion of the limescale-preventing agent in the total ionic bonded salt exceeds 95% by mass.

10. The limescale-preventing composition according to any one of claims 1 to 9, wherein the limescale-preventing agent is contained in a proportion of 0.01 to 50 parts by mass per 100 parts by mass of the resin.

11. A molded article comprising the limescale-preventing composition according to any one of claims 1 to 10.

12. A method for producing a molded article, comprising the steps of preparing a mixture containing a limescale-preventing composition and a solvent according to any one of claims 1 to 10, and molding the mixture.

13. The following formula (1): 【Chemistry 4】 In the above formula (1), Q is an alkali metal, an alkaline earth metal, or a nitrogen-containing compound. A is a linear or branched alkylene group having 2 to 4 carbon atoms. m represents the average number of moles of AO added, and is between 1 and 200. Y is a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms. n is either 0 or 1, R １ is a hydrogen atom or a methyl group, R ２ This is a group represented by the following formula (2), 【Transformation 5】 In the above formula (2), R ３ and R ４ Each of these is independently a hydrogen atom or a methyl group, and * represents a linking point. l is 1 to 3, p is Q ＋ It represents the valence, which is 1 or 2. As shown, A limescale inhibitor used to manufacture molded articles by mixing it with a resin and a solvent, applying it to a substrate, and curing the resulting coating.

14. Compound 5 below: 【Transformation 6】 As shown, A limescale inhibitor used to manufacture molded articles by mixing it with a resin and a solvent, applying it to a substrate, and curing the resulting coating.

15. In the above formula (1), Q ＋ These are alkali metal cations, ammonium cations (NH ４ ＋ The limescale inhibitor according to claim 13, which is a nitrogen-containing compound cation having an alkyl group.

Images