Resin composition, resin, and product to be used in home in contact with water

Abstract

The present disclosure provides a resin composition capable of improving the mechanical characteristics, hot water resistance characteristics, and chemical resistance characteristics of a resin obtained by curing. The resin composition includes: a resin containing an ethylenically unsaturated group; modified lignin; and an organic peroxide. A part or all of the hydroxy groups of the modified lignin are acylated.

Description

Resin composition, resin and water-related products

[0001] The present disclosure relates to a resin composition, a resin, and a wet product, and more particularly to a resin composition containing modified lignin, a resin containing a cured product of this resin composition, and a wet product made from this resin.

[0002] In recent years, biomass-derived materials have been used to prevent environmental destruction, replacing petroleum-derived raw materials such as polyethylene powder and mined materials such as calcium carbonate fillers. Lignin derivatives, which can be extracted from wood such as cedar, are also biomass-derived materials, and their use as thermosetting resin materials is being considered.

[0003] Patent Documents 1 and 2 disclose resins using lignin derivatives. The resin in Patent Document 1 is a heat-resistant lignin-based polymer that contains a 1,1-diphenylpropane unit in which a phenol derivative is grafted to the α-position of the phenylpropane unit of lignin, and has ester moieties in which one or more hydroxyl groups are acylated. The resin in Patent Document 2 is a thermoplastic resin to which a resin modifier or an ultraviolet absorber consisting of a glycol alkylene oxide adduct in which an alkylene oxide is added to glycol lignin has been added.

[0004] However, the conventional resins obtained using lignin derivatives have the disadvantages of low mechanical properties such as bending strength and Izod impact strength, and also poor hot water resistance such as appearance after immersion in hot water, and poor chemical resistance such as appearance after application of chemicals.

[0005] JP 2011-256381 A JP 2023-137637 A

[0006] An object of the present disclosure is to provide a resin composition, a resin, and a wet-related product that can improve the mechanical properties, hot water resistance, and chemical resistance of the resin obtained by curing.

[0007] A resin composition according to one embodiment of the present disclosure contains a resin containing an ethylenically unsaturated group, a modified lignin, and an organic peroxide, and some or all of the hydroxy groups of the modified lignin are acylated.

[0008] A resin according to one embodiment of the present disclosure includes a cured product of a resin composition containing a resin having an ethylenically unsaturated group, an acylated modified lignin, and an organic peroxide.

[0009] A plumbing product according to one aspect of the present disclosure is made from the resin.

[0010] 1. Overview The resin composition according to this embodiment (hereinafter also referred to as composition (X)) contains a resin containing an ethylenically unsaturated group (hereinafter also referred to as resin (A)), a modified lignin (hereinafter also referred to as modified lignin (B)), and an organic peroxide (hereinafter also referred to as organic peroxide (C)). Some or all of the hydroxy groups of the modified lignin (B) are acylated.

[0011] The inventors have conducted extensive research to solve the above-mentioned problems, and have found that in a resin (hereinafter also referred to as resin (Y)) obtained by curing a composition (X) containing resin (A), modified lignin (B), and organic peroxide (C), the mechanical properties, hot water resistance, chemical resistance, etc. of resin (Y) can be changed by modifying the modified lignin (B), and have completed the present disclosure.

[0012] Composition (X) can improve the mechanical properties, hot water resistance, and chemical resistance of resin (Y) obtained by curing. The reason why composition (X) exhibits the above-described effects due to its configuration is not entirely clear, but it can be speculated, for example, as follows. Heating composition (X) causes decomposition of organic peroxide (C) to generate radicals, polymerizing resin (A) containing ethylenically unsaturated groups, and forming resin (Y) containing modified lignin (B) in the polymer of resin (A). The modified lignin (B) in composition (X) changes from a hydrophilic structure to a hydrophobic structure due to partial or complete acylation of hydroxy groups, making it possible to dissolve or finely disperse in monomers such as styrene and (meth)acrylic acid esters in resin (A). Therefore, in the formed resin (Y), there is no interface between the polymer of resin (A) and modified lignin (B), which is thought to result in improved mechanical properties such as flexural strength and Izod impact strength of the cured product of composition (X). Furthermore, since there is no interface between the polymer of resin (A) and the modified lignin (B), water penetration is suppressed, which is thought to reduce discoloration such as fading of resin (Y) during hot water immersion treatment and improve hot water resistance. Also, since penetration of chemicals and the like is suppressed, color change of resin (Y) after chemical application is reduced and chemical resistance is thought to improve.

[0013] Resin (Y) according to this embodiment contains a cured product of composition (X) containing resin (A) containing an ethylenically unsaturated group, acylated modified lignin (B), and organic peroxide (C). Because resin (Y) contains the cured product of composition (X), it has improved mechanical properties, hot water resistance, and chemical resistance.

[0014] The plumbing product according to this embodiment (hereinafter also referred to as plumbing product (Z)) is made of resin (Y). As described above, the plumbing product (Z) uses resin (Y) which has improved hot water resistance, mechanical properties, and chemical resistance, and therefore can be suitably used as plumbing components, products, etc. which require high durability in plumbing applications.

[0015] As described above, the present disclosure provides a resin composition that can improve the mechanical properties, hot water resistance, and chemical resistance of the resin obtained by curing, a resin containing a cured product of the resin composition, and a plumbing product made from the resin. Furthermore, the present disclosure can help prevent environmental destruction by promoting the distribution of products using resins that use biomass materials and have improved mechanical properties, hot water resistance, and chemical resistance.

[0016] 2. Details <Resin Composition> Composition (X) contains resin (A), modified lignin (B), and organic peroxide (C), and some or all of the hydroxy groups of the modified lignin (B) are acylated. Composition (X) may further contain components other than components (A) to (C) within a range that does not impair the effects of the present disclosure. Each component will be described below.

[0017] [Resin (A)] The resin (A) is a resin containing an ethylenically unsaturated group. One or more types of resin (A) can be used.

[0018] "Resin containing an ethylenically unsaturated group" refers to a resin containing a polymer, oligomer, or a combination thereof, and one or more ethylenically unsaturated groups. Therefore, resin (A) includes a mixture of a polymer and / or oligomer that does not have an ethylenically unsaturated group and a monomer that has an ethylenically unsaturated group, such as a (meth)acrylic acid ester or styrene. In this specification, "(meth)acrylic" means either or both of acrylic and methacrylic.

[0019] The term "ethylenically unsaturated group" refers to a group containing a carbon-carbon double bond other than the conjugated double bond of an aromatic ring. When composition (X) is heated, radicals generated by decomposition of organic peroxide (C) polymerize resin (A) containing an ethylenically unsaturated group, and composition (X) is cured. In other words, resin (A) is a thermosetting resin. By curing composition (X), resin (Y) is formed, which is a mixture of a polymer of resin (A) and modified lignin (B).

[0020] Examples of the ethylenically unsaturated group include monovalent groups such as vinyl, allyl, styryl and (meth)acryloyl groups; and divalent groups such as vinylene groups.

[0021] Examples of the resin (A) include vinyl ester resins, acrylic resins, unsaturated polyester resins, resins containing polymers of compounds having vinyl groups and compounds having vinyl groups, and polymers of compounds having conjugated double bonds.

[0022] The term "vinyl ester resin" refers to a resin in which a vinyl ester is dissolved in a monomer having an ethylenically unsaturated group. The term "vinyl ester" refers to a resin containing an ester group formed by the reaction of an epoxy group of an epoxy resin with a carboxy group of an unsaturated carboxylic acid having a vinyl group, such as (meth)acrylic acid.

[0023] Examples of vinyl esters include epoxy (meth)acrylates such as (meth)acrylate-modified bisphenol epoxy resins such as bisphenol A epoxy resins. Examples of monomers having an ethylenically unsaturated group include styrene and (meth)acrylic acid esters.

[0024] The vinyl ester resin is preferably a resin containing a vinyl ester and a styrene monomer, and more preferably a resin containing a (meth)acrylate-modified bisphenol-type epoxy resin and a styrene monomer.

[0025] The term "acrylic resin" refers to an acrylic syrup which is a mixture of a polymer of a monomer containing (meth)acrylic acid and / or a (meth)acrylic acid ester and a monomer containing (meth)acrylic acid and / or a (meth)acrylic acid ester.

[0026] Examples of acrylic resins include mixtures of polymers such as poly(meth)acrylic acid esters, such as polymethyl (meth)acrylate, and monomers such as (meth)acrylic acid esters, such as methyl (meth)acrylate.

[0027] The term "unsaturated polyester resin" refers to a resin in which an unsaturated polyester is dissolved in a monomer having an ethylenically unsaturated group. The term "unsaturated polyester" refers to a polyester resin having an ethylenically unsaturated group.

[0028] Examples of unsaturated polyesters include resins obtained by esterifying an unsaturated dicarboxylic acid or its anhydride, such as maleic anhydride or fumaric acid, a saturated carboxylic acid or its anhydride, such as phthalic anhydride or isophthalic acid, and an aliphatic diol, such as ethylene glycol or propylene glycol. Examples of monomers having an ethylenically unsaturated group include styrene and (meth)acrylic acid esters.

[0029] The unsaturated polyester resin is preferably a resin containing a polycondensate of a saturated dicarboxylic acid, an unsaturated dicarboxylic acid and an aliphatic diol, and a styrene monomer.

[0030] Examples of the resin containing a polymer of a compound having a vinyl group and a compound having a vinyl group include a mixture of polystyrene, which is a polymer of a styrene monomer, and a styrene monomer.

[0031] Examples of polymers of compounds having conjugated double bonds include polymers of compounds containing conjugated double bonds such as butadiene and isoprene.

[0032] Resin (A) preferably contains at least one resin selected from the group consisting of vinyl ester resins, acrylic resins, and unsaturated polyester resins, which can further improve the mechanical properties, hot water resistance, and chemical resistance of resin (Y) obtained by curing composition (X).

[0033] The proportion of resin (A) relative to composition (X) is, for example, 40% by mass or more and 95% by mass or less, preferably 50% by mass or more and 90% by mass or less, more preferably 60% by mass or more and 85% by mass or less, and particularly preferably 70% by mass or more and 80% by mass or less.

[0034] [Modified Lignin (B)] Modified lignin (B) is a lignin in which some or all of the hydroxy groups have been acylated. That is, modified lignin (B) is a lignin derivative (hereinafter also referred to as lignin derivative (B0)) shown below that has been subjected to an acylation treatment. "Acylation" refers to a reaction in which the hydrogen atoms of the hydroxy groups are substituted with acyl groups (R-C(=O)-, where R is a monovalent hydrocarbon group). One or more types of modified lignin (B) can be used.

[0035] (Lignin Derivative (B0)) In this specification, the lignin derivative (B0) refers to a substance obtained by subjecting lignin (a polymeric compound present in wood together with cellulose and having substituents such as hydroxyl groups and methoxy groups on aromatic rings) to at least one modification treatment selected from the group consisting of hydrolysis treatment, solvolysis treatment, steam treatment, oxidation treatment, reduction treatment, alkali treatment, acid treatment, electromagnetic wave treatment, enzyme treatment, microbial treatment, subcritical fluid treatment, supercritical fluid treatment, heavy treatment, and pyrolysis treatment, or a substance obtained by removing cellulose from this substance.

[0036] Examples of the lignin derivative (B0) include glycol lignin, sulfate lignin, lignosulfonic acid, sulfite lignin, and kraft lignin. The lignin derivative (B0) preferably contains at least one of glycol lignin and sulfate lignin. That is, the modified lignin (B) is preferably derived from at least one of glycol lignin and sulfate lignin. In this case, the mechanical properties, hot water resistance, and chemical resistance of the resin (Y) can all be further improved.

[0037] Glycol lignin refers to glycol-modified lignin obtained by solvolysis or digestion of lignocellulose using glycols such as polyethylene glycol, polypropylene glycol, polyethylene polypropylene glycol, and ethylene glycol as a solvent. In this specification, "glycol lignin" refers to polyethylene glycol-modified lignin (PEG lignin) obtained using polyethylene glycol as a solvent. In other words, glycol lignin is a lignin in which some or all of the hydrogen atoms of the alcoholic hydroxy groups at the benzylic positions are substituted with polyethylene glycol chains, and in the following formula (1) showing the partial structure of glycol lignin, R １ is the oxygen atom of a phenolic hydroxy group, and R ２ is an alcoholic hydroxy group at the benzylic position or a polyethylene glycol chain (in formula (1), * indicates the bonding site to a methyl group or an adjacent partial structure).

[0038]

[0039] The molecular formula weight of the polyethylene glycol chain in the glycol lignin is, for example, from 100 to 800, and preferably from 200 to 600. The weight average molecular weight of the glycol lignin (a value calculated as a standard polystyrene by GPC measurement) is, for example, from 5,000 to 20,000, and preferably from 8,000 to 12,000. The amount of hydroxy groups in the glycol lignin is, for example, from 3 mmol / g to 8 mmol / g, and preferably from 4.5 mmol / g to 6.5 mmol / g.

[0040] "Sulfuric acid lignin" means lignin obtained after hydrolysis of wood with sulfuric acid and removal of cellulose.

[0041] The lignin derivative (B0) has, as hydroxy groups, an alcoholic hydroxy group and a phenolic hydroxy group. Examples of the alcoholic hydroxy group in the lignin derivative (B0) include a hydroxy group at the benzyl position of an aromatic ring, a hydroxy group at the α-position of a propane chain bonded to an aromatic ring, and a terminal hydroxy group of a polyethylene glycol chain of glycol lignin.

[0042] By subjecting the lignin derivative (B0) to an acylation treatment, some or all of the hydroxy groups of the lignin derivative (B0) are acylated, forming acyloxy groups (R—C(═O)—O—, where R is a monovalent hydrocarbon group).

[0043] The hydrocarbon group represented by R is, for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include saturated hydrocarbon groups and unsaturated hydrocarbon groups. Examples of saturated hydrocarbon groups include chain hydrocarbon groups such as methyl, ethyl, propyl, butyl, hexyl, and 2-ethylhexyl groups; alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, and tricyclodecyl groups; and aromatic hydrocarbon groups such as phenyl, benzyl, naphthyl, and naphthylmethyl groups. Examples of unsaturated hydrocarbon groups include chain hydrocarbon groups such as ethenyl, 2-propenyl, and butenyl groups; alicyclic hydrocarbon groups such as cyclopentenyl, cyclohexenyl, and tricyclodecenyl groups; and aromatic hydrocarbon groups such as phenylethenyl and naphthylethenyl groups.

[0044] Examples of carboxylic acids used in the acylation treatment include saturated carboxylic acids in which the hydrocarbon group of R is a saturated hydrocarbon group, and unsaturated carboxylic acids in which the hydrocarbon group of R is an unsaturated hydrocarbon group. Examples of saturated carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, stearic acid, and benzoic acid. Among these, acetic acid is preferred. Examples of unsaturated carboxylic acids include (meth)acrylic acid, propiolic acid, crotonic acid, and oleic acid. Among these, (meth)acrylic acid is preferred, and methacrylic acid is more preferred. In addition to these carboxylic acids, the corresponding acid anhydrides, acid halides, etc. can also be used in the acylation treatment.

[0045] The modified lignin (B) is preferably acylated with at least one selected from the group consisting of saturated carboxylic acids, their acid anhydrides, and their acid halides (hereinafter also referred to as saturated carboxylic acid compound (a)). In this case, the mechanical properties, hot water resistance, and chemical resistance of the resin (Y) can all be further improved. As the acylation with the saturated carboxylic acid compound (a), acetylation with at least one of acetic acid and acetic anhydride is preferred, and acetylation with acetic anhydride is more preferred.

[0046] The modified lignin (B) is preferably acylated with at least one selected from the group consisting of unsaturated carboxylic acids, their acid anhydrides, and their acid halides (hereinafter also referred to as unsaturated carboxylic acid compound (b)). In this case, since the modified lignin (B) has an unsaturated double bond in the acyl group, the resin (A) and the modified lignin (B) are chemically bonded in the resin (Y), thereby forming a crosslinked structure between the resin (A) and the modified lignin (B). As a result, the resin (Y) can further improve mechanical properties, hot water resistance, and chemical resistance compared to a resin acylated with the saturated carboxylic acid compound (a). As the acylation with the unsaturated carboxylic acid compound (b), (meth)acrylation with at least one of (meth)acrylic acid and (meth)acrylic anhydride is preferred, and (meth)acrylation with (meth)acrylic anhydride is more preferred.

[0047] The acylation rate in the modified lignin (B) is, for example, 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more. The higher the acylation rate in the modified lignin (B), the more preferable it is, and it may be 98 mol% or more, or even 100 mol%. In this case, the mechanical properties, hot water resistance, and chemical resistance of the resin (Y) can all be further improved. The "acylation rate" in the modified lignin (B) refers to the ratio (mol %) of the number of moles of acylated hydroxy groups in the modified lignin (B) obtained by the acylation treatment to the number of moles of hydroxy groups in one molecule of the lignin derivative (B0) before the acylation treatment.

[0048] The carboxylic acid, acid anhydride, or acid halide used for acylation of the lignin derivative (B0) may be one type, or two or more types may be used. That is, the acylation of the lignin derivative (B0) may be carried out using a saturated carboxylic acid compound (a) and an unsaturated carboxylic acid compound (b) in combination. That is, the modified lignin (B) may be acylated with the saturated carboxylic acid compound (a) and the unsaturated carboxylic acid compound (b). In this case, the Izod impact strength of the resin (Y) can be further improved.

[0049] When the acylation of the lignin derivative (B0) is carried out using a saturated carboxylic acid compound (a) and an unsaturated carboxylic acid compound (b) in combination, the acylation rate of the saturated carboxylic acid compound (a) in the resulting modified lignin (B) is, for example, 20 mol% or more, preferably 70 mol% or more. This acylation rate is, for example, 90 mol% or less, preferably 80 mol% or less. Furthermore, the acylation rate of the unsaturated carboxylic acid compound (b) in the resulting modified lignin (B) is, for example, 10 mol% or more, preferably 20 mol% or more. This acylation rate is, for example, 80 mol% or less, preferably 30 mol% or less.

[0050] The molar ratio of acyl groups of the unsaturated carboxylic acid compound (b) to acyl groups of the saturated carboxylic acid compound (a) in the resulting modified lignin (B) (unsaturated carboxylic acid compound (b) / saturated carboxylic acid compound (a)) is, for example, 10 / 90 or more, preferably 20 / 80 or more. This molar ratio is, for example, 80 / 20 or less, preferably 70 / 30 or less. In this case, the Izod impact strength of the resin (Y) can be further improved.

[0051] The proportion of the modified lignin (B) is preferably 50 parts by mass or less relative to 100 parts by mass of the resin (A). In this case, the acylated modified lignin (B) can be dissolved or finely dispersed in the resin (A), thereby further improving the mechanical properties, hot water resistance, and chemical resistance of the resin (Y). This proportion is more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, and particularly preferably 30 parts by mass or less. If this proportion exceeds 30 parts by mass, the viscosity of the composition (X) may increase, and the handleability may decrease. The proportion of the modified lignin (B) is, for example, 1 part by mass or more relative to 100 parts by mass of the resin (A). If this proportion is less than 1 part by mass, the effect of improving the mechanical properties, hot water resistance, and chemical resistance of the resin (Y) may not be clearly manifested. The proportion of the modified lignin (B) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, and particularly preferably 25 parts by mass or more.

[0052] The proportion of the modified lignin (B) relative to the composition (X) is preferably 35% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass. The proportion of the modified lignin (B) relative to the composition (X) is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 20% by mass or more.

[0053] [Organic Peroxide (C)] An "organic peroxide" refers to an organic compound having one or more oxygen-oxygen bonds in one molecule, and is represented, for example, by the formula: RO-OR' (R and R' are organic groups having 1 to 20 carbon atoms). One or more types of organic peroxides (C) can be used.

[0054] Examples of the organic peroxide (C) include alkyl peroxy esters, peroxy carbonates, diacyl peroxides, peroxy ketals, dialkyl peroxides, and hydroperoxides.

[0055] The 10-hour half-life temperature of the organic peroxide (C) is, for example, 10°C or higher and 150°C or lower, and preferably 20°C or higher and 110°C or lower.

[0056] From the viewpoint of the 10-hour half-life temperature, the organic peroxide (C) preferably contains at least one selected from the group consisting of alkyl peroxy esters, peroxy carbonates, and diacyl peroxides. In this case, the polymerization reaction of the resin (A) during curing of the composition (X) can be appropriately carried out, and the mechanical properties, hot water resistance, and chemical resistance of the resulting resin (Y) can all be further improved.

[0057] Examples of alkyl peroxy esters include 3-hydroxy-1,1-dimethylbutyl peroxy neodecanoate, α-cumyl peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-amyl peroxy neodecanoate, t-amyl peroxy benzoate, and t-hexyl peroxy-2-ethylhexanoate.

[0058] Examples of peroxycarbonates include t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, t-amylperoxyisopropyl carbonate, and di(sec-butyl)peroxydicarbonate.

[0059] Examples of diacyl peroxides include diisononanoyl peroxide, dilauroyl peroxide, and dibenzoyl peroxide.

[0060] The proportion of the organic peroxide (C) is preferably 0.5 parts by mass or more relative to 100 parts by mass of the resin (A). If this proportion is less than 0.5 parts by mass, the curing time of the composition (X) may be prolonged. This proportion is more preferably 0.8 parts by mass or more, and even more preferably 0.9 parts by mass or more. Furthermore, this proportion is preferably 3 parts by mass or less. If this proportion exceeds 3 parts by mass, defects such as cracks and unevenness may occur in the appearance of the cured product of the composition (X), and costs may also increase. This proportion is more preferably 2 parts by mass or less, even more preferably 1.2 parts by mass or less, and particularly preferably 1.1 parts by mass or less.

[0061] The proportion of the organic peroxide (C) relative to the composition (X) is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 0.9% by mass or more. The proportion of the organic peroxide (C) relative to the composition (X) is, for example, 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1.1% by mass or less.

[0062] [Other Components] Examples of other components include fillers, antifoaming agents, colorants, patterning agents, etc. One or more of the other components may be used.

[0063] One or more fillers can be selected and used depending on the location where the resin (Y) is used and the required quality. Examples of fillers include inorganic fillers such as silica, aluminum hydroxide, and calcium carbonate. When the composition (X) contains a filler, the proportion of the filler is preferably 100 parts by mass or more, and more preferably 200 parts by mass or more, per 100 parts by mass of the resin (A). This proportion is preferably 350 parts by mass or less, and more preferably 300 parts by mass or less.

[0064] When composition (X) contains components other than the filler, the proportion of the other components is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, relative to 100 parts by mass of resin (A). The lower limit of this proportion is, for example, 0.1 parts by mass or more.

[0065] <Method for Producing Resin Composition> Composition (X) can be produced as follows. First, other components, such as liquid materials such as an antifoaming agent and a colorant, are blended with resin (A). Next, modified lignin (B) is blended and the mixture is stirred and mixed. Since modified lignin (B) is in powder form, it is dispersed in resin (A). Organic peroxide (C) is blended with the resulting mixture, and the mixture is mixed with a stirrer and degassed, whereby modified lignin (B) becomes dissolved or finely dispersed in resin (A), and composition (X) is obtained.

[0066] <Resin> Resin (Y) includes a cured product of the above-mentioned composition (X). That is, resin (Y) includes a cured product of composition (X) containing resin (A), acylated modified lignin (B), and organic peroxide (C). Resin (Y) is obtained by curing composition (X) in which acylated modified lignin (B) is dissolved or finely dispersed in resin (A), and is considered to be a homogeneous mixture of a polymer of resin (A) and modified lignin (B) without an interface. Resin (Y) has improved mechanical properties, hot water resistance, and chemical resistance. The mechanical properties of resin (Y) can be evaluated, for example, by bending strength, Izod impact strength, etc. The hot water resistance of resin (Y) can be evaluated, for example, by the appearance after hot water immersion treatment, the color difference before and after hot water immersion treatment, etc. The chemical resistance of resin (Y) can be evaluated by applying a detergent such as an acidic detergent, alkaline detergent, or neutral detergent to the cured product, and observing changes in the color and surface properties of the cured product after about one week.

[0067] The flexural strength of resin (Y) is preferably 50 MPa or more, more preferably 55 MPa or more, even more preferably 90 MPa or more, particularly preferably 100 MPa or more, and even more particularly preferably 110 MPa or more. The higher the flexural strength of resin (Y), the better, but the upper limit is, for example, 150 MPa or less. The flexural strength of resin (Y) can be measured by a method in accordance with JIS-K7171.

[0068] The Izod impact strength of resin (Y) is 7 kJ / m ２ It is preferable that the concentration is 8 kJ / m or more. ２ More preferably, it is 8.5 kJ / m or more. ２ More preferably, it is 9 kJ / m or more. ２ It is particularly preferable that the concentration is 11 kJ / m or more. ２ More particularly preferably, 13 kJ / m or more ２ The higher the Izod impact strength of the resin (Y), the better, but the upper limit is, for example, 15 kJ / m ２ The Izod impact strength of the resin (Y) can be measured by a method in accordance with JIS-K7110.

[0069] The color difference (ΔE) of resin (Y) before and after hot water immersion treatment is preferably 3 or less, more preferably 2 or less, and even more preferably 1 or less. The smaller the color difference (ΔE) of resin (Y) before and after hot water immersion treatment, the more preferable, but the lower limit is, for example, 0.5 or more. The color difference (ΔE) of resin (Y) before and after hot water immersion treatment can be measured by the method described in the examples below.

[0070] It is preferable that the resin (Y) is coated with a detergent such as an acidic detergent, a neutral detergent, or an alkaline detergent, and thereafter, one week later, the appearance of the surface of the resin (Y) does not change significantly. In this case, the chemical resistance of the resin (Y) is considered to be further improved.

[0071] <Method for Producing Resin> Resin (Y) can be produced as follows. First, composition (X) is injected into a mold having a desired inner surface shape to fill it. Next, the mold filled with composition (X) is heated to obtain resin (Y), which is a cured product of composition (X). The heating temperature is preferably 70°C or higher and 100°C or lower, and the heating time is preferably 30 minutes or higher and 60 minutes or lower.

[0072] <Water-related Product> The water-related product (Z) is a product made of the above-mentioned resin (Y). That is, the water-related product (Z) is formed of the resin (Y).

[0073] The plumbing product (Z) may be any product that can be wetted by liquid, and examples thereof include products used in kitchens, washrooms, toilets, baths, etc. Examples of the plumbing product (Z) include kitchen counters, sinks, range hoods, etc. in kitchens, washbasins, faucets, bowls, etc. in washrooms, toilet seats, toilet bowls, etc. in toilets, and bathtubs, bathroom doors, bathroom racks, shower heads, etc. in baths. The plumbing product (Z) may also be a product that can be wetted by liquid when used outdoors.

[0074] The plumbing product (Z) may be produced by curing the composition (X) using a formwork having an inner surface shape corresponding to the desired product shape, or by cutting the cured product of the composition (X) into the desired product shape.

[0075] The present disclosure will be described in more detail below using examples, but the present disclosure is not limited to only these examples.

[0076] Examples 1 to 4 and Comparative Examples 1 and 2 Preparation of Resin Composition First, the types and amounts of components (A) to (C) shown in Table 1 below were weighed. Next, modified lignin (B) was blended into resin (A) and mixed by stirring. Next, organic peroxide (C) was blended, and the mixture was mixed with a stirrer ("L2814-S-1" manufactured by Chuo Rika Co., Ltd.) and degassed to obtain composition (X) in which modified lignin (B) was dissolved or finely dispersed in resin (A).

[0077] [Components] (Resin (A)) Vinyl ester resin: bisphenol A vinyl ester resin ("Prominate H6600" manufactured by Japan Composite Co., Ltd.)

[0078] (Modified lignin (B)) Glycol lignin Untreated material (glycol lignin): polyethylene glycol modified lignin ("SD4" manufactured by Lignomateria) Acetylated / methacrylated hybrid treated material: untreated glycol lignin subjected to both acetylation treatment with acetic anhydride and methacrylate treatment with methacrylic anhydride Acetylated material: untreated glycol lignin subjected to acetylation treatment with acetic anhydride Methacrylated material: untreated glycol lignin subjected to methacrylate treatment with methacrylic anhydride Sulfuric acid lignin Untreated material (sulfuric acid lignin): "SSEIF-BD" manufactured by Lignum Methacrylated material: untreated sulfuric acid lignin subjected to methacrylate treatment with methacrylic anhydride

[0079] The acetylated-methacrylated hybrid glycol lignin was synthesized as follows. 30 g of pyridine and 0.25 equivalents of methacrylic anhydride relative to the hydroxyl groups of the glycol lignin were added to 10 g of untreated glycol lignin, and the mixture was stirred at room temperature for 2 hours to carry out a methacrylation reaction. Next, an amount of acetic anhydride sufficient to react with the hydroxyl groups of the glycol lignin was added, and the reaction was continued for another 6 hours. The resulting reaction solution was added to 300 g of cyclohexane to obtain a viscous material. This viscous material was dissolved in a small amount of acetone, then added to 300 g of water. The precipitate was collected by filtration and dried for 6 hours to obtain an acetylated-methacrylated hybrid.

[0080] An acetylated glycol lignin was synthesized as follows. 30 g of pyridine and 30 g of acetic anhydride were added to 10 g of untreated glycol lignin, and the mixture was stirred at room temperature for 2 hours to carry out an acetylation reaction. The resulting reaction solution was added to 300 g of cyclohexane to obtain a viscous material. This viscous material was dissolved in a small amount of acetone and then added to 300 g of water. The precipitate was collected by filtration and dried for 6 hours to obtain an acetylated glycol lignin. A methacrylated glycol lignin was also synthesized in the same manner as above, using methacrylic anhydride instead of acetic anhydride.

[0081] The methacrylated product of sulfuric acid lignin was synthesized as follows. 30 g of pyridine and 30 g of methacrylic anhydride were added to 10 g of untreated sulfuric acid lignin, and the mixture was stirred at room temperature for 2 hours to carry out a methacrylate reaction. The solid matter in the resulting reaction solution was filtered, washed with cyclohexane, and dried for 6 hours to obtain a methacrylated product.

[0082] (Organic Peroxide (C)) t-Hexylperoxy-2-ethylhexanoate ("Perhexyl O" manufactured by NOF Corporation)

[0083] <Production of Resin> Each of the compositions (X) prepared above was injected into a predetermined mold and filled. The mold filled with each composition (X) was heated at 90°C for 60 minutes using a heating and drying oven. In this way, resin (Y) (dimensions: length 200 mm, width 150 mm, thickness 8 mm) consisting of a cured product of composition (X) was obtained.

[0084] <Evaluation> [Mechanical Properties] The resin (Y) produced above was cut to a predetermined size (160 mm long, 15 mm wide, 8 mm thick) to prepare a test piece, and using this test piece, the bending strength and Izod impact strength were measured as mechanical properties by the following measurement methods. The measured values ​​of the bending strength and Izod impact strength of resin (Y) are shown in Table 1 below.

[0085] (Bending Strength) Using the prepared test piece, a bending test was carried out at room temperature in accordance with JIS-K7171 using a precision universal testing machine ("Autograph AG-X" manufactured by Shimadzu Corporation). The bending strength (MPa) was measured seven times, and the arithmetic mean value was taken as the measured value. The bending strength can be evaluated as A (very good) when it is 100 MPa or more, B (good) when it is 55 MPa or more and less than 100 MPa, and C (poor) when it is less than 55 MPa.

[0086] (Izod impact strength) Using the prepared test specimen, an Izod impact test was carried out at room temperature in accordance with JIS-K7110 using an Izod impact tester (manufactured by Tester Sangyo Co., Ltd.). ２ The Izod impact strength was 9 kJ / m ２ If it is more than 7 kJ / m, it is rated as A (very good). ２ 9kJ / m or more ２ If it is less than 7 kJ / m, it is rated B (good). ２ If it is less than this, it can be evaluated as C (poor).

[0087] [Hot Water Resistance] The prepared test piece was completely submerged in hot water at 80°C and then removed after 300 hours. The removed test piece was visually observed for its appearance after immersion in hot water to assess its hot water resistance. The observed appearance of the resin (Y) was evaluated as A (good) when no discoloration was observed, and as B (poor) when significant discoloration was observed. In addition, the L of each test piece before and after immersion in hot water was ＊ a ＊ b ＊ The values ​​in the color system were measured using a spectrophotometer ("CM-26dG" manufactured by Konica Minolta, Inc.) to determine the color difference (ΔE) before and after immersion in hot water. The measured values ​​of the color difference (ΔE) are shown in Table 1 below. A color difference (ΔE) of 3 or less can be evaluated as A (good), and a color difference of more than 3 can be evaluated as B (poor).

[0088] [Chemical Resistance] The resin (Y) thus produced was coated with an acidic detergent or an alkaline detergent, and after one week had passed, the resin (Y) was washed and the color change on the surface of the resin (Y) was visually confirmed. The chemical resistance was evaluated as A (good) when no color change was observed, and as B (poor) when a gloss change was observed.

[0089]

[0090] As is clear from the results in Table 1, the resin compositions of the Examples have improved mechanical properties, hot water resistance, and chemical resistance of the resins obtained by curing compared to the resin compositions of the Comparative Examples. In particular, the modified lignin subjected to the acetylation / methacrylate hybrid treatment has improved Izod impact strength compared to the modified lignins that have been acetylated only or methacrylated only.

[0091] (Summary) As is clear from the above embodiments, the present disclosure includes the following aspects: A resin composition (X) of a first aspect contains a resin (A) containing an ethylenically unsaturated group, a modified lignin (B), and an organic peroxide (C), and some or all of the hydroxy groups of the modified lignin (B) are acylated.

[0092] According to the first aspect, the mechanical properties, hot water resistance, and chemical resistance of the resin (Y) obtained by curing can all be improved. Furthermore, by promoting the distribution of products using the resin (Y) that uses a biomass material and has improved mechanical properties, hot water resistance, and chemical resistance, it is possible to prevent environmental destruction.

[0093] The resin composition (X) of the second embodiment is the resin composition of the first embodiment, wherein the modified lignin (B) is derived from at least one of glycol lignin and sulfate lignin.

[0094] According to the second aspect, the mechanical properties, hot water resistance, and chemical resistance of the resin (Y) obtained by curing can all be further improved.

[0095] In the resin composition (X) of the third aspect, in the first or second aspect, the resin (A) containing an ethylenically unsaturated group contains at least one selected from the group consisting of a vinyl ester resin, an acrylic resin, and an unsaturated polyester resin.

[0096] According to the third aspect, by using these resins as the resin (A), it is possible to further improve the mechanical properties, hot water resistance and chemical resistance of the resin (Y).

[0097] In the resin composition (X) of the fourth aspect, in any one of the first to third aspects, the organic peroxide (C) includes at least one selected from the group consisting of alkyl peroxy esters, peroxycarbonates, and diacyl peroxides.

[0098] According to the fourth aspect, by using an organic peroxide (C) having an appropriate 10-hour half-life temperature, it is possible to further improve all of the mechanical properties, hot water resistance, and chemical resistance of the resin (Y).

[0099] In the resin composition (X) of the fifth aspect, in any one of the first to fourth aspects, the proportion of the organic peroxide (C) is 0.5 parts by mass or more and 3 parts by mass or less per 100 parts by mass of the resin (A).

[0100] According to the fifth aspect, the curing time of the resin composition (X) can be made appropriate, defects such as cracks and unevenness in the appearance of the resin (Y) can be suppressed, and an increase in costs can be suppressed.

[0101] In the resin composition (X) of the sixth aspect, in any one of the first to fifth aspects, the modified lignin (B) is acylated with at least one selected from the group consisting of saturated carboxylic acids, acid anhydrides thereof, and acid halides thereof.

[0102] According to the sixth aspect, the mechanical properties, hot water resistance, and chemical resistance of the resin (Y) can all be further improved.

[0103] In the seventh aspect of the resin composition (X), in any one of the first to sixth aspects, the modified lignin (B) is acylated with at least one selected from the group consisting of unsaturated carboxylic acids, acid anhydrides thereof, and acid halides thereof.

[0104] According to the seventh aspect, since the modified lignin (B) has an unsaturated double bond in the acyl group, the resin (A) and the modified lignin (B) are chemically bonded to each other in the resin (Y), thereby forming a crosslinked structure between the resin (A) and the modified lignin (B). As a result, the resin (Y) can further improve all of the mechanical properties, hot water resistance, and chemical resistance.

[0105] In the resin composition (X) of the eighth aspect, in any one of the first to seventh aspects, the modified lignin (B) is acylated with at least one selected from the group consisting of saturated carboxylic acids, acid anhydrides thereof, and acid halides thereof, and at least one selected from the group consisting of unsaturated carboxylic acids, acid anhydrides thereof, and acid halides thereof.

[0106] According to the eighth aspect, the resin (Y) can further improve the Izod impact strength in particular.

[0107] In the resin composition (X) of a ninth aspect, in any one of the first to eighth aspects, the proportion of the modified lignin (B) is 50 parts by mass or less per 100 parts by mass of the resin (A).

[0108] According to the ninth aspect, in the resin composition (X), the acylated modified lignin (B) can be dissolved or finely dispersed in the resin (A), and the mechanical properties, hot water resistance, and chemical resistance of the resin (Y) can all be further improved.

[0109] The resin (Y) of the tenth aspect includes a cured product of a resin composition (X) containing a resin (A) having an ethylenically unsaturated group, an acylated modified lignin (B), and an organic peroxide (C).

[0110] According to the tenth aspect, the resin (Y) can improve all of the mechanical properties, hot water resistance, and chemical resistance.

[0111] The plumbing product (Z) of the eleventh embodiment is composed of the resin (Y) of the tenth embodiment.

[0112] According to the eleventh aspect, the resin (Y) can be suitably used as a water-related member, product, or the like that requires high durability.

Claims

1. A resin composition comprising a resin containing an ethylenically unsaturated group, modified lignin, and an organic peroxide, in which some or all of the hydroxy groups of the modified lignin are acylated.

2. The resin composition according to claim 1, wherein the modified lignin is derived from at least one of glycol lignin and sulfuric acid lignin.

3. The resin composition according to claim 1, wherein the resin containing an ethylenically unsaturated group comprises at least one resin selected from the group consisting of vinyl ester resins, acrylic resins and unsaturated polyester resins.

4. The resin composition according to claim 1, wherein the organic peroxide comprises at least one selected from the group consisting of alkyl peroxy esters, peroxy carbonates, and diacyl peroxides.

5. The resin composition according to claim 1, wherein the ratio of said organic peroxide is 0.5 parts by mass or more and 3 parts by mass or less per 100 parts by mass of said resin containing an ethylenically unsaturated group.

6. The resin composition according to claim 1, wherein the modified lignin is acylated with at least one selected from the group consisting of saturated carboxylic acids, their acid anhydrides, and their acid halides.

7. The resin composition according to claim 1, wherein the modified lignin is acylated with at least one member selected from the group consisting of unsaturated carboxylic acids, their acid anhydrides, and their acid halides.

8. The resin composition according to claim 1, wherein the modified lignin is acylated with at least one selected from the group consisting of saturated carboxylic acids, their acid anhydrides, and their acid halides, and at least one selected from the group consisting of unsaturated carboxylic acids, their acid anhydrides, and their acid halides.

9. The resin composition according to claim 1, wherein the proportion of the modified lignin is 50 parts by mass or less per 100 parts by mass of the resin containing an ethylenically unsaturated group.

10. A resin comprising a cured product of a resin composition containing a resin having an ethylenically unsaturated group, an acylated modified lignin, and an organic peroxide.

11. A plumbing product made from the resin described in claim 10.

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