Resin modifier, ultraviolet absorber, and resin composition containing them

Abstract

To provide a resin modifier and an ultraviolet absorber derived from natural materials, which can dissolve in resin without use of special dispersion means.SOLUTION: A glycol lignin alkylene oxide adduct, with alkylene oxide added to glycol lignin, is used as a resin modifier or an ultraviolet absorber.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a resin modifier, an ultraviolet absorber, and a resin composition containing them. The present invention also relates to a coating composition, a molded article, a coating film, etc., made of the resin composition. [Background technology]

[0002] Ultraviolet rays from the sun and other sources are one of the causes of degradation of polymeric materials, and it is important to protect polymeric materials using ultraviolet absorbers to prevent degradation due to ultraviolet rays. In addition, ultraviolet rays are harmful to the human body, so it is also essential to protect the human body with sunglasses, sunscreen, etc. For these reasons, the demand for ultraviolet absorbers is increasing day by day.

[0003] Conventionally, known common ultraviolet absorbers include those composed of benzotriazole-based compounds, etc. For example, Patent Documents 1 to 3 disclose techniques for adding a benzotriazole-based compound to a resin composition such as a coating composition for the purpose of protecting a coated surface from sunlight.

[0004] On the other hand, benzotriazole compounds are also substances of concern due to their harmful effects. Furthermore, in response to the strengthening of global chemical substance regulations, there is a demand for the development of UV absorbers made from environmentally friendly materials, such as natural products. As UV absorbers derived from natural products, UV absorbers containing low-modification lignin as an active ingredient have been reported (see, for example, Patent Document 4). As described in Patent Document 4, lignin is a polymer compound formed by the condensation of basic units consisting of hydroxyphenylpropane, and is typically present in wood at approximately 20 to 30% as a cell wall component. Furthermore, lignin has a structure in which π-conjugation is linked, and has an aromatic main chain structure and phenolic hydroxyl groups that can become organic radicals, thereby providing UV absorption capabilities.

[0005] Incidentally, Patent Document 5 discloses a glycol lignin alkylene oxide adduct, a novel lignin derivative obtained by adding an alkylene oxide to glycol lignin. Furthermore, it is also disclosed that this adduct is compatible with water, water-soluble organic solvents, and water-insoluble organic solvents (e.g., aromatic organic solvents), and is therefore suitable for use as a dispersant that can improve the dispersibility of dispersed materials such as inorganic and organic pigments, pesticides, and oilfield drilling sludge. The use (dispersant) disclosed in Patent Document 5 is not intended to modify resins. Furthermore, there is no specific mention of the UV absorption ability of the adduct, nor is there any disclosure that the adduct exhibits excellent solubility in various resins. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-213941 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-246344 [Patent Document 3] Japanese Patent Publication No. 2019-202235 [Patent Document 4] Japanese Patent Publication No. 2020-204005 [Patent Document 5] Patent Publication No. 2021-147409 Summary of the Invention [Problem to be solved by the invention]

[0007] The low-modified lignin described in Patent Document 4 has low solubility in water and organic solvents. Therefore, when the low-modified lignin is added to a resin as a resin modifier or UV absorber to obtain a resin composition, it must be added in the form of a dispersion in a solvent such as water, as disclosed in Patent Document 4. Furthermore, to obtain a dispersion by dispersing the low-modified lignin in a solvent in this manner, it is necessary to use dispersion means such as a special stirrer, device, or dispersant, which makes the operation complicated and increases the time and cost required to produce the resin composition.

[0008] Therefore, an object of the present invention is to provide a resin modifier and an ultraviolet absorber derived from natural products that can be dissolved in resin without using any special dispersion means. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above problems, and as a result, have found that the above problems can be solved by using the glycol lignin alkylene oxide adduct disclosed in Patent Document 5 as a resin modifier, thereby completing the present invention.

[0010] That is, according to one embodiment of the present invention, there is provided a resin modifier comprising a glycol lignin alkylene oxide adduct in which an alkylene oxide is added to glycol lignin.

[0011] According to another aspect of the present invention, there is also provided an ultraviolet absorber comprising a glycol lignin alkylene oxide adduct in which an alkylene oxide is added to glycol lignin. [Effects of the Invention]

[0012] According to the present invention, there are provided resin modifiers and ultraviolet absorbers derived from natural products that can be dissolved in resins without the use of special dispersion means. [Brief explanation of the drawings]

[0013] [Figure 1]1 is a photograph showing the state of solubility when the solubility of glycol lignin, glycol lignin ethylene oxide adduct, and soda lignin ethylene oxide adduct in emulsion-polymerized polymers was evaluated in the Examples section described later. [Figure 2] 1 is a photograph showing the state of solubility when the solubility of glycol lignin, glycol lignin ethylene oxide adduct, and soda lignin ethylene oxide adduct in solution-polymerized polymers was evaluated in the Examples section described later. [Figure 3] This is a graph showing absorption spectra obtained by measuring absorbance in a wavelength range of 200 to 400 nm for a solution-polymerized polymer solution of 2-hydroxy-4-methoxybenzophenone and a solution-polymerized polymer solution of a glycol lignin ethylene oxide adduct, together with blank results, in the Examples section described below. DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. Furthermore, in this specification, the range "X to Y" means "X or more and Y or less," and "weight" and "mass," "wt%" and "mass%," and "parts by weight" and "parts by mass" are treated as synonyms. Furthermore, unless otherwise specified, measurements of operations and physical properties are performed at room temperature (20 to 25°C) and a relative humidity of 40 to 60%.

[0015] As used herein, the term "(meth)acrylic" encompasses both acrylic and methacrylic. Thus, for example, the term "(meth)acrylic acid" encompasses both acrylic acid and methacrylic acid. Similarly, the term "(meth)acrylate" encompasses both acrylate and methacrylate, and the term "(meth)acrylamide" encompasses both acrylamide and methacrylamide.

[0016] Furthermore, in this specification, when a certain structural unit is said to be "derived from" a certain monomer, it means that the structural unit is a divalent structural unit generated by cleavage of one of the polymerizable unsaturated double bonds of the corresponding monomer.

[0017] [Resin modifier and UV absorber] One aspect of the present invention is a resin modifier comprising a glycol lignin alkylene oxide adduct in which an alkylene oxide is added to glycol lignin. Another aspect of the present invention is an ultraviolet absorber comprising a glycol lignin alkylene oxide adduct in which an alkylene oxide is added to glycol lignin.

[0018] First, the glycol lignin alkylene oxide adduct (hereinafter simply referred to as "the adduct of the present invention"), which is the active ingredient of the resin modifier and ultraviolet absorber according to the present invention, will be described below.

[0019] (glycol lignin alkylene oxide adduct) The glycol lignin alkylene oxide adduct is a compound in which an alkylene oxide is added to glycol lignin. For details thereof, for example, the disclosure of Patent Document 5 (JP 2021-147409 A) can be referenced.

[0020] Glycol lignin is a modified lignin obtained by solvolysis of lignocellulose in a glycol solvent in the presence of an acid catalyst (see, for example, JP 2017-197517 A, Takata et al., BioResources 11(2), 4446-4458 (2016), TTNge et al., ACS Sustainable Chem. Eng. 2018, 6, 7841-7848).

[0021] Lignocellulose, as used herein, is the main component of woody or herbaceous biomass and is composed of polysaccharide polymers such as cellulose and hemicellulose and the phenolic polymer lignin. Plants from which lignocellulose is derived include coniferous trees such as cedar, fir, cypress, and pine; broad-leaved trees such as eucalyptus, acacia, birch, beech, and oak; and herbaceous plants such as rice straw, grain, bagasse, bamboo, kenaf, and reed. Wood derived from coniferous trees is preferred from the viewpoint of obtaining a material with a uniform chemical structure. Lignocellulose can be used in various forms, such as woody or herbaceous pieces, woody or herbaceous chips, and woody or herbaceous powder, but powder form is preferred.

[0022] Specific methods for producing glycol lignin from lignocellulose include those disclosed in JP 2017-197517 A (see Figure 1), Takata et al., BioResources 11(2), 4446-4458 (2016) (see Figure 1), and TTNge et al., ACS Sustainable Chem. Eng. 2018, 6, 7841-7848 (see Experimental Section).

[0023] For example, cedar wood flour, which is lignocellulose, is subjected to a heat treatment (for example, at a temperature of 120 to 180°C, more preferably 130 to 140°C, for 0.5 to 4 hours, more preferably 1 to 3 hours, and even more preferably 1 to 1.5 hours) in the presence of an acid catalyst (for example, a predetermined catalytic amount of sulfuric acid; the catalytic amount is preferably 0.1 to 2.0 mass%, more preferably 0.2 to 1.0 mass%) using glycol (for example, polyethylene glycol 200) as a solvent.

[0024] The pulp residue fraction (main components: cellulose and hemicellulose) is then separated through a neutralization step (e.g., by adding a sodium hydroxide solution of a predetermined concentration, preferably adjusted to a pH of 10.5 or higher) to obtain a soluble fraction. The soluble fraction is then returned to an acidic state (e.g., by adding sulfuric acid of a predetermined concentration), and the resulting precipitate is separated, washed, and dried by conventional methods to obtain glycol lignin.

[0025] The glycol used as the digestion solvent for solvolysis may be, for example, one or more selected from the group consisting of ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, polyethylenepolypropylene glycol, glycerin, and polyglycerin, and at least one oxyethylene group in the polyethylene glycol may be replaced with an oxypropylene group, or at least one oxypropylene group in the polypropylene glycol may be replaced with an oxyethylene group.

[0026] When the cooking solvent used is a polymer such as polyethylene glycol, polypropylene glycol, polyethylene polypropylene glycol, or polyglycerin, the molecular weight of the polymer can be selected depending on the thermal fusibility of the resulting glycol lignin. For example, when polyethylene glycol is selected as the cooking solvent, polyethylene glycol having a weight-average molecular weight of 100 to 2,000, more preferably 200 to 600, can be used.

[0027] The amount of glycol used as the cooking solvent is preferably 2 to 10 parts by mass, more preferably 3 to 6 parts by mass, per part by mass of lignocellulose. For an example of the chemical structure of glycol lignin, see Figure 2 (Scheme 2) in TTNge et al., ACS Sustainable Chem. Eng. 2018, 6, 7841-7848. According to this, during acid-catalyzed solvolysis, the benzylic hydroxyl groups of lignin in lignocellulose are replaced by glycol chains (e.g., (poly)ethylene glycol chains) derived from the glycol solvent. It has also been noted that condensation (repolymerization) reactions and rearrangement reactions can also lead to the formation of new substructures.

[0028] That is, while lignin contains phenolic hydroxyl groups, benzylic hydroxyl groups, and other hydroxyl groups (see, for example, Table 5 in Yokoyama et al., Journal of Industrial Chemistry, Vol. 72, No. 1, pp. 353-358, 1969), glycol lignin has a basic structure in which the benzylic hydroxyl groups in the lignin basic skeleton are replaced by glycol chains.

[0029] The glycol chain referred to here may include not only a glycol chain derived directly from the glycol solvent, but also a glycol chain whose chain length is extended by polycondensation of two or more molecules of the glycol solvent. Also, the (poly)alkylene glycol chain refers to a glycol chain in which one terminal hydroxyl group of a glycol made of a polyalkylene glycol such as a monoalkylene glycol or a dialkylene glycol is ether-bonded to the lignin skeleton.

[0030] The presumed chemical structures of glycol lignin and glycol lignin alkylene oxide adducts are shown below. In glycol lignin, R in the chemical formula below is a hydroxyl group (-OH group (phenolic hydroxyl group)), and R' is a hydroxyl group at the benzylic position substituted with a glycol chain.

[0031] [ka]

[0032] The glycol lignin alkylene oxide adduct, an active ingredient of the resin modifier or UV absorber according to the present invention, is a modified lignin having a structure in which alkylene oxide is added primarily to the phenolic hydroxyl group (R) of the glycol lignin described above. That is, the glycol lignin alkylene oxide adduct according to the present invention is considered to have a glycol chain derived from the glycol lignin raw material substituted at the benzyl position (R') and also to have a glycol chain derived from alkylene oxide (i.e., a (poly)alkylene glycol chain) at the phenolic hydroxyl group (R). The glycol chain derived from the glycol lignin raw material substituted at the benzyl position may be further chain-extended with alkylene oxide. It is impossible, or extremely difficult, and therefore impractical, to unambiguously identify the structure of glycol lignin or its alkylene oxide adduct. Therefore, the chemical structures described above are merely speculations at this time, and their accuracy does not affect the technical scope of the present invention.

[0033] This glycol lignin alkylene oxide adduct is produced by reacting glycol lignin with alkylene oxide in the presence of an alkali. As will be described in detail later, the alkylene oxide can be, for example, an alkylene oxide having 2 to 18 carbon atoms, more preferably 2 to 8 carbon atoms. More specific examples include aliphatic epoxides such as ethylene oxide, propylene oxide (e.g., 1,2-epoxypropane), isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylethylene oxide, butadiene monoxide, dipentaneethylene oxide, and dihexaneethylene oxide; alicyclic epoxides such as trimethylene oxide, tetramethylene oxide, tetrahydrofuran, and octylene oxide; and aromatic epoxides such as styrene oxide and 1,1-diphenylethyleneoxide.

[0034] From the viewpoint of use as a resin modifier (for example, an ultraviolet absorber), the alkylene oxide is preferably ethylene oxide, propylene oxide, or butylene oxide (1,2-butylene oxide or 2,3-butylene oxide), and more preferably ethylene oxide.

[0035] The content of phenolic hydroxyl groups in the glycol lignin alkylene oxide adduct according to the present invention can be an index showing the degree of modification by alkylene oxide, but from the viewpoint of improving compatibility with solvents and resins, it is preferably less than 1.0 mmol, more preferably less than 0.5 mmol, and even more preferably less than 0.3 mmol per gram of glycol lignin alkylene oxide adduct. The content of phenolic hydroxyl groups can be measured by ionization differential spectroscopy.

[0036] The ratio of glycol chain content (% by mass) per unit lignin content (% by mass), which is an index showing the amount of glycol chains introduced into lignin, is preferably 0.4 to 5.0, more preferably 0.8 to 4.0, and even more preferably 1.5 to 3.0. A value within such a range is preferred because it provides excellent solubility in various solvents and resins.

[0037] Here, the lignin content (mass%) is the value (UV lignin content) obtained by the method of [lignin amount based on 280 nm UV absorption (UV lignin method)]. The glycol chain content (mass%) is the value obtained by subtracting the sum (mass%) of the lignin content (mass%) and the solvent content (mass%) from 100 mass%. The solvent content (mass%) refers to the content of a solvent that may be optionally contained in the glycol lignin alkylene oxide adduct of the present invention. This solvent content is, for example, the sum of the content (mass%) of a (poly)alkylene glycol solvent derived from the alkylene oxide used as a reaction reagent when adding alkylene oxide to glycol lignin, and the content (mass%) of a solvent used as a reaction solvent (e.g., dimethylacetamide). The (poly)alkylene glycol solvent content can be measured by the Weibull method. Here, the term "(poly)alkylene glycol" is used as a concept that encompasses polyalkylene glycols such as monoalkylene glycols and dialkylene glycols. The specific value of the solvent content is not particularly limited, but is preferably 1 to 65 mass%, more preferably 5 to 60 mass%, even more preferably 10 to 55 mass%, still more preferably 15 to 50 mass%, particularly preferably 20 to 45 mass%, and most preferably 25 to 40 mass%.

[0038] The molecular weight of the glycol lignin alkylene oxide adduct according to the present invention is, for example, in a range suitable for use as a resin modifier, a weight average molecular weight (Mw) of preferably 1,000 to 200,000, more preferably 3,000 to 100,000, and even more preferably 5,000 to 100,000. The weight average molecular weight (Mw) is a value determined by GPC (gel permeation chromatography) from a calibration curve using polyethylene oxide as a standard substance for preparing the calibration curve.

[0039] The glycol lignin alkylene oxide adduct according to the present invention can be produced by referring to the description in paragraphs "0027" to "0031" of Patent Document 5, for example.

[0040] (Uses of glycol lignin alkylene oxide adducts) The glycol lignin alkylene oxide adduct of the present invention is used, for example, as a resin modifier. In this specification, the term "resin modifier" refers to an agent used to improve some property of a resin by contacting the resin. The glycol lignin alkylene oxide adduct of the present invention is also useful, for example, as an ultraviolet absorber. This ultraviolet absorber may be a resin modifier or may be used without contacting the resin. However, one preferred embodiment of the present invention is an ultraviolet absorber as a resin modifier.

[0041] The glycol lignin alkylene oxide adduct of the present invention exhibits excellent solubility in various resins without the use of special dispersion methods. Therefore, various functionalities (e.g., ultraviolet absorption performance) can be imparted to resins at low cost and easily. Patent Document 5, which discloses glycol lignin alkylene oxide adducts, discloses that the adducts exhibit high solubility in ion-exchanged water and toluene. However, this fact does not mean that a person skilled in the art could have predicted that the glycol lignin alkylene oxide adduct of the present invention would exhibit excellent solubility in various resins. This is supported by, for example, paragraph "0010" of Japanese Patent Laid-Open Publication No. 2020-194171, which states that many conventional organic ultraviolet absorbers, such as benzotriazoles, benzophenones, triazines, cyanoacrylates, and salicylates (all of which are soluble in organic solvents), have limited compatibility with matrix resins, making it difficult to achieve uniform dissolution at high concentrations. In other words, the fact that the glycol lignin alkylene oxide adduct of the present invention exhibits excellent solubility in various resins without the use of special dispersion means was discovered only after the present inventors conducted actual experiments, and it can be said that this finding could not have been reasonably predicted by a person skilled in the art from the prior art.

[0042] When the glycol lignin alkylene oxide adduct of the present invention is used as an ultraviolet absorber, the critical wavelength of the ultraviolet absorber is preferably 360 nm or more, more preferably 361 nm or more, even more preferably 362 nm or more, particularly preferably 363 nm or more, and most preferably 364 nm or more. Here, the "critical wavelength" refers to the wavelength at which, in an ultraviolet absorption spectrum measured using a spectrophotometer, the area of ​​the absorption spectrum from that wavelength to the lower wavelength side accounts for 90% of the entire absorption spectrum. The larger the critical wavelength, the higher the proportion of ultraviolet light in the UV-A region that is absorbed. Ultraviolet light is generally known to be one of the causes of resin degradation, and ultraviolet light in the UV-A region (wavelengths 320 to 400 nm) is particularly involved in resin degradation. Therefore, a high absorption of ultraviolet light in the UV-A region (i.e., a large critical wavelength) means that the ultraviolet absorber is extremely effective in preventing resin degradation.

[0043] In the present invention, when the glycol lignin alkylene oxide adduct is used as a resin modifier or an ultraviolet absorber, it may be mixed with other resin modifiers or additives having antistatic properties, water resistance, weather resistance, etc.

[0044] [Resin composition] According to yet another aspect of the present invention, there is provided a resin composition comprising the resin modifier or UV absorber according to the above aspect and a resin. The resin is preferably a thermoplastic resin and / or a thermosetting resin, more preferably a thermoplastic resin. Each resin is described below. In this specification, the term "resin" includes monomers, oligomers, prepolymers, and polymers.

[0045] (thermoplastic resin) The thermoplastic resin used in the present invention is not particularly limited, but examples thereof include (meth)acrylic resins, styrene resins, olefin resins (including cyclic olefin resins), polyester resins, polycarbonate resins, polyamide resins, polyphenylene ether resins, polyphenylene sulfide resins, halogen-containing resins (such as polyvinyl chloride, polyvinylidene chloride, and fluororesins), polysulfone resins (such as polyethersulfone and polysulfone), cellulose derivatives (such as cellulose esters, cellulose carbamates, and cellulose ethers), silicone resins (such as polydimethylsiloxane and polymethylphenylsiloxane), polyvinyl ester resins such as polyvinyl acetate, polyvinyl alcohol resins and their derivative resins, rubbers or elastomers (such as diene rubbers such as polybutadiene and polyisoprene, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, acrylic rubbers, urethane rubbers, and silicone rubbers). The above thermoplastic resins can be used alone or in combination of two or more.

[0046] Specific examples of the (meth)acrylic resin include monofunctional (meth)acrylic monomers and homopolymers or copolymers thereof, polyfunctional (meth)acrylic monomers and homopolymers or copolymers thereof, and copolymers of monofunctional or polyfunctional (meth)acrylic monomers and other monomers.

[0047] Specific examples of monofunctional (meth)acrylic monomers include (meth)acrylic acid, (meth)acrylic acid esters having 1 to 10 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and (meth)acrylonitrile.

[0048] Specific examples of polyfunctional (meth)acrylic monomers include polyethylene glycol diacrylate, decanediol diacrylate, nonanediol diacrylate, hexanediol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0049] Specific examples of the homopolymer or copolymer of the (meth)acrylic monomer include poly(meth)acrylic acid ester, acrylic acid ester-methacrylic acid ester copolymer, polyacrylonitrile, etc. Specific examples of the copolymer of the (meth)acrylic monomer with other monomer include (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), methyl methacrylate-butadiene-styrene copolymer (MBS resin), etc.

[0050] Specific 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).

[0051] Olefin resins include homopolymers of olefin monomers, copolymers of olefin monomers, and copolymers of olefin monomers with other copolymerizable monomers. Specific examples of olefin monomers include linear olefins (e.g., α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene), and cyclic olefins (e.g., cycloalkenes having 4 to 10 carbon atoms, such as cyclopentene; cycloalkadienes having 4 to 10 carbon atoms, such as cyclopentene; bicycloalkenes or bicycloalkadienes having 7 to 20 carbon atoms, such as norbornene and norbornadiene; and tricycloalkenes or tricycloalkadienes having 10 to 25 carbon atoms, such as dihydrodicyclopentadiene and dicyclopentadiene). These olefin monomers can be used alone or in combination. Of the above olefin monomers, chain olefins such as α-olefins having 2 to 4 carbon atoms, such as ethylene, propylene, and 1-butene, are preferred.

[0052] Specific examples of other copolymerizable monomers copolymerizable with the olefin monomer include fatty acid vinyl esters such as vinyl acetate and vinyl propionate; (meth)acrylic monomers such as (meth)acrylic acid, alkyl (meth)acrylates, and glycidyl (meth)acrylate; unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, fumaric acid, and maleic anhydride; vinyl esters of carboxylic acids (e.g., vinyl acetate and vinyl propionate); cyclic olefins such as norbornene and cyclopentadiene; and dienes such as butadiene and isoprene. These copolymerizable monomers can be used alone or in combination of two or more.

[0053] More specific examples of the olefin resin include (co)polymers of linear olefins (particularly α-olefins having 2 to 4 carbon atoms), such as polyethylene (low-density polyethylene, medium-density polyethylene, high-density polyethylene, or linear low-density polyethylene), polypropylene (homopolypropylene, block polypropylene, random polypropylene, etc.), ethylene-propylene copolymers, and ethylene-propylene-butene terpolymers. Specific examples of copolymers of olefin monomers with other copolymerizable monomers include copolymers of linear olefins (particularly 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 linear olefins and (meth)acrylic monomers [copolymers of linear olefins (particularly 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.); copolymers of linear olefins (particularly α-olefins having 2 to 4 carbon atoms) with alkyl ( copolymers of chain olefins (particularly α-olefins having 2 to 4 carbon atoms) and dienes (for example, ethylene-butadiene copolymers); modified polyolefins such as epoxy-modified polyolefins (for example, ethylene-glycidyl (meth)acrylate copolymers), carboxy-modified polyolefins (for example, ethylene-maleic anhydride copolymers), and epoxy- and carboxy-modified polyolefins (for example, ethylene-maleic anhydride-glycidyl (meth)acrylate copolymers); olefin elastomers (for example, ethylene-propylene rubbers).

[0054] 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 derivatives thereof and diols or derivatives thereof, (b) hydroxycarboxylic acids or derivatives thereof, and (c) lactones.

[0055] Examples of the dicarboxylic acid or a derivative thereof 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'-diphenyletherdicarboxylic acid, 5-tetrabutylphosphoniumisophthalate, and 5-sodiumsulfoisophthalic acid; aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, and dimer acid; and 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Examples of the diol or derivative include aliphatic glycols having 2 to 20 carbon atoms, such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, and dimer diol; long-chain glycols having a molecular weight of 200 to 100,000, such as polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol; aromatic dioxy compounds, such as 4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, and bisphenol F; and derivatives thereof. Examples of the hydroxycarboxylic acid 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 lactone include caprolactone, valerolactone, propiolactone, undecalactone, 1,5-oxepan-2-one, etc. The polyester resin also includes polyester elastomers.

[0056] Specific examples of polycarbonate resins include thermoplastic resins obtained by reacting a divalent or higher phenol compound with a carbonic acid diester compound such as phosgene or diphenyl carbonate.

[0057] Examples of the divalent or higher phenolic 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, 1,2-bis(4-hydroxyphenyl)ethane, 1,3-bis(4-hydroxyphenyl)ethane, 1,4-bis(4-hydroxyphenyl)ethane, 1,5-bis(4-hydroxyphenyl)ethane, 1,6-bis(4-hydroxyphenyl)ethane, 1,7-bis(4-hydroxyphenyl)ethane, 1,8-bis(4-hydroxyphenyl)ethane, 1,9-bis(4-hydroxyphenyl) ...5-bis(4-hydroxyphenyl)ethane, 1,5-bis(4-hydroxyphenyl)ethane, 1,5-bis(4-hydroxyphenyl)ethane, 1,5-bis(4-hydroxyphenyl)ethane, 1,5- -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)propane, 2,2-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 Dihydroxydiarylalkanes such as 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(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,Dihydroxydiarylcycloalkanes such as 1-bis(4-hydroxyphenyl)cyclodecane, 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, 4,4'-dihydroxybenzophenone, 3,3',5,5'-tetramethyl-4,4'-dihydrobenzophenone, Examples of suitable dihydric phenol compounds include dihydroxydiaryl ketones such as hydroxybenzophenone, dihydroxydiaryl sulfides such as bis(4-hydroxyphenyl) sulfide, bis(3-methyl-4-hydroxyphenyl) sulfide, and bis(3,5-dimethyl-4-hydroxyphenyl) sulfide, dihydroxydiaryl sulfoxides 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 above dihydric phenol compounds, dihydroxybenzenes such as hydroquinone, resorcinol, and methylhydroquinone, and dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene can also be used as dihydric phenol compounds.

[0058] These divalent or higher phenolic compounds may be used alone or in combination of two or more. Furthermore, linear aliphatic dicarboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid may also be used as copolymerization components.

[0059] Specific examples of polyamide resins include 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-cyclohexanamide; aromatic polyamides such as polyamide 6T, polyamide 9T, and polyamide MXD; and copolyamides formed from at least two different polyamide-forming components among these polyamides. The polyamide resins also include polyamide elastomers.

[0060] Specific examples of polyphenylene ether resins include 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 based on these homopolymers; and modified graft copolymers in which a styrene polymer is grafted onto a polyphenylene ether homopolymer or its copolymer.

[0061] Specific examples of polyphenylene sulfide resins include polyphenylene sulfide, polyphenylene sulfide ketone, polybiphenylene sulfide, and polyphenylene sulfide sulfone.

[0062] The thermoplastic resin may be a synthetic product or a commercially available product. In the case of a synthetic product, a resin (resin polymer) may be synthesized by a known method such as high-pressure radical polymerization, medium-low pressure polymerization, solution polymerization, slurry polymerization, bulk polymerization, emulsion polymerization, or gas phase polymerization, and may be used in the resin composition.

[0063] When the thermoplastic resin is a copolymer, the copolymer may be in the form of a block copolymer, a random copolymer, a graft copolymer, or an alternating copolymer.

[0064] The thermoplastic resin preferably includes at least one selected from the group consisting of a (meth)acrylic resin, a styrene resin, an olefin resin, and a polyester resin, and more preferably includes a (meth)acrylic resin.

[0065] (thermosetting resin) The thermosetting resin used in the present invention is not particularly limited, and examples thereof include phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, polyurethane resin, polyimide resin, diallyl phthalate resin, etc. The thermosetting resin may be a synthetic product or a commercially available product.

[0066] Among the various resins mentioned above, one or more resins selected from the group consisting of (meth)acrylic resins, styrene resins, olefin resins, polyester resins, melamine resins, epoxy resins, silicone resins and polyurethane resins are preferably used.

[0067] In the resin composition according to the present invention, the content of the resin modifier or UV absorber comprising the glycol lignin alkylene oxide adduct is preferably 0.1 to 400 parts by mass, more preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.1 part by mass or more but less than 5 parts by mass, relative to 100 parts by mass of the resin. By keeping the content within this range, an excellent modifying effect on the resin (for example, improved UV absorption performance) can be achieved.

[0068] The resin composition of the present invention may contain other additives, such as polymerization initiators, antioxidants, fillers, lubricants, dyes, organic pigments, inorganic pigments, plasticizers, processing aids, light stabilizers, foaming agents, waxes, crystal nucleating agents, mold release agents, hydrolysis inhibitors, antiblocking agents, antistatic agents, radical scavengers, antifogging agents, antifogging agents, ion trapping agents, flame retardants, flame retardant aids, and surfactants, as long as the additives do not impair the objectives of the present invention. For example, when a resin composition (coating composition) containing a resin monomer is applied to a substrate and cured, the resin composition preferably contains a polymerization initiator to promote curing of the applied resin composition (coating composition). Examples of polymerization initiators include thermal polymerization initiators and photopolymerization initiators.

[0069] Examples of the thermal polymerization initiator include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methylacetoacetate peroxide, acetylacetate peroxide, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)-cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, 1,1-bis(t -butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 1,1-bis(t-butylperoxy)butane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α,α'-bis(t-butylperoxy)diisopropyl Pyrbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoylbenzoyl peroxide, benzoyl peroxide, di-n-propyl Dipropyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-s-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3-Tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate , t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisobutyrate, t-butylperoxymalate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butylperoxyacetate, t-butylperoxy-m-tolube organic peroxide initiators such as benzoate, t-butyl peroxybenzoate, bis(t-butylperoxy)isophthalate, 2,5-dimethyl-2,5-bis(m-toluylperoxy)hexane, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 2,3-dimethyl-2,3-diphenylbutane; 2-Phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl)azo]formamide, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis(2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-Azobis[N-(4-chlorophenyl)-2-methylpropionamidine]dihydridochloride, 2,2'-Azobis[N-(4-hydrophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'-Azobis[2-methyl-N-(phenylmethyl)propionamidine]dihydrochloride, 2,2'-Azobis[2-methyl-N-(2-propenyl)propionamidine]dihydrochloride, 2,2'-Azobis[N-(2-hydroxyethyl)-2-methylpropionamidine dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(5- hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane] dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl) )ethyl]propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2-methylpropionamide), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), dimethyl-2,2-azobis(2-methylpropionate), 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis[2-(hydroxymethyl)propionitrile], and the like. These thermal polymerization initiators may be used alone or in combination of two or more.

[0070] Examples of photopolymerization initiators include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, Acetophenones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer; benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'- Benzophenones such as tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethanaminium bromide, and (4-benzoylbenzyl)trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-(3-di Examples of the photopolymerization initiator include thioxanthones such as methylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride; acylphosphonoxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; oxime esters; cationic photopolymerization initiators; and intramolecular hydrogen abstraction photopolymerization initiators. These photopolymerization initiators may be used alone or in combination of two or more.

[0071] The form of the resin composition according to the present invention is not particularly limited and may be, for example, a solid, emulsion, translucent solution, transparent solution, or the like. However, from the viewpoint of reducing environmental impact, an emulsion is preferred. When the resin composition is in the form of an emulsion or solution, the solvent used for the resin composition may be water or an organic solvent. When the resin composition is in the form of an emulsion, the solvent is typically water. On the other hand, when the resin composition is in the form of a solution, the solvent is typically an organic solvent. Examples of organic solvents include aliphatic hydrocarbons such as hexane; alcohols such as methanol, ethanol, isopropanol, methoxyethanol, ethoxyethanol, methoxycarbitol, and benzyl alcohol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenated solvents such as methylene chloride and chloroform; ethers such as diethyl ether and propylene glycol monomethyl ether; aromatics such as toluene and xylene; esters such as n-butyl acetate and ethyl acetate; methylpyrrolidone, dimethyl sulfoxide, and the like. However, from the viewpoint of resin solubility, polar solvents such as alcohols, ketones, and esters are preferred.

[0072] The resin composition according to the present invention can be produced by mixing the resin modifier or UV absorber comprising the glycol lignin alkylene oxide adduct, the resin, and, if necessary, the above-mentioned additives, by stirring or melt-kneading, etc. The melt-kneading method is not particularly limited, and can be, for example, a method using a single-screw extruder, a twin-screw extruder, a heat roll, a Banbury mixer, a Henschel mixer, a tumbler mixer, or various kneaders.

[0073] [Coating composition] The resin composition according to the present invention can be suitably used as a coating composition. Specifically, a coating film can be obtained by applying a coating composition comprising the resin composition according to the present invention to the surface of a substrate and drying or curing the coating composition. The resulting coating film is endowed with various properties (e.g., ultraviolet absorption properties) due to the presence of the resin modifier or ultraviolet absorber contained in the coating composition.

[0074] The coating composition preferably further contains a solvent in addition to the various components described above as constituents of the resin composition of the present invention. Examples of the solvent used in the coating composition include water or an organic solvent. Examples of organic solvents include aliphatic hydrocarbons such as hexane; alcohols such as methanol, ethanol, isopropanol, methoxyethanol, ethoxyethanol, methoxycarbitol, and benzyl alcohol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenated solvents such as methylene chloride and chloroform; ethers such as diethyl ether and propylene glycol monomethyl ether; aromatic solvents such as toluene and xylene; esters such as n-butyl acetate and ethyl acetate; and methylpyrrolidone and dimethyl sulfoxide. From the viewpoint of resin solubility, polar solvents such as alcohols, ketones, and esters are preferred.

[0075] The substrate on which a coating film is formed by applying a coating composition is not particularly limited, and examples thereof include films, plastics, glass, fibers, sheets, tapes, etc. Furthermore, as a method for applying the coating composition to form a coating film, known coating methods can be appropriately used, such as spin coating, roll coating, gravure coating, reverse coating, spray coating, air knife coating, curtain coating, roll brushing, impregnation, and coating with a bar coater.

[0076] Drying conditions can be adjusted appropriately depending on the heat resistance of the substrate, the boiling point of the solvent contained in the coating composition, etc. The drying temperature is not particularly limited, but is, for example, 50 to 180°C, 80 to 150°C, or 110 to 130°C. The drying time is also not particularly limited, but is, for example, 0.5 to 120 minutes, 1 to 60 minutes, or 1 to 10 minutes. The drying atmosphere is also not particularly limited, but is, for example, air, an inert gas (e.g., nitrogen), or vacuum.

[0077] The curing method may be either photocuring or thermal curing, but photocuring is preferred from the viewpoint of short-term curing and reduced damage to the substrate. In the case of photocuring, it is preferred to use a light source that generates ultraviolet light, and a mercury lamp (e.g., a high-pressure mercury lamp or a low-pressure mercury lamp), a metal halide lamp, or the like can be used. The irradiation conditions of the ultraviolet light are not particularly limited, but the cumulative light dose is preferably 100 to 1000 mJ / cm. 2 is preferred, and 200 to 500 mJ / cm 2 is more preferable. In the case of thermal curing, it may be carried out under the same conditions as the drying described above. That is, drying and thermal curing may proceed simultaneously. Furthermore, when forming a coating film, both drying and curing may be carried out at different times. For example, photocuring may be carried out after removing the solvent contained in the coating composition by pre-drying.

[0078] The thickness of the coating film formed is preferably 1 to 50 μm, more preferably 5 to 20 μm, and even more preferably 10 to 15 μm, as a dry film thickness. Within such a range, a coating film having various properties can be formed on the surface of a substrate while maintaining good surface hardness before and after coating film formation.

[0079] The content of the glycol lignin alkylene oxide adduct in the coating film thus formed is preferably 0.1 to 800 mass% and more preferably 0.5 to 400 mass% relative to 100 mass% of the resin. Within this range, various properties can be imparted to the surface of the substrate without impairing the properties of the substrate. This content is substantially equivalent to the ratio of the mass of the glycol lignin alkylene oxide adduct to the total mass of the resin (e.g., resin monomer).

[0080] Another use of the resin modifier or UV absorber according to the present invention is, for example, mixing it with raw materials for producing a molded article made from the resin composition. That is, according to yet another aspect of the present invention, a molded article made from the above-described resin composition is provided. The shape (form) of the molded article is not particularly limited, and examples thereof include films, plastics, glass, fibers, sheets, and tapes. Other uses of the resin composition according to the present invention include, for example, paints, adhesives, pressure-sensitive adhesives, fiber auxiliaries, building material films, protective films such as hard coats, housings for home appliances, papermaking applications (surface coating agents, etc.), and civil engineering applications (concrete admixtures, etc.). A molded article made from the resin composition according to the present invention may be used for these applications. Molded articles can be produced by known methods such as injection molding, extrusion molding, transfer molding, inflation molding, and compression molding. These methods can be appropriately selected depending on the shape of the molded article to be obtained. [Example]

[0081] 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, operations were performed at 25°C. Furthermore, unless otherwise specified, "%" and "parts" mean "% by mass" and "parts by mass," respectively.

[0082] [Synthesis Example 1: Synthesis of glycol lignin] Lignin modified with polyethylene glycol having an average molecular weight of 400 (hereinafter also simply referred to as "glycol lignin") was synthesized by the following method.

[0083] Specifically, 230 parts by mass of commercially available polyethylene glycol (PEG400) with an average molecular weight of 400 and 0.68 parts by mass of sulfuric acid (0.3 parts by mass per 100 parts by mass of PEG400) as an acid catalyst were placed in a reaction vessel and stirred. Next, 46 parts by mass of bone-dried cedar wood flour was added to the reaction vessel, and the temperature was raised to 140°C under normal pressure, and the mixture was reacted for 90 minutes with stirring.

[0084] The reaction vessel was then cooled, and after confirming that the temperature had dropped to 40°C or less, 280 parts by mass of sodium hydroxide (0.2 mol / L) was added and stirred for 30 minutes. The resulting solid component (pulp) was then removed using a filter press, and the solution component was recovered.

[0085] Then, sulfuric acid was added to the obtained solution components to adjust the pH to 1.8. This resulted in a suspension of glycol lignin. The glycol lignin was then recovered by centrifugation. Subsequently, the glycol lignin was suspended in water and washed with stirring, then recovered by centrifugation and dried. Note that the glycol lignin thus obtained was substantially free of residual solvent derived from polyethylene glycol and the like used in the reaction.

[0086] [Synthesis Example 2: Synthesis of glycol lignin ethylene oxide adduct (1)] An autoclave equipped with a stirrer and temperature controller was charged with 30 parts by mass of the glycol lignin obtained in Synthesis Example 1 described above, 30 parts by mass of dimethylacetamide, and 0.3 parts by mass of sodium hydroxide. Nitrogen purge (0.1 MPa ⇔ 0.5 MPa) was repeated five times to remove air from the vessel. After nitrogen purge, the autoclave was heated to 105°C for 120 minutes to dehydrate the glycol lignin, and the glycol lignin was treated with sodium hydroxide. Subsequently, 30 parts by mass of ethylene oxide was intermittently introduced into the autoclave over 6.5 hours at 130-140°C and reacted. The reaction was then continued for 13 hours at a reaction temperature of 130-140°C. After completion of the reaction, simple vacuum distillation (5 kPa) was performed at 130-140°C. After the simple vacuum distillation, the temperature was lowered to room temperature, yielding 89 parts by mass of the crude glycol lignin ethylene oxide adduct (1) (yield: 99.8%).

[0087] [Synthesis Example 3: Preparation of glycol lignin ethylene oxide adducts (2) to (4)] Glycol lignin ethylene oxide adducts (2) to (4) were synthesized in the same manner as in Synthesis Example 2 above, except that the GL / EO mass ratio, which is the ratio of the mass of glycol lignin (GL) as the raw material to the mass of ethylene oxide (EO) to be added, was changed to 1 / 2, 1 / 3, and 1 / 4, respectively.

[0088] [Synthesis Example 4: Preparation of soda lignin ethylene oxide adduct] A soda lignin ethylene oxide adduct was synthesized in the same manner as in Synthesis Example 2, except that the "30 parts by mass of glycol lignin obtained in Synthesis Example 1" in Synthesis Example 2 was replaced with "30 parts by mass of soda lignin." The soda lignin is lignin prepared by soda-anthraquinone cooking of cedar.

[0089] The following values ​​are shown in Table 1 for the glycol lignin, glycol lignin alkylene oxide adducts (1) to (4) and soda lignin ethylene oxide adduct thus obtained.

[0090] (molar amount of phenolic hydroxyl groups [mmol / g]) The molar amount of phenolic hydroxyl groups [mmol] per 1 g of adduct (including solvents ((poly)ethylene glycol and dimethylacetamide)). Measurement was performed by ionization differential spectroscopy. The value in parentheses is the molar amount of phenolic hydroxyl groups when converted to per 1 g of adduct after removing the solvent.

[0091] (UV lignin rate L [mass%]) This is the mass percentage of the lignin skeleton (excluding glycol chains) in the adduct (including the solvent). Measurement was performed by the UV lignin method (a method for measuring the amount of lignin based on UV absorption at 280 nm).

[0092] (Glycol chain content G [mass%]) This is the value obtained by subtracting the total mass percentage of the UV lignin rate L [mass %] and the solvent content [mass %] from 100%.

[0093] (GL·EO adduct content L+G [mass%]) This is the mass percentage of glycol lignin ethylene oxide adduct (GL·EO adduct) in the adduct (including solvent). Specifically, it is the value obtained by adding the glycol chain content G [mass%] and the UV lignin content L [mass%].

[0094] (G / L) This is the value obtained by dividing the glycol chain content G [mass%] by the UV lignin content L [mass%].

[0095] (Dimethylacetamide solvent content A [mass%]) This is the mass percentage of dimethylacetamide derived from the reaction solvent in the adduct (including the solvent). Specifically, it was calculated from the non-volatile content after heating at 180°C for 1 hour.

[0096] ((Poly)ethylene glycol solvent content E [mass%]) This is the mass percentage of the (poly)ethylene glycol solvent derived from ethylene oxide in the adduct (including the solvent). Measurement was performed by the Weibull method.

[0097] (Solvent content A+E [mass%]) This is the value obtained by adding the dimethylacetamide solvent content A [mass %] and the (poly)ethylene glycol solvent content E [mass %].

[0098] [Table 1]

[0099] [Measurement of critical wavelength as an ultraviolet absorber] The critical wavelengths of the glycol lignins and glycol lignin ethylene oxide adducts (1) to (4) synthesized in the above synthesis examples as ultraviolet absorbers were measured by the following method. The critical wavelengths were also measured in the same manner for 2-dihydroxy-4-methoxybenzophenone, 2-(2-hydroxy-5-methylphenyl)-benzotriazole, and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate, which are ultraviolet absorbers conventionally used in resin compositions. The chemical structures of these ultraviolet absorbers are as follows:

[0100] [ka]

[0101] (Preparation of measurement sample) (1) Preparation of 2-hydroxy-4-methoxybenzophenone solution A 0.25% by mass benzophenone solution was obtained by adding 0.25 parts by mass of 2-hydroxy-4-methoxybenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 99.75 parts by mass of methanol to a beaker and mixing them. Next, 1 part by mass of the 0.25% by mass benzophenone solution and 99 parts by mass of methanol were added to the beaker and mixed to obtain a 0.0025% by mass 2-hydroxy-4-methoxybenzophenone solution.

[0102] (2) Preparation of 2-(2-hydroxy-5-methylphenyl)benzotriazole solution 2-(2-hydroxy-5-methylphenyl)benzotriazole (Tokyo Chemical Industry Co., Ltd.) was diluted in the same manner as in (1) above to obtain a 0.0025 mass % 2-(2-hydroxy-5-methylphenyl)benzotriazole solution.

[0103] (3) Preparation of 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid aqueous solution 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was diluted in the same manner as in (1) above, except that ion-exchanged water was used as the solvent, to obtain a 0.0023 mass% aqueous solution of 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid.

[0104] (4) Preparation of glycol lignin solution The glycol lignin synthesized in the above-mentioned Synthesis Example 1 was diluted in the same manner as in (1) above to obtain a 0.0025 mass % glycol lignin solution.

[0105] (5) Preparation of glycol lignin ethylene oxide adduct aqueous solution For each of the glycol lignin ethylene oxide adducts (1) to (4) synthesized in Synthesis Examples 2 and 3 described above, 0.1 parts by mass of the adduct and 99.9 parts by mass of ion-exchanged water were added to a beaker and mixed to obtain a 0.1% by mass aqueous solution of glycol lignin ethylene oxide adduct. Next, 10 parts by mass of the 0.1% by mass aqueous solution of glycol lignin ethylene oxide adduct and 90 parts by mass of ion-exchanged water were added to a beaker and mixed to obtain a 0.01% by mass aqueous solution of glycol lignin EO adduct. The active ingredient concentrations in the solutions differ from those of (1) to (4) above because the absorbance of the measurement sample was adjusted to 1 to 2 abs.

[0106] (Measurement of critical wavelength) Each measurement sample prepared above was placed in a quartz cell to a height of approximately 70%. Next, absorbance was measured in the wavelength range of 200 to 400 nm using a UV-Visible Spectrophotometer V-550 (manufactured by JASCO Corporation) to obtain an absorption spectrum. The obtained absorption spectrum was divided into two so that the area of ​​the absorbance obtained was 9:1 (short wavelength side: long wavelength side), and the wavelength corresponding to the dividing boundary was defined as the critical wavelength. The results are shown in Table 2 below.

[0107] [Table 2]

[0108] The results shown in Table 2 indicate that the glycol lignin alkylene oxide adduct of the present invention exhibits a larger critical wavelength than various compounds conventionally known as ultraviolet absorbents. This suggests that when the glycol lignin alkylene oxide adduct of the present invention is added to, for example, a resin composition as an ultraviolet absorber, it can effectively prevent deterioration of the resin contained in the resin composition by absorbing ultraviolet rays in the UV-A region.

[0109] [Evaluation of solubility in resin] The solubility in resin of the glycol lignin synthesized in Synthesis Example 1, the glycol lignin ethylene oxide adduct (4) synthesized in Synthesis Example 3, and the soda lignin ethylene oxide adduct synthesized in Synthesis Example 4 was evaluated by the following method.

[0110] (Polymer synthesis (emulsion polymerization)) A monomer mixture was prepared by adding 30 parts by weight of cyclohexyl methacrylate (Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent), 37 parts by weight of methyl methacrylate (Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent), 31 parts by weight of 2-ethylhexyl acrylate (Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent), and 2 parts by weight of acrylic acid (Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) to an Erlenmeyer flask. Meanwhile, a separate Erlenmeyer flask was charged with 59.9 parts by weight of deionized water and 2.5 parts by weight of Newcol® 707-SF (Nippon Nyukazai Co., Ltd., polyoxyethylene polycyclic phenyl ether sulfate ester ammonium salt, pure content 30% by weight) as an emulsifier, and mixing was performed with a stirrer. The monomer mixture prepared above was added to this Erlenmeyer flask in five separate portions. After thorough mixing, 2.0 parts by weight of a 10% by weight aqueous solution of ammonium persulfate (Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) was added to prepare a pre-emulsion. A four-neck flask equipped with a stirrer, thermometer, nitrogen inlet, reflux condenser, and dropping funnel was charged with 50 parts by weight of deionized water and 7.9 parts by weight (5% by weight of the pre-emulsion prepared above). The mixture was heated to 80°C and maintained at 80°C for 30 minutes to allow for pre-polymerization. After the pre-polymerization, the remaining pre-emulsion was added dropwise over 3 hours to allow for polymerization. The mixture was then aged at 80°C for 1 hour and cooled to room temperature. The pH was then adjusted to 8.0 using 25% by weight aqueous ammonia solution to obtain a resin emulsion with a solids content of 50.7% by weight (composition: cyclohexyl methacrylate / methyl methacrylate / 2-ethylhexyl acrylate / acrylic acid = 30 / 37 / 31 / 2 (mass ratio)).

[0111] (Polymer synthesis (solution polymerization)) A four-neck flask equipped with a stirrer, thermometer, nitrogen inlet, reflux condenser, and dropping funnel was charged with 50 parts by mass of butyl acrylate (Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent), 50 parts by mass of methyl methacrylate (Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent), and 233 parts by mass of propylene glycol monomethyl ether (MFG) (Nippon Nyukazai Co., Ltd.) and mixed. The mixture was then heated to 40°C, and 1 part by mass of AIBN (Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent azobisisobutyronitrile) was added. The mixture was then heated to 80°C and stirred for 10 hours.

[0112] After the reaction, the mixture was cooled to room temperature, and 30 parts by mass of MFG was added to adjust the purity to 30%, to obtain a solution resin (composition: butyl acrylate / methyl methacrylate=50 / 50 (mass ratio)).

[0113] (Solubility test for emulsion polymers) (1) Solubility of glycol lignin Ten parts by mass of the emulsion-polymerized polymer prepared above was added to a screw vial. Next, 0.08 parts by mass of glycol lignin was added, and the vial was capped and thoroughly mixed by shaking up and down to obtain a glycol lignin emulsion-polymerized polymer solution. Visual inspection of the resulting solution revealed that it was black and cloudy, with precipitates present. This suggested that glycol lignin did not exhibit sufficient solubility in the emulsion-polymerized polymer. A photograph showing this solubility is shown in Figure 1 ("GL" in Figure 1).

[0114] (2) Solubility of glycol lignin ethylene oxide adduct The glycol lignin ethylene oxide adduct (4) synthesized in Synthesis Example 3 above was mixed with an emulsion-polymerized polymer in the same manner as in (1) above to obtain a glycol lignin ethylene oxide adduct emulsion-polymerized polymer solution. Visual inspection of the resulting solution revealed a uniform milky white color with no visible precipitate. This suggests that the glycol lignin ethylene oxide adduct exhibits excellent solubility in the emulsion-polymerized polymer. A photograph showing this solubility is shown in Figure 1 ("GL·EO Adduct" in Figure 1).

[0115] (3) Solubility of soda lignin ethylene oxide adduct The soda lignin ethylene oxide adduct synthesized in Synthesis Example 4 above was mixed with an emulsion-polymerized polymer in the same manner as in (1) above to obtain a soda lignin ethylene oxide adduct emulsion-polymerized polymer solution. Visual inspection of the resulting solution confirmed the presence of suspended matter and precipitates, although the solution was not black and cloudy. This suggests that the soda lignin ethylene oxide adduct does not exhibit sufficient solubility in the emulsion-polymerized polymer. A photograph showing this solubility is shown in Figure 1 ("SL" in Figure 1).

[0116] (Solubility test for solution polymer) (1) Solubility of glycol lignin Ten parts by mass of the solution-polymerized polymer prepared above was added to a screw vial. Next, 0.04 parts by mass of glycol lignin was added, and the vial was capped and shaken up and down to thoroughly mix, yielding a glycol lignin solution-polymerized polymer solution. Visual inspection of the resulting solution revealed that it was brown and cloudy, with suspended matter present. This suggested that glycol lignin did not exhibit sufficient solubility in the solution-polymerized polymer. A photograph showing this solubility is shown in Figure 2 ("GL" in Figure 2).

[0117] (2) Solubility of glycol lignin ethylene oxide adduct The glycol lignin ethylene oxide adduct (4) synthesized in Synthesis Example 3 above was mixed with a solution-polymerized polymer in the same manner as in (1) above to obtain a glycol lignin ethylene oxide adduct solution-polymerized polymer solution. Visual inspection of the resulting solution revealed that it was a uniform, transparent, light brown solution with no suspended matter. This indicated that the glycol lignin ethylene oxide adduct exhibited excellent solubility in the solution-polymerized polymer. A photograph showing this solubility is shown in Figure 2 ("GL·EO Adduct" in Figure 2).

[0118] (3) Solubility of soda lignin ethylene oxide adduct The soda lignin ethylene oxide adduct synthesized in Synthesis Example 4 above was mixed with a solution-polymerized polymer in the same manner as in (1) above to obtain a soda lignin ethylene oxide adduct solution-polymerized polymer solution. Visual inspection of the resulting solution confirmed the presence of a precipitate, although it was not brown and cloudy. This suggests that the soda lignin ethylene oxide adduct does not exhibit sufficient solubility in the solution-polymerized polymer. A photograph showing this solubility is shown in Figure 2 ("SL" in Figure 2).

[0119] From the above, it can be seen that the glycol lignin alkylene oxide adduct of the present invention is useful as a resin modifier and an ultraviolet absorber that exhibits excellent solubility in resins without the use of special dispersion means.

[0120] [Measurement of absorbance in resin composition state] (Preparation of measurement sample) (1) Solution polymerization of 2-hydroxy-4-methoxybenzophenone Preparation of polymer solution 9.9 parts by mass of the solution-polymerized polymer prepared above was added to a screw vial. Next, 0.1 parts by mass of 2-hydroxy-4-methoxybenzophenone was added and thoroughly mixed to obtain a 1% by mass 2-hydroxy-4-methoxybenzophenone solution-polymerized polymer solution. Then, 9.9 parts by mass of the same solution-polymerized polymer as above was added to another screw vial, and 0.1 parts by mass of the 1% by mass 2-hydroxy-4-methoxybenzophenone solution-polymerized polymer solution prepared above was added and thoroughly mixed to obtain a 0.01% by mass 2-hydroxy-4-methoxybenzophenone solution-polymerized polymer solution.

[0121] (2) Solution polymerization of glycol lignin ethylene oxide adduct Preparation of polymer solution 99.88 parts by mass of the solution-polymerized polymer prepared above was added to a screw vial, followed by 0.12 parts by mass of the glycol lignin ethylene oxide adduct (4) synthesized in Synthesis Example 3 above, and mixing thoroughly to obtain a 0.12% by mass glycol lignin ethylene oxide adduct solution-polymerized polymer solution.

[0122] (Absorbance measurement) The 0.01% by mass 2-hydroxy-4-methoxybenzophenone solution-polymerized polymer solution prepared in (1) above and the 0.12% by mass glycol lignin ethylene oxide adduct solution-polymerized polymer solution prepared in (2) above were each poured into a quartz cell to a height of approximately 70%. The absorbance was then measured in the wavelength range of 200 to 400 nm using a UV-Visible Spectrophotometer V-550 (JASCO Corporation) to obtain an absorption spectrum. As a blank, the absorbance was measured in the same manner using the solution-polymerized polymer prepared above. The obtained absorption spectrum (wavelength range 250 to 400 nm) is shown in Figure 3.

[0123] As shown in Figure 3, the glycol lignin ethylene oxide adduct exhibits excellent ultraviolet absorption performance even in the form of a resin composition (solution-polymerized polymer solution). Furthermore, since it has a higher absorbance in the UV-A region compared to conventional benzophenone-based ultraviolet absorbers, it is clear that the glycol lignin alkylene oxide adduct of the present invention is extremely useful for preventing resin degradation when used as an ultraviolet absorber.

[0124] Commercially available resin solutions (solution-polymerized polymers) of styrene resin, olefin resin, polyester resin, melamine resin, epoxy resin, silicone resin, and polyurethane resin were obtained and the solubility test and absorbance measurement were carried out as described above. As a result, it was confirmed that the same results as those described above were obtained regardless of which resin solution was used.

Claims

1. A resin modifier comprising a glycol lignin alkylene oxide adduct in which an alkylene oxide is added to glycol lignin.

2. The resin modifier of claim 1 , wherein the alkylene oxide comprises ethylene oxide.

3. The resin modifier according to claim 1 or 2, wherein the glycol lignin has a chemical structure derived from cedar.

4. The resin modifier according to any one of claims 1 to 3, wherein the glycol lignin alkylene oxide adduct has a phenolic hydroxyl group content of less than 1.0 mmol per 1 g.

5. The resin modifier according to any one of claims 1 to 4, wherein the ratio of the mass of oxyalkylene chain to the mass of lignin in the glycol lignin alkylene oxide adduct is 0.4 to 5.

0.

6. An ultraviolet absorber comprising a glycol lignin alkylene oxide adduct in which an alkylene oxide is added to glycol lignin.

7. The ultraviolet absorber according to claim 6, wherein the critical wavelength is 360 nm or more.

8. A resin composition comprising the resin modifier according to any one of claims 1 to 5 or the ultraviolet absorber according to claim 6 or 7, and a resin.

9. 9. The resin composition according to claim 8, wherein the resin is at least one selected from the group consisting of a (meth)acrylic resin, a styrene resin, an olefin resin, a polyester resin, a melamine resin, an epoxy resin, a silicone resin, and a polyurethane resin.

10. A coating composition comprising the resin composition according to claim 8 or 9.

11. A molded article made of the resin composition according to claim 8 or 9.

12. A coating film comprising the resin composition according to claim 8 or 9 or the coating composition according to claim 10.

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