Additive

Abstract

Provided is an additive which has a maximum absorption wavelength at 280-310 nm in order to efficiently absorb the UV-B region (280-320 nm), suppresses discoloration during heating, has a high decomposition initiation temperature during heating, and has excellent heat resistance. This additive is represented by general formula (1): [Chemical Formula 1] # imgabs0 # (In general formula (1), R1 and R2 each independently represent an alkoxy group having 1-10 carbon atoms or form a ring by bonding with a divalent group, R3 to R7 each independently represent at least one selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1-10 carbon atoms, a sulfur-containing group, a nitrogen-containing group, and a halogen, or any two of R3 to R7 are bonded to a divalent group to form a ring.

Description

Technical Field

[0001] The present invention relates to additives. Background Art

[0002] In the past, in order to impart various functions to organic materials and inorganic materials, various additives have been used in organic materials and inorganic materials. For example, it is known that ultraviolet absorbers are added to organic materials and inorganic materials to cut off light of a specific wavelength, absorb ultraviolet rays, and improve the light resistance of organic materials such as resins. As ultraviolet absorbers of organic compounds, benzotriazole compounds, benzophenone compounds, triazine compounds, malonic acid derivatives, etc. are used. Although malonic acid derivatives are known as ultraviolet absorbers that absorb short-wavelength UV-B regions in ultraviolet rays (see Japanese Patent Documents 1 to 3, etc.), it is expected that there is an ultraviolet absorber that can absorb the UV-B region more efficiently, for example, when the resin is added to a resin, and can suppress coloring when the resin is subjected to heat processing, and has a high decomposition starting temperature when heated, that is, an ultraviolet absorber with excellent heat resistance, good appearance, and no damage to the ultraviolet absorption ability.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2022-052594

[0006] Patent Document 2: Japanese Patent Application Publication No. 2021-181528

[0007] Patent Document 3: Japanese Patent Application Publication No. 50-008844 Summary of the invention

[0008] Problem that the invention aims to solve

[0009] The present invention is completed in view of the above problems, and aims to provide an additive having a maximum absorption wavelength of 280 to 310 nm in order to efficiently absorb the UV-B region (280 to 320 nm), suppressing coloration during heating, having a high decomposition starting temperature during heating and excellent heat resistance.

[0010] Solutions for solving problems

[0011] In order to solve the above-mentioned problems, the additive of the present invention is characterized by being represented by the following general formula (1).

[0012] [Chemical formula 1]

[0013]

[0014] (In the general formula, R 1 , R2 R each independently represents an alkoxy group having 1 to 10 carbon atoms, or is bonded to a divalent group to form a ring. 3 ~R 7 Each independently represents at least one selected from a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a sulfur-containing group, a nitrogen-containing group and a halogen, or R 3 ~R 7 Any two of them are bonded to a divalent group to form a ring.

[0015] The ultraviolet absorber of the present invention is characterized in that it is an additive represented by the above-mentioned general formula (1).

[0016] Effects of the Invention

[0017] The additive of the present invention has a maximum absorption wavelength of 280 to 310 nm and can therefore efficiently absorb the UV-B region, and can suppress coloration during heating, has a high decomposition start temperature during heating, and is excellent in heat resistance. DETAILED DESCRIPTION

[0018] Hereinafter, specific embodiments of the present invention will be described.

[0019] It should be noted that, in the present invention, the numerical value of the number of carbon atoms represents an integer.

[0020] (additive)

[0021] The additive of the present invention is represented by the above-mentioned general formula (1).

[0022] In the above general formula (1), R 1 , R 2 Each independently represents an alkoxy group having 1 to 10 carbon atoms, or is bonded to a divalent group to form a ring. 1 , R 2 It is an alkoxy group having 1 to 10 carbon atoms.

[0023] The hydrocarbon group forming the alkoxy group is preferably an aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group. In addition, the hydrocarbon group forming the alkoxy group may be linear or branched.

[0024] The alkoxy group is not particularly limited, and examples thereof include methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 2-methyl-1-propoxy, 2-methyl-2-propoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, etc. The alkoxy group preferably has 1 to 4 carbon atoms, and more preferably methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 2-methyl-1-propoxy, 2-methyl-2-propoxy, further preferably methoxy, ethoxy, propoxy, 1-methylethoxy, 1-methylethoxy, and particularly preferably methoxy having 1 to 3 carbon atoms.

[0025] The divalent group forming the ring is not particularly limited, and examples thereof include a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, and a sulfur-containing group.

[0026] As the hydrocarbon group, for example, the following R 3 ~R 7 A group obtained by removing one hydrogen atom from the monovalent hydrocarbon group listed in the formula (a). Among them, an aliphatic hydrocarbon group is preferred, and a saturated aliphatic hydrocarbon group is more preferred. In addition, the hydrocarbon group may be straight-chain or branched.

[0027] The oxygen-containing group has, for example, 1 to 10 carbon atoms. Examples of the oxygen-containing group having 1 to 10 carbon atoms include an ether group-containing group, an ester group-containing group, a carbonyl group-containing group, and a carboxyl group-containing group.

[0028] The nitrogen-containing group, for example, has 1 to 10 carbon atoms. Examples of the nitrogen-containing group having 1 to 10 carbon atoms include primary amino groups, secondary amino groups, or tertiary amino groups (including groups that become amide groups (-NHCO-), imide groups (-CONRCO-), or urea groups (-NHCONH-) by the above-mentioned bonding at the terminal site containing a divalent group), amide group-containing groups, imide group-containing groups, urea group-containing groups, and carbamate group-containing groups.

[0029] The sulfur-containing group has, for example, 1 to 10 carbon atoms. Examples of the sulfur-containing group having 1 to 10 carbon atoms include a thioether group-containing group, a thioether group-containing group, a disulfide group-containing group, a thioester group-containing group, a thioamide group-containing group, a sulfonyl group-containing group, a thiocarbonyl group-containing group, a thiourea group-containing group, a thiocarbamate group-containing group, and a dithiocarbamate group-containing group.

[0030] Among them, a group that forms an amide group, an imide group, or a urea group by the above bond at a site having 1 to 5 carbon atoms and including the terminal of the divalent group is preferred, and a group that forms a urea group by the above bond is more preferred.

[0031] In the above formula (1), R 3 ~R 7 Each independently represents at least one selected from a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a sulfur-containing group, a nitrogen-containing group and a halogen, or R 3 ~R 7 Any two of them are bonded to a divalent group to form a ring.

[0032] Examples of the hydrocarbon group include a saturated or unsaturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

[0033] Examples of the saturated or unsaturated aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups having 1 to 10 carbon atoms, and among these, linear or branched alkyl groups are preferred. The linear or branched alkyl group is not particularly limited, and examples thereof include methyl, ethane-1-yl, propane-1-yl, 1-methylethane-1-yl, butane-1-yl, 1-methylpropane-1-yl, 2-methylpropane-1-yl, 2-methylpropane-2-yl, pentane-1-yl, pentane-2-yl, hexane-1-yl, heptane-1-yl, octane-1-yl, nonane-1-yl, and decane-1-yl.

[0034] The alicyclic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, and is not particularly limited. Examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, and groups containing the above groups as a skeleton.

[0035] The aromatic hydrocarbon group includes an aromatic ring such as a benzene ring, a naphthalene ring, and an anthracene ring, and the number of carbon atoms is preferably 6 to 10. The aromatic hydrocarbon group is not particularly limited, and examples thereof include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,5-trimethylphenyl, 2,4,6-trimethylphenyl, 1-naphthyl, 2-naphthyl, or groups containing skeletons of the above groups.

[0036] The sulfur-containing group is not particularly limited, and examples thereof include a thiophenyl group-containing group, a thiazole group-containing group, a thiol group-containing group, a thioether group-containing group, a thioalkoxy group-containing group, a sulfonic acid group-containing group, a thioether group-containing group, a disulfide group-containing group, a thioester group-containing group, a thioamide group-containing group, a sulfonyl group-containing group, a thiocarbonyl group-containing group, a thiourea group-containing group, a thiocarbamate group-containing group, and a dithiocarbamate group-containing group. The number of carbon atoms is preferably 0 to 10.

[0037] The nitrogen-containing group is not particularly limited, and examples thereof include a cyano group-containing group, a cyanate group-containing group, an isocyanate group-containing group, a nitro group-containing group, a nitroalkyl-containing group, an amide group-containing group, a urea group-containing group, a carbamate group-containing group, an imide group-containing group, a carbodiimide group-containing group, an azo group-containing group, a pyridyl group-containing group, an imidazole group, an amino group (a primary amino group-containing group, a secondary amino group-containing group, a tertiary amino group-containing group), an aminoalkyl-containing group, and the like. The number of carbon atoms thereof is preferably 0 to 10.

[0038] The halogen is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0039] Among them, R 3 ~R 7 Preferred are a hydrogen atom, a hydrocarbon group, and a halogen. Particularly preferred are a combination of a hydrogen atom and a hydrocarbon group, and a combination of a hydrogen atom and a halogen.

[0040] In addition, among the hydrocarbon groups, an aliphatic hydrocarbon group is preferred, and a saturated aliphatic hydrocarbon group is more preferred. The hydrocarbon group has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 5 carbon atoms.

[0041] In R 3 ~R 7 When any two of the above are bonded to a divalent group to form a ring, the divalent group forming the ring is not particularly limited, and examples thereof include a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, and the like. 1 , R 2 The above descriptions represent divalent groups that form a ring by bonding.

[0042] From the viewpoint of being able to efficiently absorb UV-B region, the maximum absorption wavelength of the additive of the present invention in a 100 μM solution is preferably 280 to 310 nm, more preferably 280 to 300 nm, and even more preferably 280 to 290 nm. The maximum absorption wavelength is measured using chloroform or dimethyl sulfoxide as a solvent, for example.

[0043] In a particularly preferred example, the maximum absorption wavelength of the additive of the present invention in a 100 μM solution is below 300 nm.

[0044] From this point of view, R in the additive of the present invention 3 ~R 7 Preferably, it is a hydrogen atom, a hydrocarbon group, and a halogen. Among the hydrocarbon groups, an aliphatic hydrocarbon group is preferred, and a saturated aliphatic hydrocarbon group is more preferred. The number of carbon atoms in the hydrocarbon group is 1 to 10, preferably 1 to 8, and more preferably 1 to 5. The halogen is preferably a chlorine atom or a fluorine atom, and more preferably a chlorine atom. In addition, at least R5 Preferred is halogen.

[0045] In addition, R 3 ~R 7 Preferably, it is composed of hydrogen atoms and hydrocarbon groups, at least one of which is a hydrogen atom and at least one is a hydrocarbon group, or R 3 ~R 7 Composed of hydrogen atoms and halogens, at least one of which is a hydrogen atom and at least one of which is a halogen; R 3 ~R 7 More preferably, it is composed of hydrogen atoms and halogens, at least one of which is a hydrogen atom and at least one of which is a halogen.

[0046] The additive of the present invention is excellent in heat resistance from the viewpoints of oxidation and coloration caused by heat in an oxygen atmosphere during heating and decomposition (decomposition start temperature) caused only by heat in a nitrogen atmosphere.

[0047] From the viewpoint of suppressing coloration during heating (heat resistance), the R of the additive of the present invention is 3 ~R 7 Preferably, it is a hydrogen atom, a hydrocarbon group, or a halogen; more preferably, it is a hydrogen atom or a halogen. Preferably, the halogen is a chlorine atom or a fluorine atom; more preferably, it is a chlorine atom. In addition, preferably, at least R 5 It is a halogen.

[0048] In addition, R 3 ~R 7 Preferably, it is composed of hydrogen atoms and hydrocarbon groups, at least one of which is a hydrogen atom and at least one is a hydrocarbon group, or R 3 ~R 7 Composed of hydrogen atoms and halogens, at least one of which is a hydrogen atom and at least one of which is a halogen; R 3 ~R 7 More preferably, it is composed of hydrogen atoms and halogens, at least one of which is a hydrogen atom and at least one of which is a halogen.

[0049] From the viewpoint of heat resistance, the decomposition starting temperature of the additive of the present invention when heated is preferably 190°C or higher, more preferably 200°C or higher, and even more preferably 210°C or higher. 3 ~R 7 Preferred are hydrogen atoms, hydrocarbon groups and halogens. 3 ~R 7 Particularly preferably, it is composed of a hydrogen atom and a hydrocarbon group, at least one of which is a hydrogen atom and at least one of which is a hydrocarbon group, or it is composed of a hydrogen atom and a halogen, at least one of which is a hydrogen atom and at least one of which is a halogen. Among the hydrocarbon groups, an aliphatic hydrocarbon group is preferred, and a saturated aliphatic hydrocarbon group is more preferred. The number of carbon atoms in the hydrocarbon group is 1 to 10, preferably 1 to 8, more preferably 1 to 5, and even more preferably 2 to 5.

[0050] The additive of the present invention may be in a solid or liquid state at 25°C. If it is solid at 25°C, it is easier to add and mix the additive to the resin, which is preferred.

[0051] Considering this point, R 3 ~R 7 Preferred are hydrogen atoms, hydrocarbon groups and halogens. 3 ~R 7 It is composed of hydrogen atoms and hydrocarbon groups, at least one of which is a hydrogen atom and at least one of which is a hydrocarbon group, or it is composed of hydrogen atoms and halogens, at least one of which is a hydrogen atom and at least one of which is a halogen. Among the hydrocarbon groups, it is preferably an aliphatic hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group. 3 ~R 7 The hydrocarbon group preferably has a quaternary carbon, or R 3 ~R 7 Three or more of them are hydrocarbon groups.

[0052] The additive of the present invention is not particularly limited, and examples thereof include benzylidenemalonic acid dialkyl compounds and benzylidenebarbituric acid compounds. The benzylidenemalonic acid dialkyl compounds are not particularly limited, and examples thereof include 2-(4-chlorobenzylidene)malonate dimethyl, 2-(4-fluorobenzylidene)malonate dimethyl, 2-(4-ethylbenzylidene)malonate dimethyl, 2-(4-isopropylbenzylidene)malonate dimethyl, 2-(4-tert-butylbenzylidene)malonate dimethyl, 2-(4-isobutylbenzylidene)malonate dimethyl, 2-(2,4,6-trimethylbenzylidene)malonate dimethyl, 2-(4-isopropylbenzylidene)malonate diisopropyl, and 2-(3,4-(methylenedioxy)benzylidene)malonate diisopropyl. The benzylidene barbituric acid compounds are not particularly limited, and examples thereof include 5-(4-chlorobenzylidene) barbituric acid, etc. Among them, from the viewpoint of high absorption in the UV-B region (280 to 320 nm) and heat resistance, dialkyl benzylidene malonates are preferred, and dimethyl 2-(4-chlorobenzylidene) malonate, dimethyl 2-(4-fluorobenzylidene) malonate, dimethyl 2-(4-ethylbenzylidene) malonate, dimethyl 2-(4-isopropylbenzylidene) malonate, dimethyl 2-(4-tert-butylbenzylidene) malonate, dimethyl 2-(4-isobutylbenzylidene) malonate, dimethyl 2-(2,4,6-trimethylbenzylidene) malonate, and diisopropyl 2-(4-isopropylbenzylidene) malonate are more preferred.

[0053] (Ultraviolet light absorber)

[0054] The additive of the present invention is useful as an ultraviolet absorber in that it can efficiently absorb UV-B region (280 to 320 nm) among ultraviolet rays that cause resin degradation. The ultraviolet absorber of the present invention has a maximum absorption wavelength at 280 to 310 nm, preferably at 280 to 300 nm, and more preferably at 280 to 290 nm.

[0055] (Manufacturing method of additive)

[0056] The method for producing the additive of the present invention is not particularly limited, and examples thereof include a method of subjecting a compound having a carbon atom sandwiched between two carbonyl carbons such as malonic acid diester and barbituric acid and having a highly acidic hydrogen atom to a condensation reaction with a benzaldehyde derivative.

[0057] (Use of additives)

[0058] The additive of the present invention can be added to organic materials, inorganic materials, etc. As organic materials, there are no particular limitations, and examples thereof include organic compounds such as materials from resins, animals and plants, and materials from crude oil; as inorganic materials, there are no particular limitations, and examples thereof include inorganic compounds such as silica materials, glass, water glass, low melting point glass, quartz, silicone resin, alkoxysilane, silane coupling agent, metal, metal oxide, and minerals obtained by a sol-gel method. Among them, the additive can be applied to the use of absorbing the UV-B region or inhibiting transmission, for example, in improving the light resistance of resins, preventing degradation, and inhibiting transmission in the UV-B region of transparent components such as glass or resin.

[0059] The additive of the present invention is excellent in that it volatilizes less and decomposes less under heating conditions when added to a resin. The additive of the present invention may be used alone or in combination of two or more.

[0060] As a method for adding the additive to the resin, a general method of adding the additive can be applied. Although not particularly limited, for example, a method of mixing the additive in a solution of the resin, a method of mixing the additive after melting the resin, a method of mixing the additive in a raw material monomer of the resin and then forming the resin, etc. can be applied.

[0061] That is, by adding the additive of the present invention to a resin, a resin composition can be formed.

[0062] The resin to which the additive of the present invention is added is not particularly limited, and conventionally known resins can be widely used, and examples thereof include thermoplastic resins and thermosetting resins, each of which includes a polymer having one type of repeating unit and a copolymer having a plurality of repeating units.

[0063] Among the above resins, thermoplastic resins are preferred. Thermoplastic resins are not particularly limited. As polymers, for example, (meth) acrylic resins, olefin resins, styrene resins, ester resins, ether resins, vinyl chloride resins, fluorine resins, ethylene resins, polycarbonate resins, polyamide resins, polyimide resins, polyamideimide resins, polymaleimide resins, polyvinyl pyrrolidone resins, polyurethane resins, polysulfone resins, polyphenylene sulfide resins, cycloolefin resins, etc. As copolymers, for example, butadiene-styrene copolymers, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, styrene-isoprene copolymers, styrene-acrylic copolymers, vinyl chloride-vinylidene chloride-acrylonitrile copolymers, etc. can be cited.

[0064] Among them, preferred are (meth)acrylic resins (acrylic resins, etc.), styrene resins (polystyrene, etc.), ester resins (polyethylene terephthalate resins, etc.), ether resins (polyacetal, etc.), polycarbonate resins (polycarbonate, etc.), polyamide resins (polyamide, etc.), polyphenylene sulfide resins, cycloolefin resins (cycloolefin polymers, etc.), and acrylonitrile-butadiene-styrene copolymers (acrylonitrile-butadiene-styrene copolymer resins, etc.).

[0065] When the additive is mixed or kneaded with organic and inorganic substances represented by resin under heating conditions, or when the resin component containing the additive is processed or molded by heating, if the heat resistance of the additive is low, thermal decomposition, thermal modification, etc. will occur, and the ultraviolet absorption effect cannot be fully exerted, which pollutes the device and loses transparency when the resin is transparent. In addition, due to thermal decomposition, thermal modification, etc., the transmittance in the visible light region is reduced, resulting in coloration. Therefore, additives with suppressed coloration during heating, high decomposition start temperature during heating, and excellent heat resistance are expected.

[0066] The additive of the present invention can be preferably used for resins having excellent heat resistance (suppressing coloration during heating, high decomposition starting temperature during heating), suppressing coloration under high temperature conditions, and reducing the function of the additive, and having a thermoforming temperature or a thermosetting temperature of 100°C or more, and further 200°C or more, or produced and used under these temperature conditions. Therefore, the additive of the present invention can be preferably used for polymers of thermoplastic resins and copolymers of thermoplastic resins, and can be particularly preferably used for polymers of thermoplastic resins and copolymers of thermoplastic resins having the above-mentioned thermoforming temperature.

[0067] For example, among thermoplastic resin polymers, styrene resins (polystyrene: PS, molding temperature 100°C), (meth) acrylic resins (polymethyl methacrylate, molding temperature 160°C), cycloolefin resins (molding temperature 100°C), polycarbonate resins (polycarbonate: PC, molding temperature above 200°C), and ester resins (polyethylene terephthalate: PET, molding temperature above 200°C) can be preferably used.

[0068] Among the copolymers of thermoplastic resins, acrylonitrile-butadiene-styrene copolymers (acrylonitrile-butadiene-styrene copolymers: ABS, molding temperature 200° C. or higher) can be preferably used.

[0069] The additive of the present invention may contain other components within the range not impairing the effects of the present invention. The other components are not particularly limited, and examples thereof include solvents, light stabilizers, antioxidants, pH adjusters, and the like.

[0070] [Example]

[0071] Hereinafter, the present invention will be described in further detail with reference to Examples, but the present invention is not limited to these Examples.

[0072] 1. Synthesis of additive compounds

[0073] Compounds 1 to 8 were synthesized by the following method.

[0074] <Compound 1>(MYUA-1M)

[0075] [Chemical formula 2]

[0076]

[0077] 4-Chlorobenzaldehyde (7.03 g), dimethyl malonate (6.61 g), piperidine (421 mg), and acetic acid (605 mg) were added to 20 mL of toluene, and the reaction water was distilled off while reflux stirring was performed until the generation of water could no longer be confirmed. After the reaction was completed, the organic layer was washed with water and purified by column chromatography to obtain Compound 1.

[0078] IR(ATR):1726cm -1 (C=O stretch)

[0079] 1 HNMR(CDCl3,400MHz):7.72(s,1H),7.36(s,4H),3.85(s,3H),3.85(s,3H)

[0080] 13CNMR(CDCl3,400MHz):166.9,164.3,141.6,141.4,131.3,130.8,130.4,129.4,129.0,126.1,53.3,52.4

[0081] <Compound 2>

[0082] [Chemical formula 3]

[0083]

[0084] 4-Fluorobenzaldehyde (6.21 g), dimethyl malonate (6.61 g), piperidine (421 mg), and acetic acid (605 mg) were added to 20 mL of toluene, and the reaction water was distilled off while reflux stirring was performed until the generation of water could no longer be confirmed. After the reaction was completed, the organic layer was washed with water and purified by column chromatography to obtain Compound 2.

[0085] IR(ATR):1729cm -1 (C=O stretch)

[0086] 1 HNMR(CDCl3,400MHz):7.73(s,1H),7.43(q,2H),7.08(t,2H),3.85(s,3H),3.85(s,3H)

[0087] 13 CNMR(CDCl3,400MHz):167.0,164.4,141.6,141.4,131.5,129.0,129.0,125.3,116.5,115.9,53.1,52.4

[0088] <Compound 3>

[0089] [Chemical formula 4]

[0090]

[0091] 4-Ethylbenzaldehyde (6.71 g), dimethyl malonate (6.61 g), piperidine (421 mg), and acetic acid (605 mg) were added to 20 mL of toluene, and the reaction water was distilled off while reflux stirring was performed until the generation of water could no longer be confirmed. After the reaction was completed, the organic layer was washed with water and purified by column chromatography to obtain Compound 3.

[0092] IR(ATR):1735cm -1 (C=O stretch)

[0093] 1HNMR(CDCl3,400MHz):7.75(s,1H),7.35(d,2H),7.21(d,2H),3.86(s,3H),3.84(s,3H),2.66(q,2H),1.24(t,3H)

[0094] 13 CNMR(CDCl3,400MHz):167.4,164.7,147.6,143.0,130.1,129.8,129.5,128.7,128.3,124.3,53.0,52.3,28.8,15.2

[0095] <Compound 4>

[0096] [Chemical formula 5]

[0097]

[0098] Cumaldehyde (4.97 g), dimethyl malonate (4.43 g), piperidine (282 mg), and acetic acid (406 mg) were added to 20 mL of toluene, and the reaction water was distilled off while reflux stirring was performed until the generation of water could no longer be confirmed. After the reaction was completed, the organic layer was washed with water and purified by column chromatography to obtain compound 4.

[0099] IR(ATR):1729cm -1 (C=O stretch)

[0100] 1 HNMR(CDCl3,400MHz):7.74(s,1H),7.36(d,2H),7.24(d,2H),3.87(s,3H),3.84(s,3H),2.92(m,1H),1.25(s,3H),1.24(s,3H)

[0101] 13 CNMR(CDCl3,400MHz):167.4,164.7,152.2,142.9,130.2,129.7,129.3,127.3,126.9,124.3,53.0,52.3,34.1,24.0,23.4

[0102] <Compound 5>

[0103] [Chemical formula 6]

[0104]

[0105] 4-tert-Butylbenzaldehyde (8.12 g), dimethyl malonate (6.61 g), piperidine (421 mg), and acetic acid (605 mg) were added to 20 mL of toluene, and the reaction water was distilled off while reflux stirring was performed until the generation of water could no longer be confirmed. After the reaction was completed, the organic layer was washed with water and purified by column chromatography to obtain Compound 5.

[0106] IR(ATR):1726cm -1 (C=O stretch)

[0107] 1 HNMR(CDCl3,400MHz):7.74(s,1H),7.36-7.42(m,4H),3.87(s,3H),3.84(s,3H),1.32(s,9H)

[0108] 13 CNMR(CDCl3,400MHz):167.5,164.7,154.5,142.8,129.8,129.7,129.4,126.1,125.8,124.3,53.7,53.0,52.3,35.0,31.3,30.8

[0109] <Compound 6>

[0110] [Chemical formula 7]

[0111]

[0112] 4-isobutylbenzaldehyde (8.11 g), dimethyl malonate (6.61 g), piperidine (421 mg), and acetic acid (605 mg) were added to 20 mL of toluene, and the reaction water was distilled off while reflux stirring was performed until the generation of water could no longer be confirmed. After the reaction was completed, the organic layer was washed with water and purified by column chromatography to obtain Compound 6.

[0113] IR(ATR):1738cm -1 (C=O stretch)

[0114] 1 HNMR(CDCl3,400MHz):7.75(s,1H),7.34(d,2H),7.16(d,2H),3.86(s,3H),3.84(s,3H),2.49(d,2H),1.87(m,1H),0.91(s,3H),0.89(s,3H)

[0115] 13CNMR(CDCl3,400MHz):167.4,164.7,145.2,143.0,130.1,130.0,129.6,129.5,129.3,124.2,53.0,52.3,45.3,30.2,22.6,22.1

[0116] <Compound 7>

[0117] [Chemical formula 8]

[0118]

[0119] Trimethylbenzaldehyde (7.41 g), dimethyl malonate (6.61 g), piperidine (421 mg), and acetic acid (605 mg) were added to 20 mL of toluene, and the reaction water was distilled off while reflux stirring was performed until the generation of water could no longer be confirmed. After the reaction was completed, the organic layer was washed with water and purified by column chromatography to obtain Compound 7.

[0120] IR(ATR):1738cm -1 (C=O stretch)

[0121] 1 HNMR(CDCl3,400MHz):7.90(s,1H),6.83(s,2H),3.87(s,3H),3.57(s,3H),2.26(s,3H),2.16(s,6H),

[0122] 13 CNMR(CDCl3,400MHz):165.6,164.2,146.4,146.2,137.9,135.0,130.2,128.4,127.7,124.2,52.9,52.3,20.2,19.9

[0123] <Compound 8>

[0124] [Chemical formula 9]

[0125]

[0126] Cumaldehyde (14.8 g), diisopropyl malonate (18.8 g), piperidine (850 mg), and acetic acid (1.21 g) were added to 40 mL of toluene, and the reaction water was distilled off while reflux stirring was performed until the generation of water could no longer be confirmed. After the reaction was completed, the organic layer was washed with water and purified by column chromatography to obtain Compound 8.

[0127] IR(ATR):1739cm -1 (C=O stretch)

[0128] 1 HNMR(CDCl3,400MHz):7.65(s,1H),7.41(d,2H),7.22(d,2H),5.27(m,1H),5.15(m,1H),2.91(m,1H),1.31(d,12H),1.24(d,6H)

[0129] 13 CNMR(CDCl3,400MHz):166.5,163.9,151.8,141.4,130.5,129.9,129.6,127.1,126.7,125.9,69.2,69.1,34.2,24.0,23.4,22.1,21.8,21.5,21.3

[0130] <Compound 9>

[0131] Dimethyl 2-(4-methoxybenzylidene)malonate was a reagent produced by Tokyo Chemical Industry Co., Ltd., Japan.

[0132] 2. Measurement of UV absorption wavelength

[0133] A 100 μM chloroform solution of each of Compounds 1 to 9 was prepared, and the absorption spectrum was measured using an ultraviolet-visible-infrared spectrophotometer (UH4150V manufactured by Hitachi High-Technologies Corporation, Japan), and the maximum absorption wavelength was confirmed (Table 1).

[0134] From the maximum absorption wavelength shown in Table 1, it can be confirmed that the additives of Compounds 1 to 8 of Examples are superior to the additive of Compound 9 of Comparative Example in that they have a maximum absorption wavelength at 280 to 310 nm in the UV-B region (280 to 320 nm) and can efficiently absorb the UV-B region.

[0135] This suggests that the additive of the present invention is useful as an ultraviolet absorber, and in particular, since it has a maximum absorption wavelength at 280 to 300 nm, it suggests that the additive of the present invention is useful as an ultraviolet absorber. 3 ~R 7 Compounds 1 to 8 of the examples having a hydrogen atom, a hydrocarbon group or a halogen are useful. In addition, since the maximum absorption wavelength is at 280 to 290 nm, it is also suggested that R 3 ~R 7 Compounds 1 and 2 of Examples having hydrogen atoms and halogens are particularly useful.

[0136] 3. Status at 25℃

[0137] The states of Compounds 1 to 9 at 25°C were visually observed and recorded as solid or liquid in Table 1. It was observed from Examples 1 and 2 that if R 5 If R 5 If it is a halogen, it will be solid at 25°C.

[0138] In addition, in Example 5, a quaternary carbon such as 2-methylpropane-2-yl having a larger functional group, or in Example 7, R 3 ~R 7 When the compound has three or more hydrocarbon groups, it is suggested that the compound will be in a solid state at 25°C.

[0139] 4. Heat resistance test (1)

[0140] Compounds 1 to 8 (1 mmol) were placed in a 30 mL sample bottle and heated in a muffle furnace set at 300° C. for 10 minutes in the atmosphere. Compounds 1 to 8 were naturally cooled, and 10 mL of chloroform was added. The coloration was visually observed and evaluated according to the following criteria. The evaluation results are recorded in Table 1.

[0141] No coloring after heating: ◎

[0142] Slightly colored after heating: ○

[0143] Colored to brown after heating: △

[0144] Colored to black after heating: ×

[0145] The test results confirmed that, in the comparison of compounds 1 to 8, if R 3 ~R 7 With halogen (compounds 1, 2,), then with R 3 ~R 7 Compared with compounds having a hydrocarbon group (Compounds 3 to 8), coloration after heating is suppressed, and particularly when the halogen is a chlorine atom, heat resistance is excellent.

[0146] These results suggest that in R 3 ~R 7 The decomposition mechanism is different between the case where it is composed of hydrogen atoms and halogens and the case where it is composed of hydrogen atoms and hydrocarbon groups. In the case where it is composed of hydrogen atoms and halogens, colored decomposition products are less likely to be generated.

[0147] 5. Heat resistance test (2)

[0148] Using a differential thermal / thermogravimetric simultaneous thermal analyzer (STA7200 manufactured by Hitachi High-Technologies, Japan), the weight changes of compounds 1 to 8 of the present invention were measured under the conditions of a heating temperature of 10°C / min, a nitrogen atmosphere, and a measurement range of 25°C to 550°C. The decomposition starting temperature was calculated based on the endothermic peak of differential thermal analysis (DTA), and the measurement results are recorded in Table 1.

[0149] It was confirmed that the decomposition starting temperatures of compounds 1 to 8 were all 190° C. or higher and had excellent heat resistance. In particular, the decomposition starting temperatures of compound 1, compounds 3 to 6, and compound 8 were 210° C. or higher, which resulted in more excellent heat resistance.

[0150] 6. Changes in transmittance in the UV-B region (300nm) during heating

[0151] Compound 1 and Compound 9 (0.1 mmol) were placed in 30 mL sample bottles and heated in a muffle furnace set at 300°C for 10 minutes. After natural cooling, 10 mL of chloroform was added and the transmittance at 300 nm was measured. The transmittance changes at each wavelength were calculated from the transmittance of Compound 1 and Compound 9 before heating and compared.

[0152] The transmittance at 300 nm before heating was 0% for both Compound 1 and Compound 9. After heating, Compound 1 was 0% and showed no change. The transmittance of Compound 9 was 47%.

[0153] While the ultraviolet absorption capacity of compound 9 decreased after heating, it was confirmed that the ultraviolet absorption capacity of compound 1 was not impaired after heating.

[0154] This suggests that the additive of the present invention has excellent heat resistance in that the loss of ultraviolet absorption capacity due to heating is suppressed.

[0155]

Claims

1. An additive represented by the following general formula (1): Chemical formula 1 In the general formula, R 1 , R 2 Each independently represents an alkoxy group having 1 to 10 carbon atoms, or is bonded to a divalent group to form a ring, and R 3 ~R 7 Each independently represents at least one selected from a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a sulfur-containing group, a nitrogen-containing group and a halogen, or R 3 ~R 7 Any two of them are bonded to a divalent group to form a ring.

2. The additive according to claim 1, wherein The additive is an ultraviolet absorber.

3. The additive according to claim 2, wherein The maximum absorption wavelength of the additive in a 100 μM solution is below 300 nm.

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