COMPOSITION, RESIN COMPOSITION, AND MOLDED ARTICLE COMPRISING THEM

Abstract

A composition that includes a compound (A) including a structure represented by general formula (I) as a first component, that includes at least one of an antioxidant (B1) different from a phosphorus-based antioxidant and a light stabilizer (B2) as a second component, and that includes a resin component (C) as a third component. (In general formula (I), R1 and R2 each independently represent a C1-6 alkyl group; a C2-6 alkenyl group; an aryl group; or an aralkyl group. R3 and R4 each independently represent a hydrogen atom; a C1-6 alkyl group; a C2-6 alkenyl group; an aryl group; or an aralkyl group.)

Description

[Technical Field]

[0001] The present invention relates to a composition containing a specific unsaturated double bond-containing compound, a resin composition, and a molded article containing the same. [Background technology]

[0002] Resins are widely used in various fields as films, coating materials, fibers, various molded articles, etc. In general, molded articles made of resin alone and the various resin products mentioned above are known to deteriorate due to reactions with oxygen in the air triggered by heat, ultraviolet light, etc., and are therefore unable to withstand long-term use. Therefore, in order to prevent resin deterioration due to light, particularly ultraviolet light, and oxygen, light stabilizers, ultraviolet absorbers, antioxidants, etc. are blended into resins.

[0003] For example, Patent Document 1 proposes the addition of a phosphorus-based antioxidant to prevent yellowing of compositions containing phenolic resins. Patent Document 2 proposes a new phenolic antioxidant to prevent oxidative degradation of resins, such as yellowing. Furthermore, Patent Document 3 proposes the addition of a hindered amine-based light stabilizer to improve the weather resistance of polyurethane / acrylic resin compositions. However, phosphorus-based antioxidants are susceptible to hydrolysis, phenolic antioxidants may oxidize and cause yellowing, and hindered amine-based light stabilizers have poor compatibility with resins, limiting the resins they can be blended with. Thus, conventional antioxidants and light stabilizers have various problems. Therefore, there is a demand for antioxidants and light stabilizers that solve these problems.

[0004] On the other hand, Patent Document 4 proposes a resin composition containing a specific unsaturated double bond-containing compound having oxygen absorbing properties. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-263940 [Patent Document 2] Japanese Patent Application Publication No. 2019-026737 [Patent Document 3] Japanese Patent Application Publication No. 10-16169 [Patent Document 4] International Publication No. 2019 / 107252 Summary of the Invention [Problem to be solved by the invention]

[0006] It is conceivable that deterioration of a resin due to oxygen can be prevented by reducing the oxygen concentration in a resin composition using an unsaturated double bond-containing compound that exhibits oxygen absorption performance, as described in Patent Document 4. However, Patent Document 4 does not fully consider the prevention of yellowing of resins and molded articles produced using the resin composition, and the reality is that there is still room for improvement. An object of the present invention is to provide a composition, a resin composition, and a molded article containing the composition or resin composition, which exhibit excellent yellowing suppression effects. [Means for solving the problem]

[0007] As a result of intensive research conducted by the present inventors to achieve the above object, they found that a composition exhibiting excellent yellowing suppression effect can be obtained by using a compound having a specific structure containing an unsaturated double bond in combination with at least one of a specific antioxidant and a specific light stabilizer, and thus completed the present invention.

[0008] That is, the present invention provides the following [1] to

[10] . [1] A composition comprising, as a first component, a compound (A) having a structure represented by the following general formula (I), as a second component, at least one of an antioxidant (B1) other than a phosphorus-based antioxidant and a light stabilizer (B2), and as a third component, a resin component (C):

[0009] [ka] (In general formula (I), R 1 and R 2 R each independently represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, or an aralkyl group. 3 and R 4 each independently represents a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group. [2] R in the general formula (I) 1 and R 2 are each independently an alkyl group having 1 to 4 carbon atoms. [3] The composition according to the above [1], wherein the compound (A) is a compound having a structure represented by the following general formula (II):

[0010] [ka] (In general formula (II), R 5 and R 6 R each independently represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, or an aralkyl group. 7 and R 8 R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, or an aralkyl group. 9 represents a hydrogen atom; a (meth)acryloyl group; an alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group. [4] As the second component, phenol The composition according to any one of the above [1] to [3], which contains a water-soluble antioxidant. [5] The composition according to any one of the above [1] to [4], comprising 0.1 to 5 parts by mass of the first component and 0.1 to 5 parts by mass of the second component per 100 parts by mass of the resin component (C). [6] The composition according to any one of the above [1] to [5], wherein the mass ratio Ma / Mb of the mass Ma of the first component to the mass Mb of the second component is 0.1 to 20. [7] The composition according to any one of the above [1] to [6], wherein the resin component (C) is a resin component of a curable resin. [8] The composition according to [7] above, wherein the curable resin is at least one of a polyurethane resin and an epoxy resin. [9] A resin composition obtained by curing the composition described in [7] or [8] above.

[10] A molded article comprising the composition according to any one of the above [1] to [8] or the resin composition according to the above [9]. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a composition, a resin composition, and a molded article thereof that exhibit excellent yellowing suppression effects. DETAILED DESCRIPTION OF THE INVENTION

[0012] [Composition] A composition according to an embodiment of the present invention comprises, as a first component, a compound (A) having a structure represented by the following general formula (I), as a second component, at least one of an antioxidant (B1) other than a phosphorus-based antioxidant and a light stabilizer (B2), and as a third component, a resin component (C).

[0013] [ka] (In general formula (I), R 1 and R 2 R each independently represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, or an aralkyl group. 3 and R 4 each independently represents a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.

[0014] The composition exhibits excellent yellowing suppression effect by using the specific compound (A) having an unsaturated double bond in combination with at least one of an antioxidant (B1) other than a phosphorus-based antioxidant and a light stabilizer (B2). The reason for this is presumed to be, but not limited to, the following. Yellowing of resins is primarily caused by their oxidation. Resin oxidation proceeds through two cycles: (i) an alkyl radical (R·), generated by UV light or other factors, reacts with oxygen to generate a peroxide radical (ROO·) (hereafter referred to as the first reaction); and (ii) ROO· abstracts hydrogen from the resin skeleton, becoming a hydroperoxide (ROOH) and generating R·. ROOH then decomposes to generate a new radical, accelerating the oxidation (hereafter referred to as the second reaction). Antioxidants and light stabilizers generally exert their antioxidant effects by decomposing or quenching ROO· and ROOH, which are factors that drive the second reaction. However, antioxidants and light stabilizers cannot stop the first reaction, which generates ROO·, and a certain amount of oxidation still occurs. In contrast, the compound (A) has oxygen absorbing properties, and when it is blended with the resin component (C), the generation of ROO·, which is a cause of the resin oxidation cycle, is reduced, thereby suppressing the first reaction. Therefore, by using the compound (A) in combination with an existing antioxidant or light stabilizer that suppresses the second reaction, both the first and second reactions are suppressed, and it is thought that a superior yellowing suppression effect that cannot be achieved with existing antioxidants or light stabilizers is exhibited.

[0015] <First ingredient> The compound (A) contained in the composition as the first component is a compound having a structure represented by general formula (I). As described above, the compound (A) has oxygen absorbing properties and inhibits the reaction of oxygen with alkyl radicals generated in resins or molded articles due to ultraviolet rays or the like.

[0016] [ka]

[0017] In general formula (I), R 1 and R 2 each independently represents an alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.

[0018] R 1 and R 2 Examples of the alkyl group having 1 to 6 carbon atoms represented by include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0019] R 1 and R 2 Examples of the alkenyl group having 2 to 6 carbon atoms represented by include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a prenyl group, a hexenyl group (such as a cis-3-hexenyl group), and a cyclohexenyl group.

[0020] R 1 and R 2 Examples of the aryl group represented by include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0021] R 1 and R 2 Examples of the aralkyl group represented by include a benzyl group, a 2-phenylethyl group, a 2-naphthylethyl group, and a diphenylmethyl group.

[0022] Among these, from the viewpoint of more effectively suppressing yellowing of resins and molded articles produced using the composition and from the viewpoint of improving the storage stability of the composition, R 1 and R 2are each independently preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group.

[0023] In general formula (I), R 3 and R 4 R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, or an aralkyl group. 3 and R 4 Examples of the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 2 to 6 carbon atoms, the aryl group, and the aralkyl group represented by the above R 1 and R 2 Therefore, the same explanation will be omitted.

[0024] Among these, R 3 and R 4 are each independently preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, or an aryl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom. Among these, from the viewpoint of improving the oxygen absorption performance of the resulting polymer, R 3 and R 4 are preferably all hydrogen atoms.

[0025] From the viewpoint of more effectively suppressing yellowing of resins and molded articles, and from the viewpoint of improving the storage stability of the composition, the compound (A) containing the structure represented by general formula (I) is preferably a compound containing a structure represented by the following general formula (II) or a compound represented by any of the following general formulas (III) to (V), and more preferably a compound represented by the following general formula (III) or the following general formula (V).

[0026] [ka] (In general formula (II), R 5 and R 6R each independently represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, or an aralkyl group. 7 and R 8 R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, or an aralkyl group. 9 represents a hydrogen atom; a (meth)acryloyl group; an alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.

[0027] In general formula (II), R 5 , R 6 , R 7 and R 8 Examples of R in general formula (I) are 1 , R 2 , R 3 and R 4 The explanation is the same as that for (1), and a duplicate explanation will be omitted.

[0028] In general formula (II), R 9 The (meth)acryloyl group represented by represents an acryloyl group or a methacryloyl group.

[0029] In general formula (II), R 9 Examples of the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 2 to 6 carbon atoms, the aryl group, and the aralkyl group represented by the formula (I) are R 1 The explanation is the same as that for (1), and a duplicate explanation will be omitted. In general formula (II), R 9 is preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, and more preferably a methyl group or a prenyl group.

[0030] [ka]

[0031] In general formula (III), R 10 , R 11 , R16 and R 17 R each independently represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, or an aralkyl group. 12 and R 13 R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, or an aralkyl group. 14 represents a hydrogen atom or a methyl group, and R 15 represents a hydroxyl group, a (meth)acryloyloxy group, a 4-vinylphenoxy group, or an alkenyloxy group having 2 to 6 carbon atoms.

[0032] In general formula (III), R 10 , R 11 , R 12 and R 13 are R in the general formula (I), respectively. 1 , R 2 , R 3 and R 4 The explanation is the same as that for (1), and a duplicate explanation will be omitted. In general formula (III), R 14 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. 15 represents a hydroxyl group, a (meth)acryloyloxy group, a 4-vinylphenoxy group, or an alkenyloxy group having 2 to 6 carbon atoms, and is preferably a hydroxyl group or a (meth)acryloyloxy group. The alkenyloxy group having 2 to 6 carbon atoms may be a vinyloxy group having 2 to 6 carbon atoms.

[0033] In general formula (III), R 15 Examples of the (meth)acryloyloxy group represented by the formula include an acryloyloxy group and a methacryloyloxy group.

[0034] In general formula (III), R 15Examples of the alkenyloxy group having 2 to 6 carbon atoms represented by the formula (I) include a vinyloxy group, an allyloxy group, a 1-propenyloxy group, an isopropenyloxy group, a 1-butenyloxy group, a 2-butenyloxy group, a 3-butenyloxy group, a 2-methylallyloxy group, a 1-cyclobutenyloxy group, a 1-pentenyloxy group, a 2-methyl-2-butenyloxy group, a 1-cyclopentenyloxy group, a 1-hexenyloxy group, a 2-methyl-2-pentenyloxy group, and a 1-cyclohexenyloxy group.

[0035] In general formula (III), R 16 and R 17 each independently represents an alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group, examples and preferred ones of which are R 1 and R 2 This is the same as that explained in Among these, R 16 and R 17 are each independently preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group.

[0036] [ka]

[0037] In general formula (IV), R 18 represents a hydrogen atom or a methyl group, and R 19 represents a hydroxyl group, a (meth)acryloyloxy group, a styryloxy group, or an alkenyloxy group having 2 to 5 carbon atoms.

[0038] In general formula (IV), R 19 The (meth)acryloyloxy group and the alkenyloxy group having 2 to 5 carbon atoms represented by R 15 This is the same as that explained in

[0039] [ka] (However, the compound represented by general formula (V) has a weight average molecular weight (Mw) in terms of polystyrene of 200 to 50,000.)

[0040] There are no particular limitations on the method for producing the compounds having a structure represented by general formula (I), the compounds having a structure represented by general formula (II), the compounds represented by general formula (III), general formula (IV), and general formula (V), and they can be produced by applying known methods alone or in combination.

[0041] The content of compound (A) in the composition is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, per 100 parts by mass of resin component (C), from the viewpoint of making it easier to express the characteristics derived from resin component (C); and in order to obtain a sufficient yellowing suppression effect, the content is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, even more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more.

[0042] <Second ingredient> The composition includes, as a second component, at least one of an antioxidant (B1) other than a phosphoric acid-based antioxidant (hereinafter simply referred to as "antioxidant (B1)") and a light stabilizer (B2). The second component functions to quench peroxide radicals and hydroperoxides. Examples of the antioxidant (B1) other than the phosphoric acid-based antioxidant include phenol-based antioxidants, sulfur-based antioxidants, hydroxylamine-based antioxidants, ascorbic acids, nitrous acids, etc. In particular, phenol-based antioxidants are preferred from the viewpoint of more effectively suppressing yellowing of resins and molded articles produced using the composition. Commercially available antioxidants include Irganox 1010, Irganox 1076, Irganox 1330, Irganox 3114, Irganox 3125 (all manufactured by BASF), Adeka Stab AO-60, Adeka Stab AO-80 (all manufactured by ADEKA Corporation), Sumilizer BHT, Sumilizer GA-80, Sumilizer GS, Sumilizer GM (all manufactured by Sumitomo Chemical Co., Ltd.), DSTP "Yoshitomi", DLTP "Yoshitomi", DMTP (Yoshitomi) (all manufactured by Mitsubishi Chemical Corporation), SEENOX 412S (manufactured by Shipro Kasei Co., Ltd.), and CYANOX 1212 (manufactured by Cyanamid). Generally, the yellowing of resins is believed to occur as a chain reaction of oxidation starting with peroxide radicals generated when carbon radicals on the resin combine with oxygen. In the above composition, compound (A) suppresses the generation of peroxide radicals by removing oxygen, thereby suppressing the yellowing of the resin to some extent. In addition, the antioxidant (B1) or light stabilizer (B2) is thought to sufficiently suppress the yellowing of the resin by quenching the peroxide radicals generated from oxygen that compound (A) was not able to completely remove. Phosphorus-based antioxidants have the ability to quench hydroperoxides, which are the product of the quenching of peroxide radicals, into stable compounds, but they are poor at quenching the peroxide radicals themselves, and therefore, when combined with compound (A), sufficient yellowing suppression is not achieved. A phosphoric acid antioxidant may be contained together with the antioxidant (B1), but the content thereof is preferably kept low from the viewpoint of minimizing hydrolysis of the phosphoric acid antioxidant. The content of the phosphoric acid antioxidant is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0% by mass, based on the mass of the entire composition.

[0043] Examples of the light stabilizer (B2) include amine-based light stabilizers. Examples of the amine-based light stabilizer include 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / dibromoethane polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl] 1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, and the like. Examples of commercially available amine-based light stabilizers include ADK STAB LA-52, LA-63P, LA-72, LA-77G, and LA-81 (manufactured by ADEKA CORPORATION), Tinuvin 249, TINUVIN 111FDL, 123, 144, 292, and 5100 (manufactured by BASF), and KAMISTAB 29 (manufactured by Chemipro Chemical Co., Ltd.).

[0044] From the viewpoint of more effective suppression of yellowing, the content of the second component in the composition is preferably 0.3 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the resin component (C).

[0045] In the composition, the mass ratio Ma / Mb of the mass Ma of the first component to the mass Mb of the second component is preferably 0.1 to 10, more preferably 0.3 to 5, and even more preferably 0.5 to 5, from the viewpoint of more effectively suppressing yellowing of a resin or molded article produced using the composition.

[0046] <Third component> The resin component (C) contained in the composition as a third component may be a resin component of a curable resin such as a thermosetting resin or an energy ray curable resin, or a resin component of a thermoplastic resin. Examples of the resin component of the curable resin include monomers, oligomers, prepolymers that constitute the curable resin, and mixtures of two or more of these. In addition to these components and mixtures, there are also those containing polymers thereof. The resin component of the thermoplastic resin may be a thermoplastic resin itself, or a material containing a thermoplastic resin as the main component and further containing a monomer, an oligomer, a prepolymer, or other components depending on the application. The resin component (C) is not particularly limited as long as it is a resin component constituting a resin used in paints, adhesives, coating agents, etc., a resin component constituting a resin used in various molded products such as containers, casings, protective members, and tubes, or a resin component constituting a resin used in films, fibers, etc., and resin components of curable resins such as thermosetting resins and energy ray-curable resins, and resin components of thermoplastic resins can be used. Resin component (C) is preferably a curable resin component, since high-temperature heating is not required to obtain the resin or molded article.

[0047] Examples of the curable resin include polyurethane resin, epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester, allyl resin, silicone resin, furan resin, etc. Among these, at least one of polyurethane resin and epoxy resin is preferred from the viewpoints of transparency, heat resistance, etc. The composition containing the resin component of the curable resin is cured by heating or irradiating with active energy rays, and becomes a resin composition, a resin, or a molded article.

[0048] As the polyurethane resin, a liquid curable compound (polyurethane curing liquid) containing a polyol component and a polyisocyanate component can be used. As the polyol component, polyester polyol, polyether polyol, low molecular weight polyol, etc. can be used. Examples of polyester polyols include polyethylene adipate polyol, polybutylene adipate polyol, polyethylene butylene adipate polyol, polyhexamethylene isophthalate adipate polyol, polyethylene succinate polyol, polybutylene succinate polyol, polyethylene sebacate polyol, polybutylene sebacate polyol, poly-ε-caprolactone polyol, and poly(3-methyl-1,5-pentylene adipate) polyol. Examples of low molecular weight polyols include ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis(hydroxyethyl)cyclohexane, and 2,7-norbornanediol.

[0049] The polyisocyanate component is a compound having at least two isocyanate groups in the molecule, and specific examples include diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluidine diisocyanate, and isophorone diisocyanate, as well as products of these isocyanates with polyols, and tri- or higher functional polyisocyanates produced by condensation of isocyanates. Commercially available polyisocyanate components include, for example, "Coronate HX," "Coronate HL-S," "Coronate L," "Coronate 2031," "Coronate 2030," "Coronate 2037," "Coronate 2234," "Coronate 2785," "Aquanate 200," and "Aquanate 210" manufactured by Tosoh Corporation; and "Sumidur N3300" and "Desmodur" manufactured by Sumika Covestro Urethane Co., Ltd. Examples of commercially available products that can be used include those sold under the trade names "Sumidur N3400" and "Sumidur N-75" manufactured by Asahi Kasei Chemicals Corporation, "Duranate E-405-80T," "Duranate 24A-100," and "Duranate TSE-100" manufactured by Asahi Kasei Chemicals Corporation, and "Takenate D-110N," "Takenate D-120N," "Takenate M-631N," and "MT-Olestar NP1200" manufactured by Mitsui Chemicals, Inc.

[0050] The epoxy resin may be a generally known epoxy resin having two or more glycidyl groups per molecule, such as bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, xylene novolac epoxy resin, bisphenol A novolac epoxy resin, brominated bisphenol A epoxy resin, trifunctional phenol epoxy resin, naphthalene epoxy resin, phenol aralkyl epoxy resin, biphenyl aralkyl epoxy resin, naphthol aralkyl epoxy resin, alicyclic epoxy resin, dicyclopentadiene epoxy resin, and aralkyl novolac epoxy resin.

[0051] The thermoplastic resin is preferably one that can be kneaded at a temperature of 200° C. or less, from the viewpoint of preventing volatilization of the compound (A) and facilitating preparation of the composition. Specific examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, AS resin, ABS resin, polyvinyl chloride, acrylic resin, methacrylic resin, polyvinylidene fluoride, nylon 12, acetal resin, and polycarbonate. Among these, ABS resin, acrylic resin, and methacrylic resin are preferred from the viewpoint of effectively suppressing yellowing of the resin.

[0052] The content of resin component (C) in the composition is preferably 70 to 99 mass%, more preferably 80 to 99 mass%, and even more preferably 90 to 99 mass%, when the total mass of the composition is 100 mass%. When the content of resin component (C) is equal to or greater than the above-mentioned lower limit, the strength of a molded article obtained from the composition is likely to be improved. When the content of resin component (C) in the composition is equal to or less than the above-mentioned upper limit, the contents of compound (A) and antioxidant (B) are relatively high, which makes it easier to more effectively suppress yellowing of a molded article produced using the composition and to improve the storage stability of the composition.

[0053] <Other ingredients> The composition may contain other components in addition to the first to third components. For example, when the resin component (C) is a curable resin, the composition may contain a polymerization initiator.

[0054] The type of the polymerization initiator is not particularly limited and can be appropriately selected depending on the type of curable resin used, etc. Specifically, a radical polymerization initiator is preferred. Examples of the radical polymerization initiator include a thermal radical polymerization initiator that generates radicals by heat and a photoradical polymerization initiator that generates radicals by light.

[0055] Examples of the thermal radical polymerization initiator include organic peroxides such as diacyl peroxides such as benzoyl peroxide; peroxy esters such as t-butyl peroxybenzoate; hydroperoxides such as cumene hydroperoxide; dialkyl peroxides such as dicumyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; peroxy ketals; alkyl peresters; and percarbonates.

[0056] As the photoradical polymerization initiator, commercially available products can be used. Examples include Irgacure (registered trademark, the same applies hereinafter) 651, Irgacure 184, Irgacure 2959, Irgacure 127, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 819, Irgacure 784, Irgacure OXE01, Irgacure OXE02, and Irgacure 754 (all manufactured by BASF). These may be used alone or in combination of two or more.

[0057] When a composition containing a radically polymerizable monomer and a curable resin is used for coating applications, etc., curing is usually carried out in an air atmosphere, and therefore the polymerization reaction is easily inhibited by oxygen in the air. However, the above composition has the advantage that the polymerization reaction is less likely to be inhibited even in air because it contains compound (A).

[0058] The content of the polymerization initiator in the composition is not particularly limited, but in order to more significantly exhibit the effects of the present invention, the content is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the composition, and is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.

[0059] The composition may contain, as appropriate, components other than the first to third components, such as a diluent, a pigment, a dye, a filler, an ultraviolet absorber, a thickener, a shrinkage reducing agent, an antioxidant, a plasticizer, an aggregate, a flame retardant, a stabilizer, a fiber reinforcement material, a leveling agent, and an anti-sagging agent. The composition may also contain, as a diluent, for example, styrene, a (meth)acrylic acid ester, etc. From the viewpoint of polymerizability, the inclusion of a (meth)acrylic acid ester is particularly preferred because the effects of the present invention are more pronounced. Examples of pigments include titanium oxide, red iron oxide, aniline black, carbon black, cyanine blue, and chrome yellow. Examples of fillers include talc, mica, kaolin, calcium carbonate, and clay.

[0060] <Method of producing the composition> The composition can be obtained by mixing the compound (A), at least one of the antioxidant (B1) and the light stabilizer (B2), and the resin component (C). At least one of The composition can be obtained by mixing the resin component (C) and, if necessary, any optional components by stirring in air or in an inert gas atmosphere. When mixing the components, if the resin component (C) is a liquid at room temperature, such as a liquid curable resin, the composition can be prepared by stirring at a temperature of 20 to 60° C. If a resin component (C) that is solid at room temperature, such as a thermoplastic resin, is used, the composition can be prepared by melt-kneading at a temperature of 100 to 300° C.

[0061] <Uses of the composition> The composition can be preferably used for applications such as paints, adhesives, coating agents, various molded articles such as containers, casings, protective members, and tubes, and various electronic material components such as films, fibers, and semiconductor sealants. In particular, the composition can be preferably used for applications requiring suppression of color tone change, such as paints and coating agents, and applications requiring translucency, such as containers, protective members, and films, because the composition provides a yellowing suppression effect.

[0062] [Resin composition and molded article] The resin composition according to the embodiment of the present invention is obtained by curing the composition. The molded article according to the embodiment of the present invention is obtained by molding the above-mentioned composition or resin composition. When molding the composition, molding may be performed while curing the resin component (C), or a composition prepared by melt-kneading may be melted and molded. In the step of curing the resin component (C), there are no particular limitations on the method as long as it can cure the resin component (C), and an appropriate method can be selected and used depending on the type of composition, polymerization initiator, etc. For example, when the composition contains a thermal radical polymerization initiator, a method of curing by heating can be used, and when the composition contains a photoradical polymerization initiator, a method of curing by irradiating with active energy rays such as UV can be used. In addition, when both are contained, the composition may be heated after irradiation with active energy rays. Although it depends on the application, the method of curing by irradiation with active energy rays is preferred because the effects of the present invention are more pronounced. When these radical polymerizable monomers are used for coating applications, etc., curing is usually carried out in an air atmosphere, and therefore the polymerization reaction is likely to be inhibited by oxygen in the air. However, by including the compound (A) described above, inhibition of the polymerization reaction can be easily suppressed. [Example]

[0063] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0064] The evaluation methods of the compositions obtained in the examples and comparative examples are described below. <Change in YI value> The YI values of the molded bodies obtained in each example and comparative example were measured using a spectrophotometer (UV3600 manufactured by Shimadzu Corporation) in accordance with JIS K7373. Next, using a super UV tester (manufactured by Iwasaki Electric Co., Ltd.: SUV-w161), at a black panel temperature of 60 °C, a relative humidity of 50%, and an irradiation energy of 100 mW / cm 2 After irradiating with ultraviolet rays for 72 h under the conditions, the YI value was measured again in the same procedure. Then, the difference in the YI value before and after ultraviolet irradiation was calculated and taken as the change in the YI value (ΔYI). The smaller ΔYI is, the less likely it is to yellow.

[0065] The raw materials and compounds used in the examples and comparative examples are as follows. <Resin component (C)> A urethane curing solution containing the following components · Isocyanate compound: Coronate 2037 (manufactured by Tosoh Corporation) · 1,4-Butanediol (BDO) (manufactured by Fujifilm Wako Pure Chemical Corporation) · Poly(3-methyl-1,5-pentylene adipate) polyol: P-2010 (manufactured by Kuraray Co., Ltd.)

[0066] <Compound (A)> · Compound (A-1): 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane · Compound (A-2): α-(3-methyl-2-butenoxy)-ω-hydroxypoly[oxy(3-methyl-2-butenoxymethylethane-1,2-diyl)]

[0067] <Antioxidant (B1)> · Hindered phenol-based antioxidant: Irganox1010 (manufactured by BASF) <Light stabilizer (B2)> · Amine-based light stabilizer: Adeka Stab LA-52 (manufactured by Adeka Corporation) <Phosphorus-based antioxidant> · Adeka Stab PEP-36 (manufactured by Adeka Corporation)

[0068] Compounds (A-1) and (A-2) were synthesized by the following method. [Production Example 1] (Production of Compound (A-1)) A reactor equipped with a stirrer, thermometer, and dropping funnel was charged with 61.8 g (0.717 mol) of 3-methyl-2-buten-1-ol and 36.84 g (0.657 mol) of potassium hydroxide under a nitrogen stream. While maintaining the internal temperature below 10°C, 19.34 g (0.209 mol) of epichlorohydrin was added dropwise with stirring. After the addition, the temperature was raised to 50°C. The internal temperature was stirred at 50°C for 6 hours and then cooled to 25°C. The reaction solution was neutralized with 4 M aqueous hydrochloric acid, and the upper layer was washed with 310 mL of ion-exchanged water. The resulting organic layer was purified by distillation to obtain 28.77 g (0.126 mol; yield 60.3%) of 1,3-bis(3-methyl-2-butenoxy)-2-hydroxypropane represented by the following formula (A-1).

[0069] [ka]

[0070] [Production Example 2] (Production of Compound (A-2)) A reactor equipped with a stirrer, thermometer, and dropping funnel was charged with 1654 g (19.2 mol) of 3-methyl-2-buten-1-ol, 1842 g (23.0 mol) of 50% aqueous sodium hydroxide, and 28 g (0.084 mol) of dodecylbenzyldimethylammonium chloride under a nitrogen stream. While maintaining the internal temperature below 60°C, 1776 g (19.2 mol) of epichlorohydrin was added dropwise with stirring. After the addition was completed, the temperature was raised to 90°C. The internal temperature was stirred at 90°C for 9 hours and then cooled to 25°C. The reaction solution was washed with 5000 g of 7.5% aqueous sodium bicarbonate, and the upper layer was washed with 5000 mL of ion-exchanged water. Water and unreacted 3-methyl-2-buten-1-ol were removed from the resulting organic layer by distillation, yielding 1,996 g (73% yield) of α-(3-methyl-2-butenoxy)-ω-hydroxypoly[oxy(3-methyl-2-butenoxymethylethane-1,2-diyl)] represented by the general formula (A-2). GPC measurement showed that the number average molecular weight of the resulting compound was 300 and the weight average molecular weight was 360 (polystyrene equivalent).

[0071] [ka]

[0072] <Examples 1 to 3 and Comparative Examples 1 to 6> Compositions were prepared by mixing the components at room temperature according to the formulations listed in Table 1. Each composition was then poured into a rectangular SUS304 mold measuring 50 mm wide x 50 mm deep x 1 mm thick, and heated at 70°C under normal pressure to mold and cure the composition into a molded product. Table 1 shows the evaluation results of the molded products obtained from each composition.

[0073] [Table 1]

[0074] As is clear from the results in Table 1, in Example 1, in which the compound (A) having the structure represented by the general formula (I) was used in combination with the antioxidant (B1) or the light stabilizer (B2), ~3It can be seen that the molded articles produced using this composition have a smaller change in YI value and are less prone to yellowing than the molded articles produced using the compositions of Comparative Examples 2, 5, and 6 which do not contain compound (A). Furthermore, as is clear from the comparison of Examples 1 and 2 with Comparative Example 3, and the comparison of Example 3 with Comparative Example 4, it is found that the combined use of compound (A) with antioxidant (B1) or light stabilizer (B2) can further reduce the change in the YI value of the molded article compared to a composition using compound (A) alone. Furthermore, as is clear from a comparison between Examples 1 and 2 and Comparative Example 1, it is found that the molded article produced using a composition containing compound (A) in combination with an antioxidant other than a phosphorus-based antioxidant or a light stabilizer can reduce the change in YI value compared to the molded article produced using a composition containing compound (A) in combination with a phosphorus-based antioxidant.

Claims

1. A composition comprising, as a first component, a compound (A) having a structure represented by the following general formula (I): an antioxidant (B1) other than a phosphorus-based antioxidant and / or a light stabilizer (B2), as a second component; and a resin component (C) as a third component, wherein a mass ratio Ma / Mb of a mass Ma of the first component to a mass Mb of the second component is 0.1 to 10: 【Chemical 1】 (In general formula (I), R １ and R ２ R each independently represents an alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group. ３ and R ４ each independently represents a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.

2. R in the general formula (I) １ and R ２ and each independently represent an alkyl group having 1 to 4 carbon atoms.

3. The composition according to claim 1, wherein the compound (A) is a compound having a structure represented by the following general formula (II): 【Chemistry 2】 (In general formula (II), R ５ and R ６ R each independently represents an alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group. ７ and R ８ R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group, or an aralkyl group. ９ represents a hydrogen atom; a (meth)acryloyl group; an alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; an aryl group; or an aralkyl group.

4. The composition according to any one of claims 1 to 3, comprising a phenolic antioxidant as the second component.

5. The composition according to any one of claims 1 to 4, comprising 0.1 to 5 parts by mass of the first component and 0.1 to 5 parts by mass of the second component per 100 parts by mass of resin component (C).

6. The composition according to any one of claims 1 to 5, wherein a mass ratio Ma / Mb of the mass Ma of the first component to the mass Mb of the second component is 0.3 to 5.

7. The composition according to any one of claims 1 to 6, wherein the resin component (C) is a resin component of a curable resin.

8. The composition according to claim 7, wherein the curable resin is at least one of a polyurethane resin and an epoxy resin.

9. A resin composition obtained by curing the composition according to claim 7 or 8.

10. A molded article comprising the composition according to any one of claims 1 to 8 or the resin composition according to claim 9.

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