Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
  • C08G65/24—Epihalohydrins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3206—Polyhydroxy compounds aliphatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
  • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
  • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/6795—Unsaturated polyethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
  • C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
  • C08G65/3312—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group acyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/005—Stabilisers against oxidation, heat, light, ozone
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
  • C08K5/134—Phenols containing ester groups
  • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3432—Six-membered rings
  • C08K5/3435—Piperidines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/06—Polyurethanes from polyesters

Definitions

• the present invention relates to a composition containing a specific unsaturated double bond-containing compound, a resin composition, and a molded product containing the same.
• Resin is widely used in various fields as films, coating materials, fibers, various molded bodies, and the like.
• molded products made of resin alone and the above-mentioned various resin products cannot withstand long-term use due to deterioration due to reaction with oxygen in the air triggered by heat or ultraviolet rays. Has been done. Therefore, in order to prevent resin deterioration due to light, particularly ultraviolet rays and oxygen, a light stabilizer, an ultraviolet absorber, an antioxidant and the like are blended with the resin and used.
• Patent Document 1 proposes the addition of a phosphorus-based antioxidant in order to prevent yellowing of a composition containing a phenol resin.
• Patent Document 2 proposes a novel phenol-based antioxidant for preventing oxidative deterioration of a resin such as yellowing.
• Patent Document 3 proposes the addition of a hindered amine-based light stabilizer in order to improve the weather resistance of the polyurethane / acrylic resin composition.
• phosphorus-based antioxidants are susceptible to hydrolysis, phenol-based antioxidants may oxidize themselves and cause yellowing, and hindered amine-based photostabilizers are compatible with resins. There is a problem that the resin that can be blended is limited. As described above, conventional antioxidants and light stabilizers have various problems. Therefore, there is a demand for antioxidants and light stabilizers that solve these problems.
• Patent Document 4 proposes a resin composition containing a specific unsaturated double bond-containing compound having oxygen absorption performance.
• An object of the present invention is to provide a composition, a resin composition, and a molded product containing them, which exhibit an excellent effect of suppressing yellowing.
• the present inventors have selected a compound having a specific structure containing an unsaturated double bond and at least one of a specific antioxidant and a light stabilizer. We have found that a composition exhibiting an excellent yellowing inhibitory effect can be obtained by using them in combination, and completed the present invention.
• the present invention provides the following [1] to [10].
• a composition comprising at least one of them as a second component and a resin component (C) as a third component.
• R 1 and R 2 each independently represent 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.
• R4 independently represent 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.
• R 5 and R 6 each independently represent 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.
• R 8 independently represent 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;
• R 9 represents a hydrogen atom; (meth).
• composition according to. [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.
• the resin component (C) is a resin component of a curable resin.
• the curable resin is at least one curable resin among a polyurethane resin and an epoxy resin.
• the present invention it is possible to provide a composition, a resin composition, and a molded product thereof, which exhibit an excellent effect of suppressing yellowing.
• composition contains a compound (A) containing a structure represented by the following general formula (I) as a first component, and is an antioxidant (B1) different from a phosphorus-based antioxidant.
• the composition comprises at least one of the photostabilizer (B2) and the light stabilizer (B2) as the second component, and the resin component (C) as the third component.
• R 1 and R 2 each independently represent 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.
• R4 independently represent 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.
• the above-mentioned specific compound (A) having an unsaturated double bond is used in combination with at least one of an antioxidant (B1) and a light stabilizer (B2) different from the phosphorus-based antioxidant.
• B1 an antioxidant
• B2 a light stabilizer
• the yellowing of the resin is mainly due to the oxidation of the resin.
• Oxidation of the resin is a reaction in which the alkyl radical (R ⁇ ) generated by [i] ultraviolet rays or the like reacts with oxygen to generate a peroxide radical (ROO ⁇ ) (hereinafter referred to as the first reaction).
• ROO ⁇ peroxide radical
• Extracts hydrogen from the resin skeleton to generate R. which itself becomes hydroperoxide (ROOH), and ROOH further decomposes to generate new radicals, thereby accelerating oxidation. It proceeds by a cycle of reaction (hereinafter referred to as a second reaction).
• ROO and ROOH hydroperoxide
• antioxidants and light stabilizers exhibit antioxidant effects by decomposing or quenching ROO and ROOH, which are factors that cause the second reaction to proceed.
• antioxidants and light stabilizers Then, the first reaction for producing ROO ⁇ cannot be stopped, and there is a problem that a certain amount of oxidation proceeds.
• the compound (A) has oxygen absorption, when it is blended with the resin component (C), the generation of ROO ⁇ , which is a factor of the resin oxidation cycle, is reduced, and the first Reaction can be suppressed. Therefore, by using the existing antioxidant or light stabilizer that suppresses the second reaction in combination with the compound (A), both the first reaction and the second reaction are suppressed, and the existing oxidation It is considered to exhibit a better yellowing suppressing effect that cannot be achieved by an inhibitor or a light stabilizer.
• the compound (A) contained as the first component in the above composition is a compound containing a structure represented by the general formula (I). As described above, the compound (A) has oxygen absorption and suppresses the reaction between oxygen and the alkyl radical generated in the resin or the molded body due to ultraviolet rays or the like.
• R 1 and R 2 independently represent 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 of the alkyl group having 1 to 6 carbon atoms represented by R 1 and R 2 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 and a tert-butyl group. Examples thereof include a group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
• Examples of the alkenyl group having 2 to 6 carbon atoms represented by R 1 and R 2 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 and a hexenyl group (cis-). 3-Hexenyl group, etc.), cyclohexenyl group, etc. can be mentioned.
• Examples of the aryl group represented by R 1 and R 2 include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like.
• Examples of the aralkyl group represented by R 1 and R 2 include a benzyl group, a 2-phenylethyl group, a 2-naphthylethyl group, a diphenylmethyl group and the like.
• R 1 and R 2 are each from the viewpoint of more effectively suppressing the yellowing of the resin or the molded product produced by using the composition and from the viewpoint of improving the storage stability of the composition, respectively.
• it is 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 further preferably a methyl group. ..
• R 3 and R 4 independently represent 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.
• the 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 R 3 and R 4 are the same as those for R 1 and R 2 above. , Omit duplicate explanations.
• R 3 and R 4 are each independently 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, preferably a hydrogen atom or an aryl group. It is more preferably a methyl group, and even more preferably a hydrogen atom. Above all, from the viewpoint of improving the oxygen absorption performance of the obtained polymer, it is preferable that both R 3 and R 4 are hydrogen atoms.
• the compound (A) containing the structure represented by the general formula (I) is described below from the viewpoint of more effectively suppressing yellowing of the resin or the molded product and improving the storage stability of the composition. It is preferable that the compound contains a structure represented by the general formula (II) or a compound represented by any of the following general formulas (III) to (V), and the following general formula (III) or the following general formula is used. It is more preferable that the compound is represented by (V).
• R 5 and R 6 each independently represent 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.
• R 8 independently represent 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;
• R 9 represents a hydrogen atom; (meth).
• Acryloyl group alkyl group having 1 to 6 carbon atoms; alkenyl group having 2 to 6 carbon atoms; aryl group; or aralkyl group.
• R 5 , R 6 , R 7 and R 8 are the same as those for R 1 , R 2 , R 3 and R 4 in general formula (I), respectively, and overlap. The explanation is omitted.
• the (meth) acryloyl group represented by R 9 represents an acryloyl group or a meta-acryloyl group.
• 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.
• R 10 , R 11 , R 16 and R 17 are independently alkyl groups having 1 to 6 carbon atoms; alkenyl groups having 2 to 6 carbon atoms; aryl groups; or aralkyl groups.
• R 12 and R 13 independently represent 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.
• R 14 represents a hydrogen atom or a methyl group
• R 15 represents a hydroxyl group; a (meth) acryloyloxy group; a 4-vinylphenoxy group; or an alkenyloxy group having 2 to 6 carbon atoms.
• R 10 , R 11 , R 12 and R 13 are the same as those for R 1 , R 2 , R 3 and R 4 in the general formula (I), respectively, and the explanations overlap. Is omitted.
• R 14 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
• R 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.
• examples of the (meth) acryloyloxy group represented by R15 include an acryloyloxy group and a metaacryloyloxy group.
• the alkenyloxy group having 2 to 6 carbon atoms represented by R15 includes a vinyloxy group, an allyloxy group, a 1-propenyloxy group, an isopropenyloxy group, a 1-butenyloxy group and a 2-butenyloxy group.
• R 16 and R 17 each independently represent 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, and examples thereof may be used. Preferred ones are the same as those described in R1 and R2 in the general formula (I). Among these, R 16 and R 17 are preferably alkyl groups having 1 to 6 carbon atoms or alkenyl groups having 2 to 6 carbon atoms, respectively, and are alkyl groups having 1 to 4 carbon atoms, respectively. Is more preferable, and it is further preferable that it is a methyl group.
• R 18 represents a hydrogen atom or a methyl group
• R 19 represents a hydroxyl group; a (meth) acryloyloxy group; a styryloxy group; or an alkenyloxy group having 2 to 5 carbon atoms.
• the compound represented by the general formula (V) has a polystyrene-equivalent weight average molecular weight (Mw) of 200 to 50,000.
• the method for producing the compound is not particularly limited, and the compound can be produced by applying a known method alone or in combination.
• the content of the compound (A) in the composition is preferably 30 parts by mass or less with respect to 100 parts by mass of the resin component (C) from the viewpoint of facilitating the expression of the characteristics derived from the resin component (C). 10 parts by mass or less is more preferable, 5 parts by mass or less is further preferable, 3 parts by mass or less is further preferable, and in order to obtain a sufficient yellowing suppressing effect, 0.1 parts by mass or more is preferable, and 0.2 parts by mass is preferable. More than parts by mass is more preferable, more than 0.3 parts by mass is further preferable, and more than 0.5 parts by mass is even more preferable.
• an antioxidant (B1) different from the phosphoric acid-based antioxidant (hereinafter, may be simply referred to as “antioxidant (B1)”) and a light stabilizer (B2). Including at least one of them.
• the second component functions to quench peroxide radicals and hydroperoxides.
• the antioxidant (B1) different from the phosphoric acid-based antioxidant include phenol-based antioxidants, sulfur-based antioxidants, hydroxylamine-based antioxidants, ascorbic acids, and nitrites.
• a phenolic antioxidant is preferable from the viewpoint of more effectively suppressing yellowing of the resin or molded product produced by using the composition.
• antioxidants include Irganox 1010, Irganox 1076, Irganox 1330, Irganox 3114, Irganox 3125 (above, manufactured by BASF), ADEKA STAB AO-60, and ADEKA STAB AO-80 (above, Co., Ltd.).
• the compound (A) suppresses the generation of peroxide radicals by removing oxygen, whereby the yellowing of the resin is suppressed to some extent.
• the antioxidant (B1) or the light stabilizer (B2) sufficiently suppresses the yellowing of the resin by quenching the peroxide radical generated from oxygen that could not be completely removed by the compound (A). It is thought that it can be done.
• the phosphorus-based antioxidant has a function of quenching a hydroperoxide, which is a product of quenching a peroxide radical, into a stable compound, but has a poor function of quenching the peroxide radical itself, and therefore the compound (A). ) Cannot provide a sufficient effect of suppressing yellowing.
• a phosphoric acid-based antioxidant may be contained together with the above-mentioned antioxidant (B1), but it is preferable to reduce the content thereof from the viewpoint of minimizing the hydrolysis of the phosphoric acid-based antioxidant.
• the content of the phosphoric acid-based antioxidant is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, still more preferably 0% by mass, based on the total mass of the composition.
• 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 and 1,6-bis (2,2).
• amine-based light stabilizers examples include ADEKA STUB LA-52, LA-63P, LA-72, LA-77G, LA-81, (manufactured by ADEKA Corporation), Tinuvin249, TINUVIN111FDL, 123, 144, 292. 5100 (manufactured by BASF), KAMISTAB29, (manufactured by Chemipro Kasei Co., Ltd.) and the like can be mentioned.
• the content of the second component in the above composition is preferably 0.3 to 5 parts by mass with respect to 100 parts by mass of the resin component (C) from the viewpoint of more effectively suppressing yellowing. It is preferably 0.3 to 3 parts by mass, and more preferably 0.5 to 3 parts by mass.
• the mass ratio Ma / Mb of the mass Ma of the first component and the mass Mb of the second component is more effective for yellowing of the resin or the molded product produced by using the composition. From the viewpoint of suppressing the above, it is preferably 0.1 to 10, more preferably 0.3 to 5, and even more preferably 0.5 to 5.
• 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
• the resin component of the curable resin include monomers, oligomers, prepolymers constituting the curable resin, and mixtures of two or more of these, and further, in addition to these components and mixtures, their polymerization. Some include things.
• the resin component of the thermoplastic resin include the thermoplastic resin itself, or a resin containing the thermoplastic resin as a main component and further containing a monomer, an oligomer, a prepolymer and other components depending on the intended use.
• the resin component (C) includes a resin component that constitutes a resin used for paints, adhesives, coating agents, etc., and a resin component that constitutes a resin used for various molded products such as containers, housings, protective members, and tubes.
• a resin component constituting the resin used for films, fibers, etc. and a curable resin component such as a thermosetting resin or an energy ray curable resin or a resin component of a thermoplastic resin should be used. Can be done. From the viewpoint that heating at a high temperature is not required to obtain a resin or a molded product, the resin component of the curable resin is preferable as the resin component (C).
• the curable resin examples include polyurethane resin, epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester, allyl resin, silicon resin, furan resin and the like. Of these, at least one of a polyurethane resin and an epoxy resin is preferable from the viewpoint of transparency and heat resistance.
• the composition containing the resin component of the curable resin is cured by heating or irradiating with active energy rays to become a resin composition, a resin, or a molded product.
• polyurethane resin a liquid curable compound (polyurethane curing liquid) containing a polyol component and a polyisocyanate component can be used.
• polyol component a polyester polyol, a polyether polyol, a low molecular weight polyol or the like can be used.
• polyester polyol examples 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, Examples thereof include poly- ⁇ -caprolactone polyols and poly (3-methyl-1,5-pentylene adipate) polyols.
• low molecular weight polyols examples 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, Examples thereof include 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis (hydroxyethyl) cyclohexane, and 2,7-norbornandiol.
• the polyisocyanate component is a compound having at least two or more isocyanate groups in the molecule, and specifically, for example, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, etc.
• Diisocyanates such as naphthylene-1,5-diisocyanate, o-toluidine diisocyanate, and isophorone diisocyanate, products of these isocyanates and polyols, and trifunctional or higher polyisocyanates produced by condensation of isocyanates. Can be mentioned.
• epoxy resin a generally known epoxy resin having two or more glycidyl groups in one molecule can be used. Specifically, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, xylene novolak type epoxy resin, bisphenol A novolak Type epoxy resin, brominated bisphenol A type epoxy resin, trifunctional phenol type epoxy resin, naphthalene type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, alicyclic epoxy resin, dicyclo Examples thereof include a pentadiene type epoxy resin and an aralkylnovolac type epoxy resin.
• the thermoplastic resin is preferably one that can be kneaded at a temperature of 200 ° C. or lower from the viewpoint of preventing the volatilization of the compound (A) and facilitating the preparation of the composition.
• the thermoplastic resin include polyethylene, polypropylene, polystyrene, AS resin, ABS resin, polyvinyl chloride, acrylic resin, methacrylic resin, polyvinylidene fluoride, nylon 12, acetal resin, polycarbonate and the like.
• ABS resin, acrylic resin, and methacrylic resin are preferable from the viewpoint of effectively suppressing yellowing of the resin.
• the content of the resin component (C) in the composition is preferably 70 to 99% by mass, more preferably 80 to 99% by mass, based on 100% by mass of the entire composition. It is more preferably 90 to 99% by mass.
• the content of the resin component (C) is at least the above lower limit value, it becomes easy to improve the strength of the molded product obtained from the composition.
• the content of the resin component (C) in the composition is not more than the above upper limit, the contents of the compound (A) and the antioxidant (B) are relatively large, so that the composition is used. It becomes easier to suppress the yellowing of the molded product produced in the above-mentioned manner more effectively, and it becomes easier to improve the storage stability of the composition.
• the above composition may contain components other than the first to third components as other components.
• the resin component (C) is a curable resin
• the composition may contain a polymerization initiator.
• the type of the above-mentioned polymerization initiator is not particularly limited and can be appropriately selected depending on the type of the curable resin used and the like, but specifically, a radical polymerization initiator is preferable.
• a radical polymerization initiator examples include a thermal radical polymerization initiator that generates radicals by heat, a photoradical polymerization initiator that generates radicals by light, and the like.
• thermal radical polymerization initiator examples include diacyl peroxides such as benzoyl peroxide; peroxyesters such as t-butylperoxybenzoate; hydroperoxides such as cumenehydroperoxide; dialkyl peroxides such as dicumyl peroxide; methylethylketone peroxides and acetylacetones.
• diacyl peroxides such as benzoyl peroxide
• peroxyesters such as t-butylperoxybenzoate
• hydroperoxides such as cumenehydroperoxide
• dialkyl peroxides such as dicumyl peroxide
• methylethylketone peroxides and acetylacetones ketotone peroxides such as peroxides Peroxides; peroxyketals; alkyl peresters; organic peroxides such as percarbonates can be mentioned.
• a commercially available product can be used as the photoradical polymerization initiator.
• Irgacure registered trademark, the same shall apply hereinafter
• Irgacure 184 Irgacure 2959, Irgacure 127, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 819, Irgacure 784, Irgacure OXE01, Irgacure OXE02, Irgacure OXE02, Irgacure SF4 and above.
• Etc. can be mentioned. These may be used alone or in combination of two or more.
• compositions containing a radically polymerizable monomer and a curable resin When a composition containing a radically polymerizable monomer and a curable resin is used for paint applications, etc., it is usually cured in an air atmosphere, so that the polymerization reaction is easily inhibited by oxygen in the air.
• the composition contains the compound (A), there is an advantage that the polymerization reaction is less likely to be inhibited even in the air.
• the content of the polymerization initiator in the above composition is not particularly limited, but it is 0.001 part by mass or more with respect to 100 parts by mass of the composition because the effect of the present invention is more remarkable. It is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less. ..
• compositions as components other than the first to third components, diluents, pigments, dyes, fillers, ultraviolet absorbers, thickeners, hyposhrinkants, antiaging agents, plasticizers, aggregates, etc.
• a flame retardant, a stabilizer, a fiber reinforcing material, a leveling agent, an anti-dripping agent and the like may be appropriately contained.
• the composition may contain, for example, styrene, (meth) acrylic acid ester or the like as a diluent, and the effect of the present invention is more remarkable when the (meth) acrylic acid ester is contained from the viewpoint of polymerizable property. It is particularly preferable because it is used.
• the pigment include titanium oxide, red iron oxide, aniline black, carbon black, cyanine blue, chrome yellow and the like.
• the filler include talc, mica, kaolin, calcium carbonate, clay and the like.
• 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). Specifically, the compound (A), the antioxidant (B1) and the light stabilizer (B2), the resin component (C), and if necessary, any component are stirred in the air or in an atmosphere of an inert gas.
• the composition can be obtained by mixing with.
• the resin component (C) is liquid at room temperature, such as a liquid curable resin
• the composition should be prepared by stirring at a temperature of 20 to 60 ° C. Can be done.
• the resin component (C) 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.
• composition is preferably used, for example, in various molded products such as paints, adhesives, coating agents, containers, housings, protective members, tubes, and electronic material parts such as films, fibers, and semiconductor encapsulants. be able to.
• various molded products such as paints, adhesives, coating agents, containers, housings, protective members, tubes, and electronic material parts such as films, fibers, and semiconductor encapsulants.
• the above composition has an effect of suppressing yellowing. Therefore, it can be used particularly preferably.
• the resin composition according to the embodiment of the present invention is obtained by curing the composition.
• the molded product according to the embodiment of the present invention can be obtained by molding the above composition or resin composition.
• molding may be performed while curing the resin component (C), or the composition prepared by melt-kneading may be melted and molded.
• the method is not particularly limited as long as the resin component (C) can be cured, and an appropriate method may be selected and used according to the type of the composition and the polymerization initiator. can.
• the composition contains a thermal radical polymerization initiator
• a method of heating and curing may be mentioned
• a method of irradiating with active energy rays such as UV to cure the composition
• heating may be performed after irradiation with active energy rays.
• the method of irradiating with active energy rays to cure is preferable.
• these radically polymerizable monomers are used for paint applications, etc., they are usually cured in an air atmosphere, so that the polymerization reaction is easily inhibited by oxygen in the air. It becomes easy to suppress the inhibition of the reaction.
• ⁇ Change in YI value> The YI value of the molded product obtained in each Example and Comparative Example was measured using a spectrophotometer (UV3600 manufactured by Shimadzu Corporation) according to JIS K7373. Next, using a super UV tester (manufactured by Iwasaki Electric Co., Ltd .: SUV-w161), ultraviolet rays were irradiated for 72 hours under the conditions of a black panel temperature of 60 ° C., a relative humidity of 50%, and an irradiation energy of 100 mW / cm 2 , and then again. The YI value was measured by the same procedure. Then, the difference in the YI value before and after the ultraviolet irradiation was calculated and used as the change in the YI value ( ⁇ YI). The smaller ⁇ YI is, the less likely it is to turn yellow.
• the reaction solution was neutralized with a 4M aqueous hydrochloric acid solution, and the upper layer was washed with 310 mL of ion-exchanged water.
• the obtained organic layer is purified by distillation, and 28.77 g (0.126 mol; 0.126 mol; 1,3-bis (3-methyl-2-butenoxy) -2-hydroxypropane represented by the following formula (A-1); Yield 60.3%) was obtained.
• Examples 1 to 3 Comparative Examples 1 to 6> A composition was prepared by mixing each component at room temperature according to the formulation shown in Table 1. Then, each of the obtained compositions is injected into a SUS304 molded mold having a width of 50 mm, a depth of 50 mm, and a thickness of 1 mm, and heated under the conditions of a temperature of 70 ° C. and a normal pressure to obtain each composition. A molded product was produced by molding while curing. Table 1 shows the evaluation results of the molded product obtained from each composition.
• Example 1 the composition of Example 1 in which the compound (A) having the structure represented by the general formula (I) and the antioxidant (B1) or the light stabilizer (B2) are used in combination.
• the molded product prepared using the above has a smaller change in YI value and is less likely to turn yellow. I understand.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=80118681

Family Applications (1)

Country Status (7)

Cited By (3)

Citations (10)

Family Cites Families (12)

• 2021
  • 2021-07-30 KR KR1020237004140A patent/KR20230048030A/ko active Pending
  • 2021-07-30 US US18/019,648 patent/US20230287199A1/en active Pending
  • 2021-07-30 JP JP2022541497A patent/JP7722996B2/ja active Active
  • 2021-07-30 WO PCT/JP2021/028222 patent/WO2022030368A1/ja not_active Ceased
  • 2021-07-30 CN CN202180057112.9A patent/CN116075550A/zh active Pending
  • 2021-07-30 EP EP21853896.5A patent/EP4194513A4/en active Pending
  • 2021-08-06 TW TW110129035A patent/TWI907476B/zh active

Patent Citations (10)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events