JP2022008048A - Additives for resins, their manufacturing methods and molded products - Google Patents

Abstract

[Problem] To provide a resin additive that has excellent dispersibility in resin while also having excellent sustained release of an organic ultraviolet absorber and/or radical scavenger, a method for producing the same, and a molded article containing the resin additive. [Solution] The resin additive includes porous particles, an organic ultraviolet absorber and/or radical scavenger incorporated in the porous particles, and a siloxane cured product in which the organic ultraviolet absorber and/or radical scavenger is sealed within the porous particles. [Selected Figure] Figure 1

Description

The present invention relates to an additive for a resin, a method for producing the same, and a molded product.

Conventionally, it has been known to improve the light resistance of a resin molded body by blending a resin with an additive for a resin such as an organic ultraviolet absorber and a radical scavenger.

For example, it has been proposed to knead a powder containing porous silica, an ultraviolet absorber incorporated into the porous silica, and silicone oil that coats the surface of the porous silica into a resin (for example,). See Patent Document 1 below.).

Jikkenhei 1-70831 Gazette

However, when the powder of Patent Document 1 is kneaded into the resin, the ultraviolet absorber is rapidly released, which causes problems such as deterioration of the light resistance of the molded product and bleeding out of the ultraviolet absorber. be.

Further, excellent dispersibility of the powder in the resin is also required.

The present invention provides a molded product containing an additive for resin, a method for producing the same, and an additive for resin, which are excellent in dispersibility in resin but also excellent in sustained release of organic ultraviolet absorber and / or radical scavenger. offer.

In the present invention (1), the porous particles, the organic ultraviolet absorber and / or the radical scavenger incorporated into the porous particles, and the organic ultraviolet absorber and / or the radical scavenger are made porous. Contains additives for resins, including cured siloxanes that seal in the particles.

In the present invention (2), the cured siloxane product is -SiR ₂ O- (two Rs may be the same or different from each other, and are monovalent saturated hydrocarbon groups and monovalent aromatic hydrocarbons, respectively. It does not contain the siloxane unit represented by at least one monovalent hydrocarbon group selected from the group consisting of groups), but contains an RO group (R indicates a monovalent saturated hydrocarbon group). The resin additive according to (1), which comprises a cured product of a siloxane composition containing a first oligomer containing an RO group-containing siloxane unit.

The present invention (3) is for the resin according to (1) or (2), wherein the cured siloxane product contains a cured product of a siloxane composition containing a second oligomer which is a condensation polymer of tetrafunctional organosilane. Contains additives.

In the present invention (4), the siloxane composition is -SiR ₂ O- (two Rs may be the same or different from each other, and a monovalent saturated hydrocarbon group and a monovalent aromatic hydrocarbon, respectively. Contains a siloxane unit represented by at least one monovalent hydrocarbon group selected from the group consisting of groups) and an RO group containing an RO group (R represents a monovalent saturated hydrocarbon group). The resin additive according to (2) or (3), which contains a third oligomer containing a siloxane unit.

In the present invention (5), the siloxane composition is -SiR ₂ O- (two Rs may be the same or different from each other, and a monovalent saturated hydrocarbon group and a monovalent aromatic hydrocarbon, respectively. The item according to any one of (2) to (4), further containing a silicone oil containing a siloxane unit represented by (1), which indicates at least one monovalent hydrocarbon group selected from the group consisting of groups. Contains additives for resins.

The present invention (6) contains the resin additive according to any one of (1) to (5), wherein the porous particles have an oil absorption amount of 80 mL / 100 g or more.

The present invention (7) includes the resin additive according to any one of (1) to (6), wherein the porous particles are inorganic particles.

The present invention (8) contains the resin additive according to (7), wherein the inorganic particles contain silica-based particles.

In the present invention (9), the porous particles in which the organic ultraviolet absorber and / or the radical trapping agent are sealed with the siloxane cured product are surface-treated with the RO group-containing silane compound, and the RO group-containing silane compound is prepared. Indicates an RO group (R represents at least one monovalent hydrocarbon group selected from the group consisting of a monovalent saturated hydrocarbon group and a monovalent aromatic hydrocarbon group) and the RO group. Includes the resin additive according to (8), which comprises said moiety that is reactive and / or compatible with the resin.

In the present invention (10), the first step of blending the porous particles, the organic ultraviolet absorber and / or the radical scavenger, and the siloxane composition, and the curing of the siloxane composition, the siloxane cured product thereof. The present invention comprises a method for producing an additive for a resin, comprising a second step of sealing the organic ultraviolet absorber and / or the radical scavenger in the porous particles.

According to the present invention (11), the resin according to (10), wherein in the first step, the organic ultraviolet absorber is blended into the porous particles, and then the radical scavenger is blended into the porous particles. Includes a method for producing additives for use.

The present invention (12) further comprises a third step of surface-treating the porous particles in which the organic ultraviolet absorber and / or the radical trapping agent is sealed with the siloxane cured product with a RO group-containing silane compound. , The RO group-containing silane compound is an RO group (R represents at least one monovalent hydrocarbon group selected from the group consisting of monovalent saturated hydrocarbon groups and monovalent aromatic hydrocarbon groups). The method for producing an additive for a resin according to (10) or (11), which comprises the portion other than the RO group and which is capable of reacting with and / or being compatible with the resin.

The present invention (13) includes a molded product containing a resin and the resin additive according to any one of (1) to (9).

The resin additive of the present invention obtained by the production method of the present invention is excellent in dispersibility in the resin, and is also excellent in sustained release of the organic ultraviolet absorber and / or radical scavenger. Therefore, the molded product of the present invention molded from the resin additive and the resin composition containing the resin is excellent in light resistance.

FIG. 1 shows the shapes and dimensions of tensile test pieces to be subjected to tensile tests of Examples 1 to 16 and Comparative Examples 1 to 4.

<Additives for resin>
The additive for resin of the present invention is an additive added to a resin and is an additive contained in a resin composition (resin molded body). Additives for resins include porous particles, organic UV absorbers and / or radical scavengers, and cured siloxanes.

<Porous particles>
Porous particles are carriers (bases) that take up organic UV absorbers and / or radical scavengers.

The specific surface area of the porous particles is, for example, 100 m ² / g or more, preferably 200 m ² / g or more, and 1000 m ² / g or less. The specific surface area of the porous particles is measured according to the BET method (nitrogen adsorption method). The oil absorption of the porous particles is, for example, 80 mL / 100 g or more, preferably 150 mL / 100 g or more, more preferably 200 mL / 100 g or more, and for example, 500 mL / 100 g or less. The oil absorption of the inorganic particles is measured according to JIS K 5101-13.2. When the oil absorption of the porous particles is equal to or higher than the above-mentioned lower limit, an organic ultraviolet absorber and / or a radical catching agent can be reliably taken in, and a siloxane cured product that seals them can also be supported.

The outer shape of the porous particles is not particularly limited, and examples thereof include a substantially spherical shape, a substantially plate shape (leaf piece shape), a substantially needle shape, a substantially polyhedral shape (tetrahedron, hexahedron (cube, etc.), etc.). From the viewpoint of obtaining excellent dispersibility, a substantially spherical shape and a substantially plate shape can be mentioned. Further, the porous particles have pores on the surface, and the pores communicate the outside and the inside, and can include hollow spherical particles having a hollow inside.

The median diameter of the porous particles is, for example, 0.5 μm or more, preferably 1 μm or more, more preferably 2 μm or more, and for example, 50 μm or less, preferably 20 μm or less, more preferably 10 μm or less. be. The median diameter of the porous particles is measured by laser diffraction. When the median diameter of the porous particles is not less than the above-mentioned lower limit and not more than the upper limit, the dispersibility of the resin additive with respect to the resin is excellent.

The porous particles are not particularly limited, and examples thereof include inorganic particles, organic particles (cellulose-based particles, etc.), composite particles thereof, and the like. These can be used alone or in combination. Preferred examples of the porous particles include inorganic particles.

Examples of the inorganic particles include silica-based particles (silica particles, silica-alumina particles, etc.), boron nitride particles, magnesium oxide particles, sericite particles, mica particles, barium sulfate particles, talc particles, calcium carbonate particles, and the like. As the inorganic particles, silica-based particles are preferable from the viewpoint of forming a chemical bond with the inorganic particles when the siloxane composition is cured. The silica-based particles are silica-based materials containing silica, and the silica particles and silica-containing composite oxide particles containing silica as a constituent unit (specifically, silica-alumina particles and silica magnesia). Particles, etc.).

Examples of the silica-based particles include wet silica such as sedimentation silica and gel silica. Further, as the silica-based particles, for example, plate-shaped silica particles (plate-shaped devitable silica particles) described in JP-A-9-295808, for example, spherical silica particles described in JP-A-5-193927, for example, hollow spherical particles. Examples include silica particles.

The silica-based particles may also include a composition (intraparticle mixture) in which the silica particles and weakly basic oxide particles such as magnesium oxide particles are mixed in the particles. When the silica-based particles are an in-particle composition, the proportion of the silica particles in the in-particle composition is, for example, 50% by mass or more, preferably 55% by mass or more, and for example, 99% by mass or less. It is preferably 90% by mass or less.

The proportion of the porous particles in the resin additive is, for example, 20% by mass or more, preferably 35% by mass or more, and for example, 75% by mass or less, preferably 50% by mass or less.

<Organic UV absorbers and radical scavengers>
Organic UV absorbers and / or radical scavengers are incorporated into the pores of the porous particles. The organic UV absorber absorbs UV light and reduces the amount of UV light directly applied to the resin. The radical scavenger captures alkyl radicals and / or peroxy radicals generated by the resin receiving ultraviolet light.

Examples of the organic ultraviolet absorber include dihydroxybenzophenone, tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, dihydroxydimethoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone (Adecastab 1413, manufactured by ADEKA), and the like. Benzophenone compounds such as 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2'-dihydroxy-4-octyroxybenzophenone, 2,2'-dihydroxy-4-butyloxybenzophenone, for example 2- (2'). -Benzotriazole compounds such as -hydroxy-5'-methylphenyl) benzotriazole, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 4-octyl Salicylic acid ester compounds such as phenyl salicylate, bisphenol A-disalicylate, 4-t-butylphenyl salicylate, phenyl salicylate, for example 2,4,6-tris (2-hydroxy-4-hexaloyloxy-3-methylphenyl). )-1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol, etc. Examples thereof include cyanoacrylate compounds such as ethyl-2-cyano-3,3-diphenylacrylate and 2-ethylhexyl-2-cyano-3,3-diphenylacrylate. Examples of the organic ultraviolet absorber include a benzophenone compound from the viewpoint of high versatility, and more preferably [2-hydroxy-4- (octyloxy) phenyl] (phenyl) metanone (adecastab 1413).

Examples of the radical scavenger include hindered amine-based radical scavengers (HALS) (Hindered amino light stabilizers), hindered phenol-based radical scavengers, aminoketone-based antioxidants, aromatic secondary amine-based antioxidants, and subphosphorus. Examples thereof include acid-based antioxidants and organic thio-based antioxidants. These can be used alone or in combination.

Examples of the hindered amine radical trapping agent include 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β', β'-. Tetramethyl-2,4,8,10-Tetraoxaspiro [5.5] Ester with undecane-3,9-diethanol (ADEKA STAB LA-63P, manufactured by ADEKA), Tetrakiss (1,2,2,6) 6-Pentamethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate (ADEKA STAB LA-52, manufactured by ADEKA), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane -1,2,3,4-tetracarboxylate (ADEKA STAB LA-57, manufactured by ADEKA) and the like can be mentioned. Preferably, Adecastab LA-63P is mentioned.

Examples of the hindered phenol-based radical trapping agent include 2,6-di (tert-butyl) -4-methylphenol (also known as dibutylhydroxytoluene, hereinafter abbreviated as BHT), [3- [. 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoyloxy] -2,2-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoyloxy] Methyl] propyl] 3- (3,5-ditert-butyl-4-hydroxyphenyl) propanoate (Irganox 1010, manufactured by Ciba Japan), octadecyl 3- (3,5-di-tert-butyl-4-) Hydroxyphenyl) propionate (Irganox 1076, manufactured by Ciba Japan Co., Ltd.) and the like can be mentioned.

Examples of the aminoketone-based antioxidant include 6-ethoxy-1,2-dihydro-2,2'-4-trimethylquinoline and the like.

Examples of the aromatic secondary amine-based antioxidant include N-phenyl-1-naphthylamine and N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine.

Examples of the phosphorous acid-based antioxidant include tris (nonylphenyl) phosphite and the like.

Examples of the organic thio-based antioxidant include dilauryl thiodipropionate.

The radical scavenger preferably includes a hindered amine-based radical scavenger (HALS).

The number of parts by mass of the organic ultraviolet absorber with respect to 100 parts by mass of the porous particles is, for example, 10 parts by mass or more, preferably 25 parts by mass or more, and for example, 250 parts by mass or less, preferably 100 parts by mass or less. Is. The proportion of the organic ultraviolet absorber in the resin additive is, for example, 5% by mass or more, preferably 10% by mass or more, and for example, 60% by mass or less, preferably 40% by mass or less.

The number of parts by mass of the radical scavenger with respect to 100 parts by mass of the porous particles is, for example, 10 parts by mass or more, preferably 25 parts by mass or more, and for example, 250 parts by mass or less, preferably 100 parts by mass or less. .. The ratio of the radical scavenger in the resin additive is, for example, 5% by mass or more, preferably 10% by mass or more, and for example, 60% by mass or less, preferably 40% by mass or less.

When the organic ultraviolet absorber and the radical scavenger are used in combination, the number of parts by mass of the radical scavenger with respect to 100 parts by mass of the organic ultraviolet absorber is, for example, 10 parts by mass or more, preferably 50 parts by mass or more. Further, for example, it is 1000 parts by mass or less, preferably 200 parts by mass or less. The total number of parts by mass of the organic ultraviolet absorber and the radical scavenger with respect to 100 parts by mass of the porous particles is, for example, 20 parts by mass or more, preferably 50 parts by mass or more, and for example, 500 parts by mass or less, preferably 500 parts by mass or less. Is 200 parts by mass or less.

<Cured siloxane>
The cured siloxane seals the organic UV absorber and / or radical scavenger incorporated into the porous particles. Specifically, the cured siloxane product seals the porous particles with an organic ultraviolet absorber and / or a radical scavenger supported on the inner surface of the pores of the porous particles. Further, in the cured siloxane product, the organic ultraviolet absorber and / or the radical scavenger may be dispersed in the cured siloxane product, and they may be incorporated into the pores of the porous particles.

The cured siloxane product is a cured product of the siloxane composition. The siloxane composition is hydrolyzed and undergoes a condensation reaction to produce a cured siloxane product. Examples of the siloxane composition include a first siloxane composition containing the first oligomer described below, a second siloxane composition containing the second oligomer, and the like.

<First siloxane composition>
The first siloxane composition contains, for example, a first oligomer, a third oligomer, and silicone oil.

The first oligomer forms a network structure in the cured siloxane product, seals the pores of the porous particles, and plays a role of fixing the ultraviolet absorber and / or the radical scavenger to the porous particles.

The first oligomer forms the main component of the cured siloxane product at the time of curing. The first oligomer is -SiR ₂ O- (the two Rs may be the same or different from each other and are at least selected from the group consisting of monovalent saturated hydrocarbon groups and monovalent aromatic hydrocarbon groups, respectively. It does not contain the siloxane unit represented by one monovalent hydrocarbon group), but contains an RO group-containing siloxane unit containing an RO group (R indicates a monovalent saturated hydrocarbon group). ..

Examples of the monovalent saturated hydrocarbon group include an alkyl group. Examples of the alkyl group include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, n-hexyl and iso-hexyl. Examples thereof include alkyl groups having 1 to 6 carbon atoms. Methyl is preferred.

Examples of the monovalent aromatic hydrocarbon group include an aryl group. Examples of the aryl group include an aryl group having 6 to 10 carbon atoms such as phenyl and naphthyl. It is preferably phenyl.

The monovalent hydrocarbon group preferably includes methyl, ethyl and / or phenyl, and more preferably methyl.

The siloxane unit not contained in the first oligomer and represented by _—SiR2O— is a linear syroxy unit contained in the third oligomer described below.

Specifically, the first oligomer is, for example, a linear siroxy unit-free-alkyl-based oligomer that does not contain the linear syroxy unit represented by -SiR ₂ O-, for example, the straight chain represented by -SiR ₂ O-. Examples thereof include linear syroxy unit-free-alkylaryl oligomers that do not contain syroxy units. The linear syroxy unit-free-alkyl oligomer contains no alkylarylsiloxane unit.

More specifically, the linear syroxyunit-free-alkyl-based oligomer preferably includes a linear syroxyunit-free-methyl-based oligomer. The linear syroxyunit-free-methyl oligomer is produced, for example, from methyltrimethoxysilane.

Examples of the linear syroxyunit-free-alkylaryl-based oligomer include linear syroxyunit-free-methylphenyl-based oligomers. The linear syroxyunit-free-methylphenyl-based oligomer is produced from, for example, phenyltrimethoxysilane and methyltrimethoxysilane.

The molecular weight of the first oligomer is, for example, 500 or more, preferably 1000 or more, and for example, 4000 or less, preferably 3000 or less.

Commercially available products are used as the first oligomer. For example, KC-89S, KR515 (manufactured by Shin-Etsu Chemical Co., Ltd.), KR500, X-40-9225 (all without linear syroxy unit-methyl oligomer, manufactured by Shin-Etsu Chemical Co., Ltd.), US-SG2403 (Toray Dow). Examples include KR401N (manufactured by Corning Co., Ltd.), KR401N (linear siloxy unit-free-methylphenyl-based oligomer, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

The proportion of the first oligomer in the first siloxane composition is, for example, 20% by mass or more, preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, and also. For example, it is less than 60% by mass, preferably 50% by mass or less.

The third oligomer forms a siloxane matrix together with the first oligomer in the cured siloxane product. Since the third oligomer has an amphoteric property for the silicone oil and the first oligomer in the first siloxane composition, the silicone oil and the siloxane matrix separated (or phase-separated) on the surface layer at the time of curing are used. It plays a role in stabilizing the interface of the siloxane to develop the hydrophobicity of the surface of the cured siloxane product. Thereby, the affinity between the resin additive and the resin is improved, thereby improving the dispersibility of the resin additive in the resin (particularly the polyolefin-based resin).

The third oligomer is -SiR ₂ O- (two Rs may be the same or different from each other and are at least selected from the group consisting of monovalent saturated hydrocarbon groups and monovalent aromatic hydrocarbon groups, respectively. It contains a siloxane unit represented by one monovalent hydrocarbon group) and an RO group-containing siloxane unit containing an RO group (R indicates a monovalent saturated hydrocarbon group).

Examples of the monovalent hydrocarbon group and RO group include the same monovalent hydrocarbon group and RO group as the above-mentioned first oligomer.

The siloxane unit represented by —SiR ₂ O— is a linear syroxy unit (skeleton) for introducing a linear siloxane bond into the cured product during the reaction. Preferred examples of the siloxane unit represented by −SiR ₂ O— include a dialkylsiloxane unit and an alkylarylsiloxane unit. The dialkylsiloxane unit is preferably a dimethylsiloxane unit. The alkylarylsiloxane unit is preferably a methylphenylsiloxane unit.

Examples of the RO group include an alkoxy group and an aryloxy group, preferably an alkoxy group, and more preferably methoxy.

Examples of the third oligomer include a dialkylsiloxane unit-containing oligomer, for example, an alkylarylsiloxane unit-containing oligomer containing an alkylarylsiloxane unit. The dialkylsiloxane unit-containing oligomer does not contain an alkylarylsiloxane unit. On the other hand, the alkylarylsiloxane unit-containing oligomer may further contain a dialkylsiloxane unit.

More specifically, examples of the dialkylsiloxane unit-containing oligomer include a dimethylsiloxane unit-containing oligomer containing a dimethylsiloxane unit. Dimethylsiloxane unit-containing oligomers are produced, for example, from methyltrimethoxysilane and dimethyldimethoxysilane.

The alkylarylsiloxane unit-containing oligomer preferably includes a methylphenylsiloxane unit-containing oligomer containing a methylphenylsiloxane unit. The methylphenylsiloxane unit-containing oligomer may further contain a dimethylsiloxane unit. Methylphenylsiloxane unit-containing oligomers are produced, for example, from methylphenyldimethoxysilane and methyltrimethoxysilane.

The molecular weight of the third oligomer is, for example, 500 or more, preferably 1000 or more, and for example, 3000 or less, preferably 2000 or less.

Commercially available products are used as the third oligomer. For example, X-40-9250 (oligomer containing a dimethylsiloxane unit, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are exemplified.

The proportion of the third oligomer in the first siloxane composition is, for example, 1% by mass or more, preferably 3% by mass or more, more preferably 6% by mass or more, and for example, less than 50% by mass, preferably less than 50% by mass. Is 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15% by mass or less.

The mass ratio of the third oligomer to the first oligomer is, for example, 0.1 or more, preferably 0.2 or more. The mass ratio of the third oligomer to the first oligomer is, for example, 0.6 or less, preferably 0.4 or less.

The ratio of the total amount of the first oligomer and the third oligomer (curing component) in the first siloxane composition is, for example, 20% by mass or more, preferably 25% by mass or more, and more preferably 30% by mass or more. When the ratio of the above-mentioned total amount is equal to or more than the above-mentioned lower limit, the cured siloxane product can be reliably formed. The ratio of the total amount of the first oligomer and the third oligomer (curing component) in the first siloxane composition is, for example, 75% by mass or less, preferably 65% by mass or less, more preferably 55% by mass or less, still more preferable. Is 50% by mass or less. When the ratio of the above-mentioned total amount is not more than the above-mentioned upper limit, the first siloxane composition can be sufficiently permeated into the pores of the porous particles.

At the time of curing, the silicone oil is layer-separated (or phase-separated) from the first oligomer and the third oligomer to develop the hydrophobicity of the surface of the cured siloxane product, thereby improving the affinity between the resin additive and the resin. It can be further improved, whereby the dispersibility of the resin additive can be improved.

The silicone oil is -SiR ₂ O- (two Rs may be the same or different from each other and are at least one selected from the group consisting of monovalent saturated hydrocarbon groups and monovalent aromatic hydrocarbon groups, respectively. It contains a siloxane unit represented by one monovalent hydrocarbon group.).

The monovalent hydrocarbon group represented by R is the same as the monovalent hydrocarbon group mentioned in the first oligomer.

Examples of the silicone oil include unmodified silicone oils such as polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Preferred is polydimethylsiloxane.

The kinematic viscosity of the silicone oil at 25 ° C. is not particularly limited and is, for example, 1 mm ² / s or more, preferably 10 mm ² / s or more, more preferably 100 mm ² / s or more, and for example, 1 million. It is mm ² / s or less, preferably 100,000 mm ² / s or less, and more preferably 10,000 mm ² / s or less. When the kinematic viscosity of the silicone oil is not more than the above-mentioned upper limit, the silicone oil can be easily handled and the first siloxane composition can be easily prepared.

Commercially available products are used as the silicone oil. For example, KF-96 series (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-965 series (manufactured by Shin-Etsu Chemical Co., Ltd.), SH200 series (manufactured by Toray Dow Corning), TSF451 series (manufactured by Momentive Performance Materials Japan). , YF-33 series (manufactured by Momentive Performance Materials Japan), etc. are used.

The ratio of the silicone oil to the first siloxane composition is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and for example, 10% by mass. By mass or less, preferably 5% by mass or less, more preferably 3% by mass or less. The number of parts by mass of the silicone oil with respect to 100 parts by mass of the third oligomer is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and for example, 100 parts by mass or less, preferably 100 parts by mass or less. Is 50 parts by mass or less, more preferably 35 parts by mass or less.

The ratio of the total amount of the first oligomer, the third oligomer and the silicone oil to the first siloxane composition is, for example, 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, and further. It is preferably 35% by mass or more. When the ratio of the total amount described above is equal to or higher than the above lower limit, it is possible to prevent the ratio of the cured component from becoming excessively small and to reliably form the cured siloxane product. The ratio of the total amount of the first oligomer, the third oligomer and the silicone oil to the first siloxane composition is, for example, 75% by mass or less, preferably 65% by mass or less, and more preferably 55% by mass or less. When the ratio of the above-mentioned total amount is not more than the above-mentioned upper limit, the first siloxane composition can be sufficiently permeated into the pores of the porous particles.

Further, the first siloxane composition can further contain a catalyst and an organic solvent.

The catalyst is a curing catalyst that reacts with water in the air to hydrolyze and condense the first oligomer and the third oligomer when the siloxane composition is cured.

Examples of the catalyst include metal alkoxides such as titanium alkoxide, zirconium alkoxide, tin alkoxide and aluminum alkoxide, and chelated metals such as titanium acetylacetonate, titaniumtetraacetylacetonate, titaniumalkylacetonate and zirconiumtetraacetylacetonate. And so on.

Examples of the metal alkoxide include titanium alkoxide and the like, and more preferably titanium tetra n-butoxide. As the catalyst, a commercially available product is used, and for example, D-25 (manufactured by Shin-Etsu Chemical Co., Ltd.) or the like is used. The number of parts of the catalyst to be blended is, for example, 1 part by mass or more, preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and more than 1 part by mass with respect to 100 parts by mass of the total amount of the first oligomer and the third oligomer. For example, it is 25 parts by mass or less, preferably 15 parts by mass or less, and more preferably 10 parts by mass or less.

The organic solvent is not particularly limited, and is, for example, an ester solvent such as ethyl acetate and butyl acetate, an alcohol solvent such as methanol, ethanol, propanol and isopropanol, and a ketone solvent such as acetone and methyl ethyl ketone, for example. Examples thereof include glycol ether solvents, paraffin solvents, naphthen solvents, aromatic solvents and the like. Preferred examples include an ester solvent, an alcohol solvent, and a ketone solvent. The organic solvent is a solvent other than the first oligomer, the third oligomer, and silicone oil. The solid content of the first siloxane composition at the time of curing is, for example, 80% by mass or less, preferably 60% by mass or less, and for example, 10% by mass or more, preferably 20% by mass or more, more preferably. , 30% by mass or more of the organic solvent is contained in the first siloxane composition.

The above-mentioned solid content is the ratio of the mass of the cured siloxane product to the mass of the first siloxane composition before curing. The mass of the cured siloxane product (and the components (specifically, silicone oil, catalyst, etc.) incorporated into the cured siloxane product) is the mass obtained by subtracting the organic solvent and the hydrolysis product from the total amount of each component. be. The mass of the cured siloxane product is also calculated from the amount of mass reduction of the first siloxane composition before and after curing.

<Second siloxane composition>
The second siloxane composition contains a second oligomer, a third oligomer, and silicone oil.

The second oligomer is a condensation polymer of tetrafunctional organosilane. Since the cured product of the second oligomer has a larger amount of desorbed alcohol during condensation and tends to be more porous than the cured product of the first oligomer, it absorbs more sealed organic ultraviolet rays than the cured product of the first oligomer. High sustained release of the agent and / or radical trapping agent.

Examples of the tetrafunctional organosilane include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, and tetraaryloxysilanes such as tetraphenoxysilane, and tetraalkoxysilane is preferable. Silanes are mentioned, more preferably tetramethoxysilanes.

Examples of the second oligomer include homocondensation oligomers such as tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, and cocondensation oligomers. From the viewpoint of increasing the velocity, a homocondensation oligomer can be mentioned, and more preferably, a homocondensation oligomer of tetramethoxysilane can be mentioned. The average degree of polymerization of the oligomer is, for example, 3 or more, preferably 4 or more, and for example, 15 or less, preferably 10 or less.

As the second oligomer, a commercially available product is used, and examples thereof include a silicate oligomer series (manufactured by Mitsubishi Chemical Corporation).

The proportion of the second oligomer in the second siloxane composition is, for example, 25% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and also. For example, it is 70% by mass or less, preferably 60% by mass or less.

The mass ratio of the third oligomer to the second oligomer is, for example, 0.05 or more, preferably 0.1 or more. The mass ratio of the third oligomer to the second oligomer is, for example, 0.5 or less, preferably 0.3 or less.

The ratio of the total amount of the second oligomer and the third oligomer (curing component) in the second siloxane composition is, for example, 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, still more preferable. Is 40% by mass or more, particularly preferably 50% by mass or more, and most preferably 55% by mass or more. When the ratio of the above-mentioned total amount is equal to or more than the above-mentioned lower limit, the cured siloxane product can be reliably formed. The ratio of the total amount of the second oligomer, the third oligomer and the (curing component) in the second siloxane composition is, for example, 80% by mass or less, preferably 75% by mass or less, more preferably 70% by mass or less, and further. It is preferably 65% by mass or less. When the ratio of the above-mentioned total amount is not more than the above-mentioned upper limit, the second siloxane composition can be sufficiently permeated into the pores of the porous particles.

The third oligomer forms a siloxane matrix with the second oligomer in the second siloxane composition. The proportion of the third oligomer is similar to that of the third oligomer in the first siloxane composition.

In the second siloxane composition, the silicone oil is layer-separated (or phase-separated) from the second oligomer and the third oligomer at the time of curing to develop the hydrophobicity of the surface of the cured siloxane product, thereby for the resin. The affinity between the additive and the resin can be improved, whereby the dispersibility of the resin additive can be improved. The proportion of silicone oil is similar to that of silicone oil in the first siloxane composition.

The ratio of the total amount of the second oligomer, the silicone oil, and the third oligomer to the second siloxane composition is, for example, 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, and further. It is preferably 35% by mass or more, more preferably 40% by mass or more, particularly preferably 50% by mass or more, and most preferably 60% by mass or more. When the ratio of the total amount described above is equal to or higher than the above lower limit, it is possible to prevent the ratio of the cured component from becoming excessively small and to reliably form the cured siloxane product. The ratio of the total amount of the second oligomer, the silicone oil, and the third oligomer to the second siloxane composition is, for example, 80% by mass or less, preferably 75% by mass or less, and preferably 65% by mass or less. When the ratio of the above-mentioned total amount is not more than the above-mentioned upper limit, the second siloxane composition can be sufficiently permeated into the pores of the porous particles.

Further, the second siloxane composition can further contain a catalyst and an organic solvent. The respective proportions of the catalyst and the organic solvent are similar to those in the first silicone composition described above. The organic solvent is a solvent other than the second oligomer, the third oligomer, and silicone oil.

The number of parts by mass of the cured siloxane product with respect to 100 parts by mass of the porous particles is, for example, 10 parts by mass or more, preferably 25 parts by mass or more, and for example, 75 parts by mass or less, preferably 60 parts by mass or less. .. The number of parts by mass of the cured siloxane product with respect to 100 parts by mass of the total amount of the organic ultraviolet absorber and the radical scavenger is, for example, 10 parts by mass or more, preferably 25 parts by mass or more, and for example, 75 parts by mass or less, preferably. Is 60 parts by mass or less.

The ratio of the cured siloxane to the resin additive is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and for example, 50% by mass or less, preferably preferably. It is 40% by mass or less, more preferably 30% by mass or less. When the mass part and / or the ratio of the cured siloxane product is at least the above lower limit, the cured siloxane product can control the sustained release properties of the organic ultraviolet absorber and the radical scavenger. When the mass part and / or the ratio of the cured siloxane product is not more than the above upper limit, the cured siloxane product can sufficiently contain the organic ultraviolet absorber and the radical scavenger.

The resin additive is a first resin additive containing an organic ultraviolet absorber and a radical scavenger, and an organic ultraviolet absorber and a radical scavenger, for the purpose of explaining the following production method. , Which is classified as a second resin additive containing or not containing one of them. Preferably, from the viewpoint of further improving the light resistance, the first resin additive can be mentioned.

<Manufacturing method of the first resin additive>
A method for producing the first resin additive will be described. The first method for producing an additive for resin is a first step of blending porous particles, an organic ultraviolet absorber and a radical scavenger, and a siloxane composition, and the siloxane composition is cured and the siloxane thereof is cured. The cured product comprises a second step of sealing the organic UV absorber and the radical scavenger in the porous particles.

As a first method for producing an additive for a resin, for example, a first method of incorporating an organic ultraviolet absorber and a radical scavenger into porous particles and then incorporating a siloxane composition into the porous particles. A second production method, for example, a second production method in which one of an organic ultraviolet absorber and a radical scavenger is incorporated into porous particles, and then a siloxane composition containing the other is incorporated into the porous particles. For example, a third production method in which a siloxane composition containing an organic ultraviolet absorber and a radical scavenger is incorporated into porous particles can be mentioned.

<First manufacturing method>
In the first step in the first production method, the porous particles, the organic ultraviolet absorber, and the radical scavenger are blended. As a result, the porous particles are supported with the organic ultraviolet absorber and the radical scavenger. As a supporting method, for example, a first supporting method in which an organic ultraviolet absorber and a radical scavenger are supported on porous particles at once, for example, an organic ultraviolet absorber and a radical scavenger are porous in this order. A second method of supporting the particles can be mentioned.

<First carrier method>
In the first carrying method, for example, if the organic ultraviolet absorber and the radical scavenger are in a solid state, the organic ultraviolet absorber and the radical scavenger are dissolved in a solvent to prepare a mixed solution, and then a mixed solution is prepared. , Mix the mixed solutions into the porous particles and stir and mix them. As a result, the organic ultraviolet absorber and the radical scavenger are incorporated (absorbed) into the pores of the porous particles.

Examples of the solvent include the above-mentioned organic solvents. The mass number of parts of the mixed solution is set so that the total volume thereof is less than the oil-absorbable volume of the porous particles, and specifically, for example, 60 parts by mass or more, preferably 60 parts by mass or more with respect to 100 parts by mass of the porous particles. , 80 parts by mass or more, and for example, 150 parts by mass or less.

As a result, the mixed solution is incorporated into the pores of the porous particles. An organic ultraviolet absorber and a radical scavenger are supported on the porous particles.

Then, the solvent is removed from the porous particles incorporating the organic ultraviolet absorber and the radical scavenger in the mixed solution. Specifically, the porous particles are left at room temperature (25 ° C.) for 24 hours or more. From the viewpoint of shortening the time, the porous particles can be heated at, for example, 100 ° C. or lower, for example, for 1 hour or more and 5 hours or less.

<Second supporting method>
In the second supporting method, an organic ultraviolet absorber is first supported on the porous particles, and then a radical scavenger is supported on the porous particles.

If the organic UV absorber is in a solid state, the organic UV absorber is dissolved in a solvent to prepare an organic UV absorber solution. If the radical scavenger is in solid form, the radical scavenger is dissolved in a solvent to prepare a radical scavenger solution. Examples of the solvent include the above-mentioned organic solvents. The mass parts of each of the organic ultraviolet absorber solution and the radical scavenger solution are set so that the total volume thereof is less than the oil-absorbable volume of the porous particles, and specifically, with respect to 100 parts by mass of the porous particles. For example, it is 60 parts by mass or more, preferably 80 parts by mass or more, and for example, 150 parts by mass or less.

First, an organic ultraviolet absorber solution is blended with the porous particles, and they are stirred and mixed. As a result, the organic ultraviolet absorber is taken in (absorbed) into the pores of the porous particles. The solvent is then removed from the porous particles. The method for removing the solvent is the same as the method for removing the solvent in the mixed solution.

Then, the radical scavenger solution is added to the porous particles, and they are stirred and mixed. As a result, the radical scavenger is incorporated (absorbed) into the pores of the porous particles. The organic ultraviolet absorber and the radical scavenger are sequentially incorporated (absorbed) into the pores of the porous particles.

Then, the solvent is removed from the porous particles. The method for removing the solvent is the same as the method for removing the solvent in the mixed solution. In the second carrier method, the organic ultraviolet absorber and the radical scavenger are preferably arranged in layers. In this case, the organic UV absorber is arranged inside (inside) and the radical scavenger is arranged outside (outside).

Of the first and second carrying methods, the second carrying method is preferable. In the second carrier method, the radical scavenger can be arranged on the front side of the organic ultraviolet absorber. Therefore, according to this arrangement, when the resin additive is added to the resin to form the molded body, the organic ultraviolet absorber can stay in the porous particles for a long time to absorb the ultraviolet rays, while the radical scavenger. Can be sustained and dispersed in the resin from the porous particles to capture alkyl radicals and / or peroxy radicals generated from the resin. That is, in the second carrying method, although the number of steps is increased, it can be arranged in a place where the functions of the organic ultraviolet absorber and the radical scavenger can be easily exerted, that is, the organic ultraviolet absorber is placed inside (in the resin). On the far side), the radical scavenger can be placed on the outside (closer to the resin).

Next, in the first production method, the siloxane composition is blended with the porous particles incorporating the organic ultraviolet absorber and the radical scavenger. As a result, the siloxane composition is newly supported on the porous particles.

The number of parts by mass of the siloxane composition with respect to 100 parts by mass of the porous particles incorporating the organic ultraviolet absorber and the radical scavenger is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, and for example, 100 parts. By mass or less, preferably 70 parts by mass or less.

Thereby, the first step of the first manufacturing method is carried out.

After that, in the first manufacturing method, the second step is carried out. In the second step, the porous particles containing the siloxane composition are left at room temperature (25 ° C.), for example. The leaving time is not particularly limited, and the organic solvent contained in the siloxane composition can be distilled off (removed) and the oligomer contained in the first siloxane composition or the second siloxane composition can be cured. Specifically, it is, for example, 30 minutes or more, preferably 1 hour or more, more preferably 10 hours or more, still more preferably 20 hours or more, and for example, 100 hours or less. From the viewpoint of shortening the time in the second step, the porous particles containing the siloxane composition can be heated, for example, at 100 ° C. or lower, for example, for 1 hour or more and 5 hours or less.

As a result, the curing reaction between the first oligomer and the third oligomer in the first siloxane composition or the curing reaction between the second oligomer and the third oligomer in the second siloxane composition proceeds.

Alcohols generated from the alkoxy groups of the first oligomer and the third oligomer in the first siloxane composition, or alcohols generated from the alkoxy groups of the second oligomer and the third oligomer in the second siloxane composition are removed ( Will be removed).

As a result, the siloxane composition is cured to obtain a cured siloxane product. The cured siloxane seals the organic photoenergy ray absorber and radical scavenger carried in the pores of the porous particles. That is, this siloxane cured product forms a sealing body that seals the organic light energy ray absorber and the radical scavenger in the pores of the porous particles.

As a result, an additive for resin containing porous particles, an organic light energy ray absorber, a radical scavenger, and a cured siloxane product is produced.

<Second manufacturing method>
In the second production method, preferably, the porous particles are first incorporated with an organic ultraviolet absorber, and then the porous particles are incorporated with a siloxane composition containing a radical scavenger.

According to this method, the radical scavenger can be arranged on the front side of the organic ultraviolet absorber, and when the resin additive is added to the resin, the organic ultraviolet absorber stays in the porous particles for a long time. While it can absorb ultraviolet light, the radical scavenger can be sustained and dispersed in the resin from the porous particles to capture the alkyl radicals and / or peroxy radicals generated from the resin.

The method of incorporating the organic ultraviolet absorber into the porous particles is the same as the method of supporting the organic ultraviolet absorber on the porous particles in the second supporting method in the above-mentioned first production method.

The siloxane composition containing the radical scavenger is prepared by blending the above-mentioned siloxane composition and the radical scavenger. Preferably, a scavenger-containing siloxane composition containing a radical scavenger is prepared. Specifically, if the siloxane composition is the first siloxane composition, a radical scavenger, a first oligomer, a third oligomer, and silicone oil are blended to prepare a scavenger-containing siloxane composition. do. If the siloxane composition is a second siloxane composition, a radical scavenger, a second oligomer, a third oligomer, and silicone oil are mixed to prepare a scavenger-containing siloxane composition.

The number of parts by mass of the scavenger-containing siloxane composition with respect to 100 parts by mass of the porous particles incorporating the organic ultraviolet absorber is, for example, 5 parts by mass or more, preferably 50 parts by mass or more, and more preferably 100 parts by mass or more. Yes, and for example, it is 200 parts by mass or less, preferably 150 parts by mass or less.

Thereby, the first step of the second manufacturing method is carried out.

After that, in the second manufacturing method, the second step is carried out. The second step in the second manufacturing method is the same as the second step in the first manufacturing method.

As a result, in the porous particles, the organic ultraviolet absorber among the organic ultraviolet absorber and the radical scavenger is supported on the inner surface of the pores, and the radical scavenger is dispersed in the cured siloxane body. , Additives for resins are obtained in which they are sealed with a cured siloxane.

<Third manufacturing method>
In the third production method, the porous particles are made to incorporate a siloxane composition containing an organic ultraviolet absorber and a radical scavenger.

The siloxane composition containing the organic UV absorber and the radical scavenger is prepared as an absorbent-scavenger-containing siloxane composition by blending the organic UV absorber, the radical scavenger and the above-mentioned siloxane composition. .. The number of parts by mass of the absorbent-scavenger-containing siloxane composition with respect to 100 parts by mass of the porous particles is, for example, 10 parts by mass or more, and for example, 200 parts by mass or less.

After that, in the third manufacturing method, the second step is carried out. The second step in the third manufacturing method is the same as the second step in the first manufacturing method.

As a result, in the porous particles, an organic ultraviolet absorber and a radical scavenger are dispersed in the cured siloxane body, and an additive for resin in which they are sealed by the cured siloxane body is obtained.

<Manufacturing method of the second resin additive>
A method for producing the second resin additive will be described. The second method for producing the resin additive is a first step of blending porous particles, one of an organic ultraviolet absorber and a radical scavenger, and a siloxane composition, and curing the siloxane composition. The siloxane cured product is provided with a second step of sealing one of them in the porous particles.

As a method for producing the second resin additive, for example, one of the organic ultraviolet absorber and the radical scavenger is incorporated into the porous particles, and then the siloxane composition is incorporated into the porous particles. A fourth production method for incorporating a siloxane composition containing one of an organic ultraviolet absorber and a radical scavenger into porous particles can be mentioned.

<Fourth manufacturing method>
As a method for incorporating one of the porous particles, for example, a method of supporting the organic ultraviolet absorber in the second supporting method in the first manufacturing method described above can be mentioned. The method of supporting the radical scavenger on the porous particles can be carried out according to the method of supporting the organic ultraviolet absorber described above on the porous particles. The method of incorporating the siloxane composition into the porous particles is the same as the method of newly supporting the siloxane composition on the porous particles in the above-mentioned first production method.

<Fifth manufacturing method>
In the fifth production method, a siloxane composition containing an organic ultraviolet absorber or a siloxane composition containing a radical scavenger is prepared. The siloxane composition containing the organic ultraviolet absorber is prepared, for example, as an absorbent-containing siloxane composition containing the organic ultraviolet absorber and the siloxane composition. The siloxane composition containing the radical scavenger is the same as the scavenger-containing siloxane composition in the second production method described above. The method of incorporating the absorbent-containing siloxane composition or the scavenger-containing siloxane composition into the porous particles and then forming the cured siloxane product is the same as the second step of the second production method.

From the fourth production method to the fifth production method, an additive for resin containing porous particles, one of an organic ultraviolet absorber and a radical scavenger, and a siloxane cured product that seals the porous particles is obtained. Be done.

The first or second resin additive produced by the first to fifth production methods is added to a resin that requires light resistance to prepare a resin composition.

<Resin>
The resin may have a functional group. Examples of the functional group include a hydroxyl group, a carboxyl group, an amino group and a vinylene group (-CH = CH-). Further, the resin may have a long-chain alkyl moiety. Specifically, the resin includes, for example, a polyolefin resin, a silicone resin, a fluororesin, a polystyrene resin, a modified polyphenylene ether resin, an ABS resin, an AS resin, a vinyl chloride (PVC) resin, and an acrylic resin (including PMMA resin). , Vinyl acetate resin, thermoplastic polyester resin, thermoplastic urethane resin, polyamide resin, polycarbonate resin and other thermoplastic resins. The resin includes rubber (elastomer). In the present application, resin and rubber (elastomer) are not distinguished, and rubber is included in the concept of resin. Examples of the rubber include styrene-butadiene (SBR) rubber, rubber (MBR) whose main raw materials are methyl methacrylate and butadiene, acrylonitrile-butadiene (NBR) rubber, isoprene rubber (IR), and chloroprene rubber (CR). Diene rubber can be mentioned. The SBR rubber contains a carboxy-modified SBR rubber. Further, examples of the rubber include non-diene rubber such as ethylene-propylene rubber (EPR, EPDM).

These resins can be used alone or in combination of two or more.

Polyolefin-based resins are preferable because of their affinity with silicone oil on the surface of the resin additive. Examples of the polyolefin-based resin include low-density polyethylene (including LLDPE), high-density polyethylene, polypropylene, ethylene propylene copolymer resin (EPR rubber), ethylene propylene diene copolymer resin (EPDM rubber), and butadiene-based thermoplastic elastomer ( (Including SBS and SEBS), isoprene-based thermoplastic elastomer (including SIS and SEPS), ethylene vinyl acetate copolymer resin, ethylene vinyl chloride copolymer resin, ionomer resin and the like.

The proportion of the resin additive in the resin composition is, for example, 0.1% by mass or more, preferably 1% by mass or more, and for example, 50% by mass or less, preferably 30% by mass or less.

To prepare a resin composition, for example, a resin additive and a resin are dry-blended (blended) and melt-kneaded using a twin-screw extruder or the like to prepare a resin composition as a compound. .. Alternatively, they are once melt-kneaded to prepare a masterbatch having a high ratio of resin additives to the resin, and then the masterbatch and the resin are melt-kneaded to prepare a resin composition. You may. The amount of the masterbatch added in the case of melt-kneading the masterbatch and the resin is such that the ratio of the resin additive is, for example, 0.1% by mass or more, preferably 0.1% by mass or more, based on the total amount of the masterbatch and the resin. It is adjusted to be 1% by mass or more, and for example, 50% by mass or less, preferably 30% by mass or less.

When the resin is prepared as latex, the resin additive and latex are wet-blended (blended) using a high-speed stirring / dispersing machine such as a colloid mill or a disper to prepare a resin composition as a latex compound. .. In order to stably disperse the resin additive, a dispersant such as sodium pyrophosphate or β-naphthalene sulfonic acid formaldehyde condensate sodium can be added (added) to the latex in advance. In addition, an antifoaming agent can be appropriately added for defoaming.

When the resin is crumb rubber, it is kneaded using a kneader, a roll, a Banbury mixer or the like to prepare a resin composition as a rubber compound. Crumb rubber is solid raw rubber that has not been vulcanized.

Then, the resin composition is produced into a molded body (resin molded body) having a desired shape by using a molding method such as extrusion molding, injection molding, pressure molding, or casting molding.

The ratio of the resin additive in the molded product is the same as the ratio of the resin additive in the above-mentioned resin composition.

<Effect>
The resin additive obtained by the above-mentioned production method is excellent in dispersibility in the resin, and is also excellent in controlling the sustained release of the organic ultraviolet absorber and / or the radical scavenger. Note that the sustained release control means controlling the sustained release rate according to the functions of the organic ultraviolet absorber and the radical scavenger. Depending on the distance from the particle surface and the porosity of the sealed siloxane cured product, it is slowly released into the resin during melt kneading and molding. Therefore, the molded product molded from the resin composition containing the resin additive is excellent in light resistance.

Specifically, the additive particles for resin are uniformly dispersed in the resin during melt-kneading and molding. Since the cured siloxane product has the property of transmitting ultraviolet rays, the ultraviolet absorber functions as an ultraviolet absorber by staying in the uniformly dispersed particles, and is less likely to cause molding defects such as bleed-out. It has an excellent feature. Therefore, it is desirable that the ultraviolet absorber is not easily released slowly, and it is a favorable condition that the ultraviolet absorber is supported in the pores of the particles and in the inner layer (innermost layer) and is sealed with a cured siloxane product having low porosity. On the other hand, the radical scavenger is released into the resin and exists as a simple substance, thereby exhibiting a function as a radical scavenger. Therefore, it is desirable that the radical scavenger is easily released slowly, and it is a favorable condition that the radical scavenger is supported on the outer layer of the particles and that the radical scavenger is sealed with a highly porous siloxane cured product. Due to the different functions of the UV absorber and the radical scavenger, it is superior due to the synergistic effect of the distance from the surface of the UV absorber and the radical scavenger (where it is contained) and the porosity (sustained release rate) of the sealed cured product. It will exert a light stabilizing effect.

Therefore, the decrease in mechanical strength (such as tensile elongation at break and tensile modulus) of the molded product exposed to light for a long time (that is, the decrease in mechanical strength of the molded product due to exposure to light) and elongation (tensile elongation at break). (That is, the decrease in the elongation of the molded product due to exposure to light) can be suppressed.

<Modification example>
In the modified example, detailed description of the same components and steps as described above will be omitted. Further, the modified example can exhibit the same action and effect as described above, except for special mention.

<Variation example of the first siloxane composition>
The first siloxane composition does not contain the third oligomer and the silicone oil, but may contain the first oligomer. In this case, the proportion of the first oligomer in the first siloxane composition is, for example, 40% by mass or more, preferably 50% by mass or more, and for example, 100% by mass or less, preferably 95% by mass. % Or less.

Further, the first siloxane composition does not contain the third oligomer, but may contain the first oligomer and silicone oil. Examples of the silicone oil include silicone oils containing the siloxane unit represented by -SiR ₂ O- described above, and further, functional groups at both ends or one end (for example, RO group exemplified by the first oligomer). Also mentioned is a silicone oil having. The silicone oil is preferably a silicone oil having a functional group at both ends or one end from the viewpoint of reactivity with the resin. Commercially available products are used as the silicone oil having a functional group. Specifically, as the silicone oil having a functional group at one end, for example, KR-4000A (alkoxy-modified), X-22-170BX (carbinol-modified). , X-22-170DX (diol denaturation, both manufactured by Shin-Etsu Chemical Co., Ltd.). As silicone oils having functional groups at both ends, for example, X-21-5841, KF-9701 (all manufactured by Shin-Etsu Chemical Co., Ltd.), XC96-C7123, XC96-C7124 (all are Momentive Performance Materials Japan). (Made by a joint venture). By using a silicone oil having a functional group at both ends or one end as the silicone oil, the role of the third oligomer and the silicone oil can be combined. In these modifications, each of the first siloxane compositions produces a cured siloxane product.

The ratio of the total amount of the first oligomer to the silicone oil in the first siloxane composition is, for example, 40% by mass or more, preferably 50% by mass or more, and for example, 100% by mass or less, preferably 95% by mass. It is less than mass%. The number of parts by mass of the silicone oil with respect to 100 parts by mass of the first oligomer is, for example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and for example, 30 parts by mass or less, preferably 30 parts by mass or less. Is 20 parts by mass or less, more preferably 10 parts by mass or less.

<Variation example of the second siloxane composition>
The second siloxane composition does not contain the third oligomer and the silicone oil, but may contain the second oligomer. In this case, the proportion of the second oligomer in the second siloxane composition is, for example, 50% by mass or more, preferably 60% by mass or more, and for example, 100% by mass or less, preferably 95% by mass. % Or less.

Further, the second siloxane composition does not contain the third oligomer, but may contain the second oligomer and the silicone oil. Examples of the silicone oil include silicone oils containing the siloxane unit represented by the above-mentioned _—SiR2O— , and further include silicone oils having functional groups at both ends or one end. As the silicone oil, a silicone oil having a functional group at both ends or one end is preferable. As the silicone oil having a functional group, the above-mentioned commercially available product is used. The silicone oil having a functional group can also serve as the third oligomer and the silicone oil. In these modifications, each of the second siloxane compositions produces a cured siloxane product.

The ratio of the total amount of the second oligomer to the silicone oil in the second siloxane composition is 50% by mass or more, preferably 60% by mass or more, and for example, 100% by mass or less, preferably 95% by mass. It is as follows. The number of parts by mass of the silicone oil with respect to 100 parts by mass of the second oligomer is, for example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and for example, 30 parts by mass or less, preferably 30 parts by mass or less. Is 20 parts by mass or less, more preferably 10 parts by mass or less.

<Third siloxane composition>
In the above description, the first siloxane composition does not contain the second oligomer and the second siloxane composition does not contain the first oligomer. However, a third siloxane composition containing the first oligomer and the second oligomer can be exemplified as a material for the cured siloxane product. Specifically, the third siloxane composition contains a first oligomer, a second oligomer, a third oligomer, and silicone oil. Examples of the silicone oil include the above-mentioned silicone oils, and preferably unmodified silicone oils.

The number of parts by mass of the second oligomer with respect to 100 parts by mass of the first oligomer is, for example, 10 parts by mass or more, preferably 50 parts by mass or more, and for example, 1000 parts by mass or less, preferably 200 parts by mass or less. .. The number of parts by mass of the third oligomer with respect to 100 parts by mass of the total amount of the first oligomer and the second oligomer is, for example, 5 parts by mass or more, preferably 20 parts by mass or more, and for example, 75 parts by mass or less, preferably 75 parts by mass or less. , 35 parts by mass or less. The number of parts by mass of the silicone oil with respect to 100 parts by mass of the total amount of the first oligomer, the second oligomer and the third oligomer is, for example, 1 part by mass or more, preferably 2 parts by mass or more, and for example, 25 parts by mass or less. It is preferably 10 parts by mass or less. The mass ratio of the total amount of the first oligomer, the second oligomer, the third oligomer and the silicone oil in the third siloxane composition is, for example, 45% by mass or more, preferably 55% by mass or more, and for example. It is 100% by mass or less, preferably 95% by mass or less.

<RO group-containing silane compound>
As a raw material for the cured siloxane product, a RO group-containing silane compound can also be mentioned. The RO group-containing silane compound will be described later. The method of sealing the organic ultraviolet absorber and / or the radical scavenger in the porous particles with the RO group-containing silane compound to obtain the resin additive can be carried out according to the above-mentioned production methods.

Further, the porous particles in which the organic ultraviolet absorber and / or the radical scavenger are sealed with a cured siloxane product may be surface-treated with a RO group-containing silane compound. In this modification, specifically, silica-based particles in which an organic ultraviolet absorber and / or a radical scavenger is sealed with a cured silica product are surface-treated with an RO group-containing silane compound.

Compared with the resin additive in which the organic ultraviolet absorber and / or the radical scavenger is sealed in the porous particles with the RO group-containing silane compound, the RO group-containing silane compound is porous from the viewpoint of reducing the manufacturing cost. Additives for resins with surface-treated particles are suitable. On the other hand, the additive for resin in which the organic ultraviolet absorber and / or the radical trapping agent is sealed in the porous particles with the RO group-containing silane compound is for the resin whose porous particles are surface-treated with the RO group-containing silane compound. Unlike additives, the surface treatment step can be omitted.

The RO group-containing silane compound includes an RO group (R represents at least one monovalent hydrocarbon group selected from the group consisting of a monovalent saturated hydrocarbon group and a monovalent aromatic hydrocarbon group). It contains a moiety other than the RO group, which is reactive and / or compatible with the resin.

As R, preferably, a monovalent saturated hydrocarbon group is mentioned, and more preferably, methyl is mentioned. Examples of the RO group include an alkoxy group and an aryloxy group, preferably an alkoxy group, and more preferably a methoxy group and an ethoxy group.

Examples of the portion other than the RO group and capable of reacting with the resin include an epoxy group, a thiol group, a sulfide group, an isocyanate group, a hydroxyl group-free group (anhydrous succinic acid group, etc.) and the like.

Examples of the portion other than the RO group, which is compatible with the resin, include a long-chain alkyl group having 8 or more carbon atoms.

Examples of the RO group-containing silane compound containing a portion that can react with the resin include an epoxy group-containing silane compound, a thiol group-containing silane compound, a sulfide group-containing silane compound, an isocyanate group-containing silane compound, and a hydroxyl group-free silane compound. Be done.

Examples of the epoxy group-containing silane compound include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxy. Examples thereof include propylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane. Preferred are 3-glycidoxypropyltrimethoxysilane.

Examples of the thiol group-containing silane compound include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. Preferred are 3-mercaptopropyltrimethoxysilane.

Examples of the sulfide group-containing silane compound include bis (triethoxypropyl) tetrasulfide and bis (triethoxypropyl) disulfide.

Examples of the isocyanate group-containing silane compound include 3-isocyanatepropyltriethoxysilane.

Examples of the hydroxyl group-free silane compound include 3-trimethoxysilylpropyl succinic anhydride.

Of these, an epoxy group-containing silane compound and a thiol group-containing silane compound are preferable.

Examples of the RO group-containing silane compound containing a portion compatible with the resin include a silyl group-containing polymer, and specific examples thereof include a vinyl polymer in which (RO) _3Si- is bonded to a side chain. Preferred is methyl polyacrylate (PMMA) in which trialkoxyryl is attached to the main chain, and more preferably, PMMA in which trimethoxysilyl is attached to the main chain. The weight average molecular weight of PMMA to which trimethoxysilyl is attached to the main chain is, for example, 10,000 or more, preferably 20,000 or more, more preferably 30,000 or more, and for example, 50,000 or less. Is. In addition, examples of the RO group-containing silane compound containing a portion compatible with the resin include compounds in which (RO) _3Si- is bonded to the side chain of a long-chain alkyl group having 8 or more carbon atoms. , Trialkoxy long chain alkylsilanes such as triethoxycaprylylsilane. The porous particles preferably do not contain silicone oil. According to this preferred example, it is possible to suppress the hindrance of the surface treatment by the RO group-containing silane compound due to the presence of the silicone oil on the surface.

To surface-treat porous particles in which an organic ultraviolet absorber and / or a radical trapping agent is sealed with a siloxane cured product using an RO group-containing silane compound, an RO group-containing silane compound and an organic ultraviolet absorber and / or Alternatively, the radical trapping agent is blended with the porous particles sealed with the cured siloxane (third step). In this modification, the porous particles in which the organic ultraviolet absorber and / or the radical scavenger are sealed with a cured siloxane product are hereinafter simply referred to as “porous particles”. Preferably, the solution containing the RO group-containing silane compound and the porous particles are blended. Further, if necessary, a catalyst is added.

The surface treatment with the RO group-containing silane compound is a third step carried out after the second step, in which the RO group is hydrolyzed and the porous particles (specifically, silica-based particles, further, siloxane) are hydrolyzed. Condensation reaction with silanol on the surface of the cured product). On the other hand, the portion other than the RO group and having reactivity does not yet react even in the above-mentioned surface treatment.

The solution contains a RO group-containing silane compound and a solvent. Examples of the solvent include the above-mentioned organic solvents. However, when the RO group-containing silane compound contains at least one of an epoxy group, an isocyanate group, and a hydroxyl group-free, a solvent containing active hydrogen such as a hydroxyl group or an amino group is not used. The proportion of the RO group-containing silane compound in the above solution is, for example, 40% by mass or more, preferably 70% by mass or more, and for example, 95% by mass or less, preferably 85% by mass or less. The mass number of parts of the RO group-containing silane compound with respect to 100 parts by mass of the porous particles is, for example, 5 parts by mass or more, preferably 15 parts by mass or more, and for example, less than 50 parts by mass, preferably 35 parts by mass or less. Is.

The catalyst promotes hydrolysis of the RO group to cause a condensation reaction with the silanol group in the porous particles (preferably silica-based particles). Examples of the catalyst include the above-mentioned curing catalyst, and preferably metal alkoxide.

The solution may be divided and blended into the porous particles. For example, a part of the solution is mixed with the porous particles and dried, and then the rest of the solution is mixed with the dried porous particles and dried.

Then they are dried by heating. The heating temperature is, for example, 40 ° C. or higher, preferably 60 ° C. or higher, and for example, 100 ° C. or lower, preferably 90 ° C. or lower.
The heating time is, for example, 0.5 hours or more, preferably 1 hour or more, and for example, 10 hours or less, preferably 4 hours or less.

The solvent is removed by the above-mentioned drying by heating, and the RO group is hydrolyzed to undergo a condensation reaction with the silanol group on the surface of the porous particles (specifically, silica-based particles and further, a cured siloxane product). do.

As a result, the surface-treated porous particles are obtained as an additive for the resin of the modified example.

When the resin additive of the modified example and the resin are blended, the catalyst can be blended in an appropriate ratio. Specifically, when the RO group-containing silane compound has an epoxy group, examples of the catalyst include a tertiary amine compound such as diazabicycloundecene. For example, when a RO group-containing silane compound having a thiol group or a sulfide group is blended in a diene-based rubber, as a catalyst, for example, an oxide metal such as zinc oxide (zinc oxide), for example, an amine-based or thiourea-based compound may be used. Examples include vulcanization accelerators.

(Effect of modified example)
The resin additive surface-treated with the RO group-containing silane compound and the resin additive not surface-treated with the RO group-containing silane compound are compared in a molded product that has not yet been exposed to light. In this state, the molded body containing the additive for resin which has not been surface-treated has a lower tensile breaking strength and a higher tensile elastic modulus than the molded body made only of resin. In some cases. This may mean a decrease in the mechanical properties of the molded body depending on the use of the molded body.

However, in the molded product containing the surface-treated resin additive, the portion existing on the surface of the porous particles (epoxide group, thiol group, PMMA chain, etc.) can react with the resin and / or be compatible with the resin. .. Therefore, the portion reacts with the resin and / or becomes compatible with the resin due to heating at the time of molding or the like. Then, the dispersibility of the resin additive in the resin is improved, and the interfacial adhesive force between the resin additive and the resin is increased. As a result, the molded body containing the surface-treated resin additive has higher tensile breaking strength, tensile elastic modulus and tensile breaking elongation than the molded body containing the non-surface-treated resin additive. ..

Specific numerical values such as the compounding ratio (content ratio), physical property values, parameters, etc. used in the following description are the compounding ratios (content ratios) corresponding to those described in the above-mentioned "mode for carrying out the invention". ), Physical property values, parameters, etc. can be replaced with the upper limit value (value defined as "less than or equal to" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess"). can. In addition, unless otherwise specified in the following description, "part" and "%" are based on mass.

Preparation Example 1
<Preparation of the first siloxane composition>
The first siloxane composition was prepared according to the formulation shown in Table 1. Specifically, in a glass container, 40.4 parts of KR500 (first oligomer), 10.0 parts of X-40-9250 (third oligomer), 2.6 parts of KF-96-1000cs (silicone oil), isopropanol. 44.1 parts (solvent) and 2.9 parts of titanium n-tetrabutoxide (catalyst, D-25, manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed and stirred at room temperature (25 ° C.) for 20 minutes using an anchor type stirrer. Then, 100.0 parts of the first siloxane composition was prepared. The mass ratio of the cured siloxane composition when the first siloxane composition was cured was 42.4% by mass with respect to the mass of the first siloxane composition before curing.

Preparation Example 2
<Preparation of second siloxane composition>
A second siloxane composition was prepared according to the formulation shown in Table 2. Specifically, in a glass container, 53.0 parts of MKC silicate MS56S (tetramethoxysilane oligomer, manufactured by Mitsubishi Chemical Corporation) as the second oligomer, 10.0 parts of X-40-9250 (third oligomer), KF. -96-1000 cs (silicone oil) 2.6 parts, isopropanol (solvent) 31.5 parts, titanium n-tetrabutoxide (catalyst, manufactured by D-25 Shin-Etsu Chemical Co., Ltd.) 2.9 parts, anchor type stirrer Was stirred at room temperature (25 ° C.) for 20 minutes to prepare 100.0 parts of the second siloxane composition. The mass ratio of the cured siloxane composition when the second siloxane composition was cured was 42.4% by mass with respect to the mass of the siloxane composition before curing.

Example 1
<Manufacturing of the first resin additive>
<Second manufacturing method>
<Supporting UV absorber on porous particles>
An organic ultraviolet absorber solution was prepared by dissolving 40 parts of an organic ultraviolet absorber (benzophenone compound, ADEKA STUB 1413, manufactured by ADEKA) in 30 parts of ethyl acetate (solvent). 80 parts of Mizupearl K-500L (silica particles, median diameter 4.6 μm, specific surface area 225 m ² / g, oil absorption 245 mL / 100 g) was charged into a stirrer (Kawata Super Mixer Piccolo), and while stirring at 300 rpm, The organic UV absorber solution was added dropwise over 2 minutes, and stirring was continued for 5 minutes until uniform. As a result, silica-based particles incorporating an organic ultraviolet absorber solution were obtained. Then, the mixture was stirred at 80 ° C. for 3 hours to distill off ethyl acetate to obtain silica-based particles in which the organic ultraviolet absorber was incorporated into the pores of the silica-based particles.

<Supporting and encapsulating a scavenger-containing siloxane composition on porous particles>
Next, 40 parts of a hindered amine radical scavenger (HALS, ADEKA STUB LA-63P, manufactured by ADEKA) was dissolved in 94.3 parts of the first siloxane composition to prepare a scavenger-containing siloxane composition. The silica-based particles incorporating the organic ultraviolet absorber are returned to room temperature (25 ° C.), and 94.3 parts of the scavenger-containing siloxane composition is added dropwise over 10 minutes while stirring at 300 rpm, and stirring is continued for 10 minutes. And mixed until uniform. The mixture was allowed to stand at 23 ° C. for 2 days to cure the siloxane composition (the first oligomer and the third oligomer) while volatilizing the isopropanol contained in the scavenger-containing siloxane composition. The obtained powder was crushed with a jet mill to obtain an additive for resin.

Example 2
<Manufacturing of the first resin additive>
<First manufacturing method>
Table 3 except that the method was changed to the first production method and the first carrier method was used in which a mixed solution containing an organic ultraviolet absorber, a radical scavenger, and acetone was blended into silica-based particles. Therefore, the same treatment as in Example 1 was carried out to obtain an additive for resin. Specifically, it is as follows.

<Supporting UV absorber on porous particles>
<First carrier method>
40 parts of an organic ultraviolet absorber (ADEKA STAB 1413, manufactured by ADEKA) and 40 parts of a hindered amine radical scavenger (HALS, ADEKA STAB LA-63P, manufactured by ADEKA) were dissolved in 60 parts of acetone (solvent). A mixed solution was prepared. 80 parts of Mizupearl K-500L (silica particles, median diameter 4.6 μm, specific surface area 225 m ² / g, oil absorption 245 mL / 100 g) was charged into a stirrer (Kawata Super Mixer Piccolo), and while stirring at 300 rpm, The mixed solution was added dropwise over 2 minutes, stirring was continued for 5 minutes and the mixture was mixed until uniform. As a result, silica-based particles incorporating the mixed solution were obtained. Then, the mixture was stirred at 80 ° C. for 3 hours to distill off acetone to obtain silica-based particles in which the organic ultraviolet absorber and the radical scavenger were incorporated into the pores of the silica-based particles.

<Seal of organic UV absorber and radical scavenger with siloxane composition>
Next, the silica-based particles incorporating the organic ultraviolet absorber and the radical scavenger were returned to room temperature (25 ° C.), and 94.3 parts of the first siloxane composition was added dropwise over 10 minutes while stirring at 300 rpm. Stirring was continued for 10 minutes and mixed until uniform. The mixture was allowed to stand at 23 ° C. for 2 days to cure the first siloxane composition (the first oligomer and the third oligomer) while volatilizing the isopropanol contained in the first siloxane composition. The obtained powder was crushed with a jet mill to obtain an additive for resin.

Example 3
<Manufacturing of a second resin additive containing an organic UV absorber>
<Fourth manufacturing method>
Same as Example 1 according to Table 3 except that the method was changed to the fourth production method and the organic ultraviolet absorber solution containing the organic ultraviolet absorber and ethyl acetate was blended into the silica-based particles. To obtain an additive for resin.

Example 4
<Manufacturing of a second resin additive containing a radical supplement>
<Fourth manufacturing method>
The treatment was carried out in the same manner as in Example 1 according to Table 3 except that the method was changed to the fourth production method and a radical scavenger solution containing a hindered amine radical scavenger and acetone was blended into the silica particles. To obtain an additive for resin.

Example 5
<Manufacturing of the first resin additive>
<First manufacturing method>
The change to the first production method, an organic ultraviolet absorber solution containing an organic ultraviolet absorber and ethyl acetate, and a radical scavenger solution containing a hindered amine radical scavenger and acetone are used. An additive for resin was obtained by treating in the same manner as in Example 2 according to Table 3 except that the second supporting method of supporting the porous particles in order was used.

Example 6
<Manufacturing of the first resin additive>
<Second manufacturing method>
As shown in Table 3, a hindered phenolic radical scavenger (Irganox 1010, manufactured by Ciba Japan) was used instead of the hindered amine radical scavenger (HALS, ADEKA STUB LA-63P, manufactured by ADEKA). Was treated in the same manner as in Example 1 to obtain an additive for resin.

Example 7
<Manufacturing of the first resin additive>
<First manufacturing method>
A resin additive was obtained by the same treatment as in Example 2 except that the second siloxane composition was used instead of the first siloxane composition.

Example 8
<Manufacturing of a second resin additive containing an organic UV absorber>
<Fourth manufacturing method>
A resin additive was obtained by the same treatment as in Example 3 except that the second siloxane composition was used instead of the first siloxane composition.

Example 9
The same treatment as in Example 5 was carried out except that the second siloxane composition was used instead of the first siloxane composition to obtain an additive for a resin.

Comparative Example 1
According to Table 4, the same treatment as in Example 2 was carried out in the same manner as in Example 2 except that the scavenger-containing siloxane composition was not blended and the cured siloxane was not formed, to obtain an additive for resin. This resin additive does not contain a cured siloxane.

Comparative Example 2
According to Table 4, the same treatment as in Example 2 was carried out except that silicone oil (KF-96-1000cs) was used instead of the siloxane composition to obtain an additive for resin. This resin additive does not contain a cured siloxane, but contains a silicone oil that coats an organic UV absorber and a radical catcher.

Comparative Example 3
According to Table 4, the same treatment as in Example 2 was carried out except that the unsaturated polyester resin composition was used instead of the first silicone resin composition to obtain an additive for resin.

The unsaturated polyester resin composition is prepared by adding 195 parts by mass of a styrene monomer to 500 parts by mass of an unsaturated polyester resin "Polyhope RHF1077M" (manufactured by Japan Composite Co., Ltd.), and then blending 0.07 parts of hydroquinone to form a room temperature gel. It was prepared by adjusting the saturation time (JIS K6901-A method (2008)) to 25 minutes. The viscosity of the unsaturated polyester resin composition (BM type viscometer, 60 rpm, 23 ° C.) was 68 mPa · s.

<Evaluation>
The following items were evaluated for the resin additives of Examples 1 to 9 and Comparative Examples 1 to 3.

<Tension fracture elongation and tensile fracture strength>
Low-density polyethylene resin "Novatec LD" LF244E (manufactured by Japan Polyethylene) 98 parts by mass and 2 parts by mass of resin additive are dry blended and a twin-screw extruder (Thermo Scientific process 11 tabletop twin-screw screw). A resin composition was prepared by kneading at 220 ° C. using an extruder). The resin composition was melted again through the extruder, and a tensile test piece (resin molded product) having the shape and dimensions shown in FIG. 1 was molded by the company's injection molding machine MiniJet Pro. Further, as the tensile test piece of Comparative Example 4, a tensile test piece (resin molded body) made of only polyethylene resin was molded without adding a resin additive. The thickness of the tensile test pieces of Examples 1 to 9 and Comparative Examples 1 to 4 was 1.5 mm.

Each tensile test piece was subjected to a light resistance acceleration test at 180 W / m ² for 640 hours using a Super Xenon Weather Meter SX75 (manufactured by Suga Test Instruments Co., Ltd.).

Then, the tensile test piece was subjected to a tensile test with an autograph AGS-10kNX manufactured by Shimadzu Corporation at a tensile speed of 2 mm / min. Then, the tensile elongation at break and the tensile strength at break were determined. The results are shown in Tables 3 to 4.

<Consideration of Comparative Examples 1 to 3 in comparison with Examples 1 to 9>
In Comparative Examples 1 and 2, the organic UV absorbers were released remarkably rapidly, and they were not uniformly dispersed with respect to the resin, so that the tensile elongation at break and the tensile strength at break were increased. , It is presumed to be lower than those of Examples 1 to 9.

On the other hand, in Comparative Example 3, since the release of the radical scavenger was remarkably slow and the additive for resin was not uniformly dispersed in the resin, the tensile elongation at break and the tensile strength at break were exhibited in Examples 1 to 1. It is presumed to be lower than those of Example 9.

<Raw materials>
The raw materials used in the following examples are described below.
3-glycidoxypropyltrimethoxysilane: RO group-containing silane compound, Fuji Film Wako Junyaku Co., Ltd. reagent 3-Mercaptopropyltrimethoxysilane: RO group-containing silane compound, Fuji Film Wako Junyaku Co., Ltd. reagent trimethoxysilyl group PMMA resin bonded to the side chain: RO group-containing silane compound, manufactured by Taisei Fine Co., Ltd., Acryt 85Q-1052, weight average molecular weight 35,000, methoxypropyl acetate 45% solution Zinchua 50% aqueous dispersion: catalyst, Osaki Kogyo Made by AZ-SW
Diazabicycloundecene: Catalyst, tertiary amine compound, Fuji Film Wako Junyaku Co., Ltd. Reagent D-25: Tetrabutoxytitanium curing catalyst Shinetsu Chemical Industry Co., Ltd. Demor NL: β-naphthalene sulfonic acid formaldehyde condensate sodium salt 41 % Aqueous solution, dispersant, carboxy-modified SBR rubber latex manufactured by Kao Co., Ltd .: Nalstar SR-116 manufactured by Nippon A & L Co., Ltd., solid content concentration 50.5%
ABS resin: Nippon A & L Inc., Clarastic GA-704, MFR: 62 cm ^3/10 min, density: 1.04 g / cm ³
PMMA resin: Sumitomo Chemical Co., Ltd., Sumipex HT55X, MFR: 2g / 10min, Density: 1.17g / cm ³

Preparation Example 3
<Preparation of silica-based particles incorporating an organic UV absorber and a radical scavenger>
A mixed solution was prepared by dissolving 32 parts of an organic ultraviolet absorber (benzophenone compound, ADEKA STUB 1413, manufactured by ADEKA) and 32 parts of a radical scavenger (ADEKA STUB LA-63P) in 48 parts of acetone (solvent). 80 parts of Mizupearl K-500L (silica particles, median diameter 4.6 μm, specific surface area 225 m ² / g, oil absorption 245 mL / 100 g) was charged into a stirrer (Kawata Super Mixer Piccolo, the same applies hereinafter) and stirred at 300 rpm. Then, the above-mentioned mixed solution was added dropwise over 2 minutes, and stirring was continued for 5 minutes until the mixture became uniform. As a result, silica-based particles incorporating the above-mentioned mixed solution were obtained. Then, the mixture was stirred at 80 ° C. for 3 hours, acetone was distilled off, and the mixture was cooled to room temperature, so that the organic ultraviolet absorber and the radical scavenger were incorporated into the pores of the silica-based particles. Obtained 144 copies.

Preparation Example 4
<Preparation of a third siloxane composition>
In a glass container, 18.0 parts of KR500 (first oligomer), 23.5 parts of MKC silicate MS56S (second oligomer), 9.4 parts of X-40-9250 (third oligomer), KF-96-1000cs (silicone). 2.5 parts of oil), 32 parts of isopropanol (solvent), 3.0 parts of titanium n-tetrabutoxide (catalyst, D-25, manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed, and at room temperature (25) using an anchor type stirrer. The mixture was stirred at (° C.) for 20 minutes to prepare 100 parts of the third siloxane composition. The mass ratio of the cured siloxane product when the third siloxane composition was cured was 43.4% by mass with respect to the mass of the third siloxane composition before curing. The formulation of Preparation Example 4 is shown in the middle column of Example 16 (described later) in Table 5.

Example 10
<Manufacture of silica particles not surface-treated by sealing an organic ultraviolet absorber and a radical scavenger with a cured silicone of a modified example of the first siloxane composition>
A solution was prepared by blending 48.0 parts of KR-500 (oligomer of methyltrimethoxycisilane, manufactured by Shin-Etsu Chemical Co., Ltd.), 32.0 parts of isopropanol, and 2.7 parts of D-25 as the first oligomer. 144 parts by mass of the silica-based particles of Preparation Example 3 were charged into a stirrer, and the above solution was added dropwise over 10 minutes while stirring at 300 rpm, and the mixture was continuously stirred for 10 minutes until uniform. The mixture was allowed to stand at 23 ° C. for 2 days to cure the siloxane composition while volatilizing isopropanol to obtain an additive for resin having a solid content of 181.7 parts by mass. This resin additive is a silica particle in which an organic ultraviolet absorber and a radical scavenger are incorporated and sealed with a cured silicone product. The formulation of Example 10 is shown in Table 5. The following Examples 11 to 20 are also shown in Tables 5 and 6.

Example 11
<Manufacture of silica particles surface-treated by sealing an organic ultraviolet absorber and a radical scavenger with a cured silicone of a modified example of the first siloxane composition>
A solution was prepared by blending 45.0 parts of KR-500 as the first oligomer, 2.7 parts of one-ended alkoxy-modified silicone oil KR-4000A, 32.0 parts of isopropanol, and 2.7 parts of D-25. 144 parts by mass of the silica-based particles of Preparation Example 3 were charged into a stirrer, and the above solution was added dropwise over 10 minutes while stirring at 300 rpm, and the mixture was continuously stirred for 10 minutes until uniform. The mixture was allowed to stand at 23 ° C. for 2 days to cure the siloxane composition while volatilizing isopropanol to obtain an additive for resin having a solid content of 181.7 parts by mass. This resin additive is a silica particle in which an organic ultraviolet absorber and a radical scavenger are incorporated and sealed with a cured silicone product. The silica particles were surface-treated with one-terminal alkoxy-modified silicone oil phase-separated on the surface.

Example 12
<Manufacture of silica particles having an effect of surface treatment by sealing an organic ultraviolet absorber and a radical scavenger with a cured silicone of a modified example of the first siloxane composition>
A solution was prepared by blending 36.0 parts of KR-500 as the first oligomer, 11.7 parts of X-40-9250 of the third oligomer, 32.0 parts of isopropanol, and 2.7 parts of D-25. 144 parts by mass of the silica-based particles of Preparation Example 3 were charged into a stirrer, and the above solution was added dropwise over 10 minutes while stirring at 300 rpm, and the mixture was continuously stirred for 10 minutes until uniform. The mixture was allowed to stand at 23 ° C. for 2 days to cure the siloxane composition while volatilizing isopropanol to obtain an additive for resin having a solid content of 181.7 parts by mass. This resin additive is a silica particle in which an organic ultraviolet absorber and a radical scavenger are incorporated and sealed with a cured silicone product. Further, in these silica particles, the polydimethylsiloxane segment was phase-separated on the surface, which was effective in surface treatment.

Example 13
<Manufacture of silica particles not surface-treated by sealing an organic ultraviolet absorber and a radical scavenger with a cured silicone of a modified example of the second siloxane composition>
A solution was prepared by blending 57.2 parts of MKC silicate MS56S (oligomer of tetramethoxysilane, manufactured by Mitsubishi Chemical Corporation), 8.0 parts of isopropanol, and 4.0 parts of D-25 as the second oligomer. 144 parts by mass of the silica-based particles of Preparation Example 3 were charged into a stirrer, and the above solution was added dropwise over 10 minutes while stirring at 300 rpm, and the mixture was continuously stirred for 10 minutes until uniform. The siloxane composition was cured by allowing it to stand at 23 ° C. for 2 days while volatilizing acetone to obtain a resin additive having a solid content of 178.5 parts by mass. This resin additive is silica particles in which an organic ultraviolet absorber and a radical scavenger are incorporated and sealed with a cured silica product.

Example 14
<Manufacture of silica particles surface-treated by sealing an organic ultraviolet absorber and a radical scavenger with a cured silicone of a modified example of the second siloxane composition>
A solution was prepared by blending 53.3 parts of MKC silicate MS56S as the second oligomer, 2.7 parts of one-ended alkoxy-modified silicone oil KR-4000A, 8.0 parts of isopropanol, and 4.0 parts of D-25. 144 parts by mass of the silica-based particles of Preparation Example 3 were charged into a stirrer, and the above solution was added dropwise over 10 minutes while stirring at 300 rpm, and the mixture was continuously stirred for 10 minutes until uniform. The siloxane composition was cured by allowing it to stand at 23 ° C. for 2 days while volatilizing acetone to obtain a resin additive having a solid content of 178.5 parts by mass. This resin additive is a silica particle in which an organic ultraviolet absorber and a radical scavenger are incorporated and sealed with a cured silicone product. The silica particles had one-terminal alkoxy-modified silicone oil phase-separated on the surface, and had an effect of surface treatment.

Example 15
<Manufacture of silica particles having an effect of surface treatment by sealing an organic ultraviolet absorber and a radical scavenger with a cured silicone of a modified example of the second siloxane composition>
A solution was prepared by blending 41.4 parts of MKC silicate MS56S as the second oligomer, 11.7 parts of the third oligomer X-40-9250, 8.0 parts of isopropanol, and 4.0 parts of D-25. 144 parts by mass of the silica-based particles of Preparation Example 3 were charged into a stirrer, and the above solution was added dropwise over 10 minutes while stirring at 300 rpm, and the mixture was continuously stirred for 10 minutes until uniform. The siloxane composition was cured by allowing it to stand at 23 ° C. for 2 days while volatilizing acetone to obtain a resin additive having a solid content of 178.5 parts by mass. This resin additive is a silica particle in which an organic ultraviolet absorber and a radical scavenger are incorporated, sealed with a cured silicone product, and a segment of polydimethylsiloxane is phase-separated on the surface.

Example 16
<Manufacture of silica particles surface-treated by sealing an organic ultraviolet absorber and a radical scavenger with a cured silicone of a third siloxane composition>
144 parts by mass of silica-based particles of Preparation Example 3 were charged into a stirrer, and the solution of Preparation Example 4 was added dropwise over 10 minutes while stirring at 300 rpm, and stirring was continued for 10 minutes and mixed until uniform. The mixture was allowed to stand at 23 ° C. for 2 days to cure the siloxane composition while volatilizing isopropanol to obtain an additive for a resin having a solid content of 182.4 parts by mass. This resin additive is a silica particle in which an organic ultraviolet absorber and a radical scavenger are incorporated and sealed with a cured silicone product. In addition, the silica particles were surface-treated with silicone oil phase-separated on the surface.

<Tension fracture elongation and tensile fracture strength>
Similar to the evaluation of tensile elongation at break and tensile strength at break in Examples 1 to 9 and Comparative Examples 1 to 3 described above, tensile test pieces (resins) from the resin additives of Examples 10 to 16 A molded product) was formed, and the tensile elongation at break and the tensile strength at break were evaluated. The results are shown in Table 5.

<Consideration of Comparative Examples 1 to 3 in comparison with Examples 10 to 16>
In Comparative Examples 1 and 2, the organic UV absorbers were released remarkably rapidly, and they were not uniformly dispersed with respect to the resin, so that the tensile elongation at break and the tensile strength at break were increased. , It is presumed to be lower than those of Examples 10 to 16.

On the other hand, in Comparative Example 3, since the release of the radical scavenger was remarkably slow and the additive for resin was not uniformly dispersed with respect to the resin, the tensile elongation at break and the tensile strength at break were exhibited in Examples 10 to 10. It is presumed to be lower than those of Example 16.

<Manufacturing of silica particles surface-treated with RO group-containing silane compound>
Example 17
A solution was prepared by adding 4.0 parts of acetone and 2.0 parts of D-25 to 32.8 parts of 3-glycidoxypropyltrimethoxysilane. 176.8 parts of unsurface-treated silica-based particles of Example 13 were charged into a stirrer, and the above solution was added dropwise over 8 minutes while stirring at 300 rpm, and stirring was continued for 8 minutes until uniform. did. After standing at 23 ° C for 1 day. It was dried at 80 ° C. for 3 hours and surface-treated with 3-glycidoxypropyltrimethoxysilane. The obtained powder was crushed by a jet mill to obtain 200 parts of a resin additive with a total charge of 215.6 parts. The resin additive has silica particles surface-treated with 3-glycidoxypropylsilane.

Example 18
A solution was prepared by adding 4.0 parts of acetone and 2.0 parts of D-25 to 36.5 parts of 3-mercaptopropyltrimethoxysilane. 176.8 parts of unsurface-treated silica-based particles of Example 13 were charged into a stirrer, and the above solution was added dropwise over 8 minutes while stirring at 300 rpm, and stirring was continued for 8 minutes until uniform. did. After allowing to stand at 23 ° C. for 1 day, it was dried at 80 ° C. for 3 hours and surface-treated with 3-mercaptopropyltrimethoxysilane. The obtained powder was crushed by a jet mill to obtain 200 parts of a resin additive with a total charge of 219.3 parts. The resin additive has silica particles surface-treated with 3-mercaptopropylsilane.

Example 19
A solution was prepared by adding 4.0 parts of acetone and 2.0 parts of D-25 to 36.5 parts of 3-mercaptopropyltrimethoxysilane. 144 parts by mass of the silica-based particles of Preparation Example 3 were charged into a stirrer, and the above solution was added dropwise over 10 minutes while stirring at 300 rpm, and the mixture was continuously stirred for 10 minutes until uniform. The siloxane composition was cured by allowing it to stand at 23 ° C. for 2 days while volatilizing acetone to obtain a resin additive having a solid content of 176.8 parts by mass. This resin additive is a silica particle in which an organic ultraviolet absorber and a radical scavenger are incorporated, sealed with a cured silicone product, and a mercapto group is present on the surface.

Example 20
A solution was prepared by adding 21.2 parts of acetone to 50.4 parts of Acritte 85Q-1052. 176.8 parts of unsurface-treated silica-based particles of Example 13 were charged into a stirrer, and while stirring at 300 rpm, half the amount of the above solution was added dropwise over 5 minutes, and stirring was continued for 5 minutes to make it uniform. It was mixed until it became. After vacuum drying at 80 ° C. for 2 hours, the mixture was cooled to 23 ° C., and the remaining amount of the above solution was mixed under stirring in the same operation. After vacuum drying at 80 ° C. for 2 hours, the mixture is cooled to 23 ° C., and a solution containing 2 parts of titanium n-tetrabutoxide (catalyst, D-25, manufactured by Shin-Etsu Chemical Co., Ltd.) and 4 parts of acetone is mixed under stirring. After allowing to stand at 23 ° C. for 1 day, the mixture was vacuum dried at 80 ° C. for 3 hours and surface-treated with Acryt 85Q-1052. The obtained powder was crushed by a jet mill to obtain 200 parts of a resin additive with a total charge of 256.4 parts. As the resin additive, silica particles are surface-treated with Acryt 85Q-1052.

<Making a latex compound and making a casting film>
Production Example 1
To 19.8 parts of carboxy-modified SBR rubber latex, 7.9 parts of a 1% aqueous solution of demol NL (dispersant) and 0.5 part of a 10% aqueous solution of diazabicycloundecene (catalyst) were added, and homodisper 2.5 type ( While performing high-speed stirring with (Primix), 8.4 parts of the resin additive of Example 17 was gradually added and dispersed, and defoamed with a stirring defoaming device (Mazelstar manufactured by Kurabou) to have a solid content concentration of 50. A 5.5% latex compound was prepared. A latex compound is poured into a square glass mold with a side of 14 cm so that the dry film thickness is about 0.3 mm, and the mixture is allowed to stand at a temperature of 23 ° C. and a humidity of 55% for 72 hours. A film was made. The cast film was released from the mold and heat-treated at 140 ° C. for 30 minutes. Then, the casting film was punched out with a dumbbell cutter (SD type lever type sample cutting machine manufactured by Dumbbell Co., Ltd.) to prepare a dumbbell-shaped test piece (JIS K6251, No. 2 type test piece).

Production Example 2 to Production Example 4 and Comparative Production Example 1
In the same manner as in Production Example 1, the latex compounds of Production Examples 2 to 4 and Comparative Production Example 1 were prepared with the formulations shown in Table 7. A cast film was prepared from the latex compound, and after heat treatment, a test piece was prepared.

<Preparation and molding of resin compound>
Production Example 5
(Preparation of compound of ABS resin and additive for resin of Example 20 and preparation of test piece)
90 parts of ABS resin and 10 parts of the resin additive of Example 20 were dry-blended to obtain a resin composition. Then, the resin composition was kneaded at 240 ° C. using a twin-screw extruder (Process 11 desktop twin-screw extruder manufactured by Thermo Scientific Co., Ltd.) to form pellets (resin molded product). The pellets were melted again through the above twin-screw extruder and molded into a dumbbell-shaped resin molded body (JIS K7161-2, 1B type test piece) by the company's injection molding machine MiniJet Pro.

Production Example 6 to Production Example 8, Comparative Production Example 2, and Comparative Production Example 3
In the same manner as in Production Example 5, the compounds of Production Example 6 to Production Example 8, Comparative Production Example 2, and Comparative Production Example 3 were prepared with the formulations shown in Table 8, and at the kneading temperature shown in Table 8, the compounds were prepared. A resin molded body (test piece) was molded.

<Tensile test of cast film between Fabrication Example 1 to Fabrication Example 4 and Comparative Fabrication Example 1>
Tensile tests of each of the cast films of Fabrication Examples 1 to 4 and Comparative Fabrication Example 1 were carried out, and the tensile strength at break, the tensile modulus, and the elongation at break at 25 ° C. were measured. The results are shown in Table 9. The tensile elastic modulus was determined as the average elastic modulus until fracture.
Tensile test standard: JIS K6251 (2017)
Measuring equipment: AGS-50NX (Autograph manufactured by Shimadzu Corporation)
Tensile speed: 200 mm / min

<Tensile test between Fabrication Example 5 to Fabrication Example 8 and Comparative Fabrication Example 2 to Comparative Fabrication Example 3>
Tensile tests were carried out on each of the molding test pieces of Production Example 5 to Production Example 8 and Comparative Production Example 2 to Comparative Production Example 3, and the tensile breaking strength, tensile elastic modulus and tensile breaking elongation at 25 ° C. were measured. did. The results are shown in Table 9.
Tensile test standard: JIS K7161-2 (2014)
Measuring equipment: AGS-10kNX (Autograph manufactured by Shimadzu Corporation)
Tensile speed: 10 mm / min

<Discussion between Production Example 1 to Production Example 4 and Comparative Production Example 1>
In the molded test piece that has not been exposed to light yet, the preparation example 4 prepared by dispersing the additive for resin which has not been surface-treated is inorganic with respect to the comparative preparation example 1 in which the additive for resin is not dispersed. A high tensile modulus was exhibited due to the effect of filling the particles, but both the tensile strength at break and the elongation at break decreased. In Production Examples 1 to 3 in which the surface-treated resin additives were dispersed, the tensile strength at break, the tensile elastic modulus, and the elongation at break were all higher than those in Production Example 4. As a result, Preparation Example 1 and Preparation Example 2 showed higher tensile strength at break and higher tensile modulus than Comparative Preparation Example 1. This is an additive for resin based on the reaction of the epoxy group with the carboxyl group of SBR in Production Example 1 and the reaction of the thiol group with the double bond residue of SBR in Production Example 2 and Production Example 3. It is considered that the interfacial adhesive strength between the and SBR has increased. Since the cast films of Preparation Examples 1 to 3 had a stronger transparency than the cast films of Preparation Example 4, it was also suggested that the dispersibility was improved.

<Discussion between Production Example 5, Production Example 6 and Comparative Production Example 2>
In the molded test piece that has not been exposed to light yet, the preparation example 6 prepared by dispersing the additive for resin which has not been surface-treated is inorganic with respect to the comparative preparation example 2 in which the additive for resin is not dispersed. A high tensile modulus was exhibited due to the effect of filling the particles, but both the tensile strength at break and the elongation at break decreased. In Production Example 5 in which the surface-treated resin additive was dispersed, the tensile breaking strength, the tensile elastic modulus and the tensile elongation at break were all higher than those in Production Example 6. As a result, Fabrication Example 5 showed higher tensile breaking strength and higher tensile modulus than Comparative Fabrication Example 2. It is considered that this is because the PMMA chain on the surface of the particles shows high affinity with the acrylonitrile-styrene copolymer (AS resin) forming the matrix of the ABS resin in Production Example 5, and thus the interfacial adhesive strength is increased.

<Discussion between Production Example 7, Production Example 8 and Comparative Production Example 3>
In the molding test piece not yet exposed to light, the preparation example 8 prepared by dispersing the resin additive not surface-treated had inorganic particles as compared with the comparative preparation example 3 in which the resin additive was not dispersed. Although it showed a high tensile modulus due to the filling effect, both the tensile strength at break and the elongation at break decreased. In Production Example 7 in which the surface-treated resin additive was dispersed, the tensile breaking strength, the tensile elastic modulus and the tensile elongation at break were all higher than those in Production Example 8. As a result, Fabrication Example 7 showed higher tensile breaking strength and higher tensile modulus than Comparative Fabrication Example 3. It is considered that in Production Example 7, the PMMA chain on the particle surface is compatible with the PMMA resin forming the matrix, and the interfacial adhesive strength is increased.

Claims (13)

Porous particles and
An organic UV absorber and / or a radical scavenger incorporated into the porous particles,
An additive for a resin, which comprises a siloxane cured product that seals the organic ultraviolet absorber and / or the radical scavenger in the porous particles. The cured siloxane product is -SiR ₂ O- (the two Rs may be the same or different from each other and are selected from the group consisting of monovalent saturated hydrocarbon groups and monovalent aromatic hydrocarbon groups, respectively. Contains an RO group-containing siloxane unit that does not contain the siloxane unit represented by at least one monovalent hydrocarbon group) but contains an RO group (R represents a monovalent saturated hydrocarbon group). The resin additive according to claim 1, which comprises a cured product of a siloxane composition containing the first oligomer. The resin additive according to claim 1 or 2, wherein the cured siloxane product contains a cured product of a siloxane composition containing a second oligomer which is a condensation polymer of tetrafunctional organosilane. The siloxane composition is -SiR ₂ O- (the two Rs may be the same or different from each other and are selected from the group consisting of monovalent saturated hydrocarbon groups and monovalent aromatic hydrocarbon groups, respectively. A siloxane unit represented by at least one monovalent hydrocarbon group) and an RO group-containing siloxane unit containing an RO group (R indicates a monovalent saturated hydrocarbon group). The resin additive according to claim 2 or 3, which comprises 3 oligomers. The siloxane composition is -SiR ₂ O- (the two Rs may be the same or different from each other and are selected from the group consisting of monovalent saturated hydrocarbon groups and monovalent aromatic hydrocarbon groups, respectively. The resin additive according to any one of claims 2 to 4, further comprising a silicone oil containing the siloxane unit represented by at least one monovalent hydrocarbon group.). .. The resin additive according to any one of claims 1 to 5, wherein the porous particles have an oil absorption amount of 80 mL / 100 g or more. The resin additive according to any one of claims 1 to 6, wherein the porous particles are inorganic particles. The resin additive according to claim 7, wherein the inorganic particles contain silica-based particles. The porous particles in which the organic ultraviolet absorber and / or the radical scavenger are sealed with the siloxane cured product are surface-treated with an RO group-containing silane compound.
The RO group-containing silane compound includes an RO group (R represents at least one monovalent hydrocarbon group selected from the group consisting of a monovalent saturated hydrocarbon group and a monovalent aromatic hydrocarbon group). The resin additive according to claim 8, wherein the moiety other than the RO group contains the moiety capable of reacting with and / or being compatible with the resin. The first step of blending the porous particles, the organic ultraviolet absorber and / or the radical scavenger, and the siloxane composition.
It is characterized by comprising a second step of curing the siloxane composition and sealing the organic ultraviolet absorber and / or the radical scavenger in the porous particles by the siloxane cured product. , Manufacturing method of additive for resin. The addition for a resin according to claim 10, wherein in the first step, the organic ultraviolet absorber is blended into the porous particles, and then the radical scavenger is blended into the porous particles. Method of manufacturing the agent. A third step of surface-treating the porous particles in which the organic ultraviolet absorber and / or the radical scavenger is sealed with the siloxane cured product with a RO group-containing silane compound is further provided.
The RO group-containing silane compound includes an RO group (R represents at least one monovalent hydrocarbon group selected from the group consisting of a monovalent saturated hydrocarbon group and a monovalent aromatic hydrocarbon group). The method for producing an additive for a resin according to claim 10 or 11, wherein the moiety other than the RO group and which is capable of reacting with and / or being compatible with the resin is contained. With resin
A molded product containing the resin additive according to any one of claims 1 to 9.

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