JP2018203942A - Modified polyolefin resin for outdoor molding bodies, outdoor molding body prepared therewith and method for producing the same - Google Patents

Abstract

To provide a modified polyolefin resin for outdoor molding bodies that suppresses bleedout, and exhibits and maintains excellent light resistance and weather resistance.SOLUTION: The present invention provides a modified polyolefin resin for outdoor molding bodies in which a cyclic hindered amine compound having a specific chemical formula is fixed to a polyolefin resin substantially by graft polymerization.SELECTED DRAWING: None

Description

  The present invention relates to a modified polyolefin resin for outdoor molded articles, an outdoor molded article using the same, and a method for producing them.

  Cyclic hindered amine light stabilizers (Hindered Amine Light Stabilizer: hereinafter abbreviated as “HALS”) are outdoor (use) molded articles, for example, films, sheets for agriculture, horticulture, fishery forestry or civil engineering, It is well known that it is used for the purpose of imparting light resistance and weather resistance to a tube or a covering material.

  Conventionally, in an outdoor (use) molded body having a layer including HALS (for example, a light-resistant layer and a weather-resistant layer), HALS moves (bleeds) to an adjacent layer due to various factors, and finally May bleed out to the outermost surface of the outdoor molded body, and as a result, sufficient light resistance and weather resistance may not be imparted to the outdoor molded body.

  In addition, during this bleed-out process, HALS generates a neutralization reaction with additives (for example, acidic substances) and external factors (sprayed acidic pesticides, acid rain, etc.) in the outdoor molded body, and light of HALS Stabilization may be inactivated, light resistance and weather resistance may be impaired, or a film as a by-product may be formed on the surface of the outdoor molded body, thereby hindering the original coating function. There was a case where the durability of was impaired.

  On the other hand, in Patent Document 1 (Japanese Patent Publication No. 63-2963), a specific homopolymer, a specific copolymer, and an initiator are used under normal pressure in order to impart extraction resistance to a desired polymer. A light stabilizer for plastics obtained by radical reaction with benzene has been proposed. However, since the light stabilizer for plastics of Cited Document 1 exists as a blocked polymer, it has been difficult to sufficiently exhibit weather resistance (light) at the time of molding of a molded article for outdoor use.

  In Patent Document 2 (Japanese Patent Laid-Open No. 4-80215), in order to provide an ethylene copolymer having improved light stability and compatibility of the copolymer, ethylene (A) and a hindered amine group in the side chain are disclosed. There has been proposed an ethylene copolymer having a small block structure obtained by subjecting a vinyl compound (B) having a high-pressure radical polymerization reaction. However, according to Patent Document 2, since it is essential to simultaneously react a plurality of monomers having different reaction rates, it has been difficult to suppress complete blocking.

  In Patent Document 3 (Japanese Patent Laid-Open No. 2002-265893), in order to provide a polyolefin resin using a polymer excellent in compatibility with a polyolefin resin, light resistance, and weather resistance, a radical polymerization reaction of ethylene is performed. Next, a polyolefin-based resin obtained by adding a cyclic amino compound and further causing a polymerization reaction has been proposed. However, according to Patent Document 3, since a plurality of polymerization reactions such as a radical polymerization reaction and other polymerization reactions are required, each manufacturing equipment, a polymerization initiator, a polymerization catalyst, a polymerization temperature adjustment and the like are necessary, which is complicated. In addition, the cost is excessive, which is not preferable.

  Therefore, still, modified polyolefin resin for outdoor moldings that suppresses bleed out and exhibits excellent light resistance and weather resistance, outdoor moldings using the same, and these manufacturing methods that realize simple, simple and low cost Development is required.

Japanese Patent Publication No. 63-2963 Japanese Patent Laid-Open No. 4-80215 JP 2002-265893 A

  The inventors focused on the structure and physical properties of a hindered amine compound (monomer) having a reactive functional group in the side chain, and the hindered amine compound (monomer) was substantially fixed to the polyolefin resin by graft polymerization. According to the modified polyolefin resin for molded articles, it has been found that bleeding out of this hindered amine compound can be suppressed at a high level, and excellent light resistance and weather resistance can be exhibited and maintained. The present invention has been made based on such knowledge.

  Therefore, according to the present invention, a hindered amine compound (monomer) having a reactive functional group in the side chain is fixed to a polyolefin resin substantially by graft polymerization, preferably under a radical initiator, thereby simplifying bleed out. The present invention provides a modified polyolefin resin for outdoor moldings, which can maintain weather resistance and light resistance for a long period of time, an outdoor molding using the same, and a method for producing them.

Therefore, one aspect of the present invention is a modified polyolefin resin for outdoor molded articles,
A cyclic hindered amine compound represented by the following chemical formula (I):
Comprising a polyolefin resin,
A modified polyolefin resin for outdoor moldings is proposed, wherein the cyclic hindered amine compound is substantially fixed to the polyolefin resin by graft polymerization.
[Chemical Formula (I)]
[In the above chemical formula (I),
R ₁ is a hydrogen atom, or a linear or branched alkyl group or alkoxyl group,
R ₂ is a (meth) acryloyl group or a vinyl group. ]

Specific examples of embodiments of the present invention are as follows.
[1] A modified polyolefin resin for outdoor moldings,
A cyclic hindered amine compound represented by the chemical formula (I);
Comprising a polyolefin resin,
A modified polyolefin resin for outdoor moldings, wherein the cyclic hindered amine compound is substantially graft-polymerized and fixed to a polyolefin resin.
[2] The amount of the unreacted cyclic hindered amine compound (monomer) is 0% by mass or more and 0.3% by mass or less based on the total mass of the modified polyolefin resin for outdoor moldings. Modified polyolefin resin for outdoor moldings.
[3] The modified polyolefin resin for outdoor molded bodies according to [1] or [2], wherein the cyclic hindered amine compound has a weight average molecular weight of 200 or more and 5000 or less.
[4] Any one of [1] to [3], wherein the content of the cyclic hindered amine compound is 0.01% by mass or more and 15% by mass or less based on the total mass of the modified polyolefin resin for outdoor moldings. The modified polyolefin resin for outdoor molded articles described in the item.
[5] The modified polyolefin resin for outdoor molding according to any one of [1] to [4], wherein the polyolefin resin is a linear low-density polyethylene.
[6] The modified polyolefin resin for outdoor molded articles according to any one of [1] to [5], further comprising a radical initiator.
[7] The content of the radical initiator is 0.01% by mass or more and 10% by mass or less based on the total mass of the cyclic hindered amine compound, the polyolefin resin, and the radical initiator. 6] Modified polyolefin resin for outdoor moldings.
[8] The modified polyolefin resin for outdoor molding according to [6] or [7], wherein an addition ratio (molar ratio) of the radical initiator and the cyclic hindered amine compound is 10: 1 or more and 1:10 or less.
[9] The modified polyolefin resin for outdoor molded bodies according to any one of [1] to [8], wherein the outdoor molded body is a film, a sheet, a tube, or a covering material.
[10] A method for producing a modified polyolefin resin for outdoor moldings,
(S1) A cyclic hindered amine compound represented by the above chemical formula (I), a polyolefin resin, and a radical initiator are prepared,
(S2) Under the radical initiator, the cyclic hindered amine compound and the polyolefin resin are graft-polymerized, and the cyclic hindered amine compound is substantially graft-polymerized and fixed to the polyolefin resin.
(S3) A method for producing a modified polyolefin resin for outdoor molded articles, comprising obtaining a modified polyolefin resin for outdoor molded articles.
[11] The production method according to [10], wherein the radical initiator is an organic peroxide.
[12] The production according to [10] or [11], comprising mixing, mixing, extruding, pressurizing, and / or heating the radical initiator, the cyclic hindered amine compound, and the polyolefin resin. Method.
[13] The production method according to [11], wherein the pressurization is performed at a pressure of 0.1 MPa to 100 MPa.
[14] An outdoor molded body,
[1] to [9] comprising the modified polyolefin resin for outdoor molded articles described in any one of
It is a sheet, film, tube / tube or covering material used outdoors.
Outdoor molded body.
[15] The outdoor molded body according to [14], wherein the outdoor molded body is for agriculture, horticulture, fishing, forestry, or civil engineering.
[16] A method for producing an outdoor molded body,
[1] to [9] Prepare a modified polyolefin resin for outdoor moldings according to any one of
Melt molding the resin for outdoor molding,
The manufacturing method which comprises obtaining the said outdoor molded object.
[17] The production method according to [16], wherein the melt molding is performed on the outdoor molded body resin by an inflation method and a T-die method.

  The modified polyolefin resin for outdoor moldings according to the present invention is produced by using a cyclic hindered amine compound “HALS”, which is a light stabilizer, substantially immobilized on the polyolefin resin by graft polymerization. In the outdoor molded body, HALS exists without bleeding out, achieves light resistance and weather resistance, suppresses neutralization reaction due to external factors (acid rain, acid pesticide, acid agent), and chemicals of HALS The effect can be exerted and maintained, the generation of a by-product coating on the surface of the outdoor molded body can be suppressed, and the physical and chemical modification of the outdoor molded body can be suppressed in a high level. And has a remarkable effect.

[Modified polyolefin resin for outdoor moldings]
(Graft polymerization fixation)
The modified polyolefin resin for outdoor molded articles according to the present invention is characterized in that the cyclic hindered amine compound represented by the chemical formula (I) is substantially fixed to the polyolefin resin by graft polymerization.

  By fixing the graft polymerization, the cyclic hindered amine compound is firmly fixed to the polyolefin resin (graft polymerization bond) as HALS, and the cyclic hindered amine compound moves by so-called bleed-out, or the outermost of the outdoor molded body. Precipitation on the surface can be suppressed in a high dimension. As a result, it becomes possible to impart excellent light resistance and weather resistance to the outdoor molded body produced with the modified polyolefin resin for outdoor molded body. Furthermore, since the cyclic hindered amine compound structural unit is appropriately dispersed and present as HALS in the outdoor molded body produced from this resin, further excellent light resistance and weather resistance are imparted to the outdoor molded body. It becomes possible.

<Substantially graft polymerization fixation>
In the present invention, “substantially graft-fixed” means that the cyclic hindered amine compound is completely fixed to the polyolefin resin by graft polymerization. That is, “substantially graft-fixed” means that the cyclic hindered amine compound (monomer) is completely graft-polymerized to the polyolefin resin, and preferably no cyclic hindered amine compound unreacted monomer exists, and / or Or it means that a gel substance (especially crosslinkable gel substance) does not occur. However, in the present invention, “substantially” is intended to allow the presence of a small amount of cyclic hindered amine compound unreacted monomer and / or unreacted polyolefin resin and the generation of a slight (crosslinkable) gel substance. is there.

<Unreacted monomer>
The abundance of the unreacted cyclic hindered amine compound (monomer) is preferably an extremely small amount based on the total mass of the modified polyolefin resin for outdoor moldings, the lower limit is 0% by mass or more, and the upper limit is 0.3 mass. % Or less, preferably 0.1% by mass or less. By setting the upper limit value to be equal to or less than the above numerical value, bleeding of the unreacted cyclic hindered amine compound is significantly suppressed, and as a result, the durability of the product can be further improved.

<Unreacted polyolefin resin / gel material>
The amount of the unreacted polyolefin resin and the gel substance are hardly present or a very small amount that is very difficult to measure, based on the total mass of the modified polyolefin resin for outdoor moldings.

(Cyclic hindered amine compounds)
In the present invention, a cyclic hindered amine compound represented by the following chemical formula (I) is used as HALS. Since R ₂ is a reactive functional group, it is firmly fixed to the polyolefin resin (graft polymerization bond), so that the modified polyolefin resin for outdoor molding and the hindered amine compound bleed in the outdoor molding using the same. Out can be suppressed in a higher dimension.
[Chemical Formula (I)]

In the chemical formula (I), R ₁ is a hydrogen atom, or a linear or branched alkyl group or alkoxyl group. The carbon number of the alkyl group or alkoxyl group has a lower limit of 1 or more and an upper limit of 20 or less. When the number of carbon atoms is in the above numerical range, the function as HALS can be sufficiently exhibited, and sufficient light resistance and weather resistance can be imparted to the film.

  Specific examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tertiary heptyl. , N-octyl, isooctyl, and tertiary octyl. Such alkoxyl groups include methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, heptyl Examples include oxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, and 2-ethylhexyloxy.

In the above chemical formula (I), R ₂ is a (meth) acryloyl group or an allyloxy group, and when bonded to the piperidine skeleton, a lower (approximately 1 to 5 carbon atoms) alkylene group is present. Also good.

Examples of the cyclic hindered amine compound represented by the chemical formula (I) include compounds in which R ₂ is a (meth) acryloyl group, and specific examples thereof include 1,2,2,6,6-pentamethyl-4-piperidyl. (Meth) acrylate, 2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, N-methoxy-2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, N-propyl Oxy-2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, N-butyloxy-2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, N-hexyloxy-2 , 2,6,6-Tetramethyl-4-piperidyl (meth) acrylate, N-octyloxy-2,2,6,6-tetramethyl-4-piperidyl And meth) acrylate, N-decyloxy-2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, and the like, preferably 1,2,2,6,6-pentamethyl-4-piperidyl ( A meth) acrylate (made by ADEKA: LA-82) or 2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate (made by ADEKA: LA-87) is exemplified.

Examples of the cyclic hindered amine compound represented by the chemical formula (I) include compounds in which R ₂ is a vinyloxy group, and specific examples thereof include 4- (allyloxy) -1,2,2,6,6-pentamethyl. Piperidine, 4- (allyloxy) -2,2,6,6-tetramethylpiperidine, N-methoxy-2,2,6,6-tetramethylpiperidine, 4- (allyloxy) -N-propyloxy-2,2 , 6,6-tetramethylpiperidine, 4- (allyloxy) -N-butyloxy-2,2,6,6-tetramethylpiperidine, 4- (allyloxy) -N-hexyloxy-2,2,6,6- Tetramethylpiperidine, 4- (allyloxy) -N-octyloxy-2,2,6,6-tetramethylpiperidine, 4- (allyloxy) -N-decyloxy -2,2,6,6-tetramethylpiperidine and the like are exemplified, preferably 4- (allyloxy) -1,2,2,6,6-pentamethylpiperidine, or 4- (allyloxy) -2,2 , 6,6-tetramethylpiperidine.

<Molecular weight>
Although the molecular weight of the cyclic hindered amine compound is not particularly limited, the weight average molecular weight is preferably 200 or more, and the upper limit is preferably 5000 or less, particularly preferably 2000 or less. The molecular weight is preferably within the above numerical range from the viewpoint of reactivity.

  When the molecular weight is not less than the above lower limit value, it can sufficiently react with the polyolefin resin without volatilizing at the processing temperature, and when the molecular weight is not more than the above upper limit value, sufficient dispersion in the polyolefin resin can be achieved. And a uniform reaction product (modified polyolefin resin for outdoor moldings) can be obtained.

<Content>
The content of the cyclic hindered amine compound is 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.1% by mass or more, based on the total mass of the modified polyolefin resin for outdoor moldings. It is 2 mass% or more, and an upper limit is 15 mass% or less, Preferably it is 10 mass% or less, More preferably, it is 7 mass% or less.

  From the viewpoint of reactivity, when the content is in the above numerical range, the graft reaction with the cyclic hindered amine compound will be performed uniformly, and blocking due to the polymerization reaction between monomers can be suppressed, It becomes possible to significantly reduce the variation in durability of the final product. As a result, it is possible to sufficiently exhibit the light resistance and weather resistance as HALS, and it is possible to significantly suppress the generation of a (crosslinkable) gel substance upon graft polymerization.

(Polyolefin resin)
The present invention uses a polyolefin resin. The polyolefin resin can firmly fix the cyclic hindered amine compound (graft polymerization bond), and can suppress bleed-out in a modified polyolefin resin for outdoor moldings and outdoor moldings using the same in a high dimension.

  Examples of the polyolefin resin include α-olefin homopolymers, copolymers of α-olefins as main components with different monomers, α-olefins and polyunsaturated compounds such as conjugated or nonconjugated dienes, acrylic A copolymer with acid, methacrylic acid, vinyl acetate or the like can be used.

Specific examples of the polyolefin resin include polyethylene. For example, high density polyethylene (density 0.92 to 0.96 g / cm ³ ; deflection temperature under load 130 ° C. or less), low density polyethylene (density 0.91 to 0.003). 92 g / cm ³ ; deflection temperature under load of 100 ° C. or less), ultra low density polyethylene (density less than 0.9 g / cm ³ ), linear low density polyethylene (density less than 0.94 g / cm ³ ), or ultra high molecular weight polyethylene (Number average molecular weight of 1.5 million or more), preferably linear low density polyethylene having a density of 0.85 g / cm ³ or more and less than 0.92 g / cm ³ .

  Polyolefin resins include polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic. An acid copolymer etc. are mentioned.

  When the polyolefin resin is a copolymer, other copolymerizable monomers constituting the copolymer include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene- Linear α-olefin such as 1; 4-methylpentene-1, 2-methylpropene-1, 3-methylpentene-1, 5-methylhexene-1, 4-methylhexene-1, 4,4-dimethylpentene Branched 留 -olefins such as -1; monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid; or monoesters thereof; methyl Acrylic acid or methacrylic acid ester such as methacrylate, methyl acrylate, ethyl acrylate, vinyl acetate, propio Vinyl esters of saturated carboxylic acids such as vinyl acid; aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene; acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, and aconitic anhydride An α, β-unsaturated nitrile such as acrylonitrile and methacrylonitrile; a diene monomer such as 1,4-hexadiene, dicyclopentadiene and ethylidenenorbornene; or acrylamide, methacrylamide and maleimide.

  These copolymerizable monomers may be used as one kind or a mixture of two or more kinds. Further, the copolymer may be any of a random type, a block type, a graft type, or a mixed type thereof. The proportion of these monomers in the copolymer is preferably 30% by mass or less, and more preferably 20% by mass or less. Preferable copolymers include propylene-ethylene copolymer, propylene-butene-1 copolymer, butene-1-ethylene copolymer, propylene-ethylene-butene-1 copolymer, and ethylene-vinyl acetate copolymer. , Ethylene-ethyl acrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-n-butyl acrylate copolymer, and the like.

<Molecular weight>
The molecular weight of the polyolefin resin is, as a weight average molecular weight, a lower limit value of 1,000 or more, preferably 5,000 or more, and an upper limit value of 1,000,000 or less, preferably 500,000 or less. .

<Content>
Regarding the content of the polyolefin resin, the lower limit is 0.01% by mass or more and the upper limit is 200% by mass or less based on the total mass of the modified polyolefin resin for outdoor molded articles.

(Radical initiator)
In the present invention, preferably, the cyclic hindered amine compound represented by the above chemical formula (I) in which R ₂ is a reactive functional group and the polyolefin resin are subjected to graft polymerization fixation in the presence of a radical initiator. Is.

  As radical initiators, azo compounds (RN = NR) such as azoisobutyl nitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobis-2-amidinopropane / hydrochloride; peroxodisulfuric acid Organic peroxides (—O—O—) such as potassium, ammonium peroxodisulfate, t-butylcumene hydroperoxide, benzoyl peroxide, lauroyl peroxide; redox initiators, triethylborane, diethylzinc, etc. are preferred, The organic peroxide can be appropriately selected depending on the processing temperature of the resin, and more preferably an organic peroxide.

  Specific examples of the radical initiator include, for example, benzoyl peroxide curing agent, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, 3,5,5-trimethylhexanoyl peroxide, di-n- Octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, dicumyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, succinic acid peroxide, 2,5-dimethyl -2,5-di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, tert-hexylperoxy-2-ethylhexanoate, 4- Methylbenzoyl peroxide, te t-butylperoxy-2-ethylhexanoate, m-toluoyl + benzoyl peroxide, benzoyl peroxide, 1,1-bis (tert-butylperoxy) -2-methylcyclohexanate, 1,1-bis (Tert-hexylperoxy) -3,3,5-trimethylcyclohexanate, 1,1-bis (tert-hexylperoxy) cyclohexanate, 1,1-bis (tert-amylperoxy) cyclohexanate 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexanate, 1,1-bis (tert-butylperoxy) cyclohexanate, 2,2-bis (4 4-di-tert-butylperoxycyclohexyl) propane, 1,1-bis (tert-butyl propane) Oxy) cyclododecane, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxymaleic acid, tert-butylperoxy-3,3,5-trimethylhexanoate, tert-butylperoxylaurate, 2, 5-dimethyl-2,5-di (methylbenzoylperoxy) hexane, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexyl monocarbonate, tert-amylperoxy-2-ethylhexyl monocarbonate, Examples include tert-hexylperoxy-2-ethylhexyl monocarbonate, tert-hexylperoxybenzoate, 2,5-di-methyl-2,5-di (benzoylperoxy) hexane, and the like. .

  The content of the radical initiator is 0.01% by mass or more, preferably 0.05% by mass or more, based on the total mass of the cyclic hindered amine compound, the polyolefin resin, and the radical initiator. Yes, more preferably 0.1% by mass or more, and the upper limit is 10% by mass or less, preferably 7% by mass or less, more preferably 5% by mass or less.

  When the lower limit value of the content of the radical initiator is the above numerical value, the cyclic hindered amine compound monomer does not remain unreacted, and as a result, the function as the HALS can be sufficiently exerted, and the light resistance In addition, the weather resistance can be sufficiently exerted, and the bleed out can be suppressed in a high dimension. Further, when the upper limit value of the content of the cyclic hindered amine compound is set to the above numerical value, generation of a (crosslinkable) gel substance at the time of graft polymerization can be significantly suppressed.

  According to a preferred embodiment of the present invention, the addition ratio (molar ratio) of the radical initiator and the cyclic hindered amine compound is 10: 1 or more, 1:10 or less, preferably 5: 1 or more, : 7 or less, more preferably 2: 1 or more, and 1: 5 or less.

(Additive)
In the present invention, an additive can be added as an optional component. Additives include anti-fogging agent, anti-fogging agent, lubricant, heat stabilizer, ultraviolet absorber, light stabilizer, organophosphate metal salt, inorganic substance, antioxidant, stabilization aid, antistatic agent, anti-mold Agents, anti-algae agents, and coloring agents.

  An additive can be used 1 type or in combination of 2 or more types. Although content of an additive can each be determined suitably, it is 0.01 mass% or more and 200 mass% or less on the basis of the total modified polyolefin resin for outdoor moldings.

<Anti-fogging agent>
A specific example of the antifogging agent is preferably a nonionic surfactant. For example, ether type of polyoxyethylene ether, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene ether, etc .; ester type of partially esterified fatty acid with polyhydric alcohol; glycerin ester polyoxyethylene Examples include ether esters such as ether and sorbitan ester polyoxylethylene ether.

<Anti-fogging agent>
Specific examples of the antifogging agent include a fluorine-based surfactant and a silicone-based surfactant.
Examples of the fluorosurfactant include surfactants in which a part or all of them are substituted with F instead of H bonded to C of the hydrophobic group of a normal surfactant. A surfactant containing a perfluoroalkenyl group may be mentioned.
Examples of the silicone surfactant include an anionic silicone surfactant, a nonionic silicone surfactant, a cationic silicone surfactant, and an amphoteric silicone surfactant. Examples of the anionic silicone surfactant include carboxylate-modified silicone, sulfonate-modified silicone, sulfate ester-modified silicone, and phosphate ester-modified silicone; nonionic silicone surfactants include Examples include polyoxyalkylene-modified silicones, (poly) glycerin-modified silicones, and sugar-modified silicones; examples of cationic silicone surfactants include quaternary ammonium-modified silicones; examples of amphoteric silicone surfactants And betaine-modified silicone.

<Lubricant / Heat Stabilization Aid Lubricant>
Examples of lubricants and / or heat stabilizers include polyethylene wax, fatty acid amides, stearic acid, zinc stearate, barium stearate, calcium stearate, barium ricinoleate, chelators such as organic phosphites, epoxy resins, etc. Is mentioned.

<Ultraviolet absorber>
Examples of the ultraviolet absorber include various ultraviolet absorbers such as benzotriazole, benzophenone, salicylic acid ester, hydroquinone, and cyanoacrylate.

  Specifically, 2- (2′-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5-methylphenyl) -5- Carboxylic acid butyl ester benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) -5,6-dichlorobenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) -5-ethylsulfone Benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2 ′ -Hydroxy-5'-aminophenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dimethylphenyl) Nzotriazole, 2- (2′-hydroxy-3 ′, 5′-dimethylphenyl) -5-methoxybenzotriazole, 2- (2′-methyl-4′-hydroxyphenyl) benzotriazole, 2- (2 ′ -Stearyloxy-3 ', 5'-dimethylphenyl) -5-methylbenzotriazole, 2- (2'-hydroxy-5-carboxylic acid phenyl) benzotriazole ethyl ester, 2- (2'-hydroxy-3'- Methyl-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3) '-T-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methoxyphenyl) Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-cyclohexylphenyl) benzotriazole, 2- (2′-hydroxy-4 ′, 5′-dimethylphenyl) -5-carboxylic acid benzotriazole butyl ester, 2- (2′-hydroxy-3 ′, 5′-dichlorophenyl) benzotriazole, 2- (2 '-Hydroxy-4', 5'-dichlorophenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dimethylphenyl) -5-ethylsulfonebenzotriazole, 2- (2'-hydroxy- 4'-octoxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-methoxyphenyl) -5-methylben Benzotriazole ultraviolet absorbers such as zotriazole, 2- (2′-hydroxy-5′-methylphenyl) -5-carboxylic acid ester benzotriazole, 2- (2′-acetoxy-5′-methylphenyl) benzotriazole 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,2'-dihydroxy- 4,4′-dimethoxybenzophenone, 2-hydroxy-4-benzoyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonebenzophenone, 2,2 ′, 4, 4'-tetrahydroxybenzof Benzophenone-based UV absorbers such as 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-5-chlorobenzophenone, bis- (2-methoxy-4-hydroxy-5-benzoylphenyl) methane Is mentioned.

[Method for producing modified polyolefin resin for outdoor molding]
In another aspect of the present invention, a method for producing a modified polyolefin resin for outdoor moldings,
(S1) A cyclic hindered amine compound represented by the above chemical formula (I), a polyolefin resin, and a radical initiator are prepared,
(S2) Under the radical initiator, the cyclic hindered amine compound and the polyolefin resin are graft-polymerized, and the cyclic hindered amine compound is substantially graft-polymerized and fixed to the polyolefin resin.
(S3) A production method comprising obtaining a modified polyolefin resin for outdoor molding can be proposed.

[Step (S1)]
The step (S1) may be the same as described in the modified polyolefin resin for outdoor moldings.

[Step (S2)]
In the present invention, a cyclic hindered amine compound and a polyolefin resin are graft-polymerized under a radical initiator. According to a preferred embodiment, it is preferable to thermally decompose a radical initiator (preferably an organic peroxide) to cause a graft polymerization reaction between the cyclic hindered amine compound and the polyolefin resin.
Preferably, a radical initiator, a cyclic hindered amine compound, and a polyolefin resin are subjected to a graft polymerization reaction by pressing and heating in an extrusion and / or pressurizer (more preferably, an extruding pressurizer). Also good.
The pressurization is about 0.1 MPa to 100 MPa, preferably about 0.5 MPa to 10 MPa. The heating (extrusion) temperature is about the melting point of the resin + 0 ° C. or more and about 50 ° C. or less, and preferably about the melting point of the resin + 10 ° C. or more and about 30 ° C. or less.

  When the lower limit of pressurization and heating (pressure and temperature) is the above numerical value, radicals are sufficiently generated, and the cyclic hindered amine compound monomer does not remain unreacted. As a result, light resistance as HALS And the weather resistance can be sufficiently exhibited, and bleeding out can be suppressed in a high dimension. Moreover, when the upper limit of pressurization and heating (pressure and temperature) is the above-mentioned numerical value, it is possible to significantly suppress carbonization of the manufactured modified polyolefin resin for outdoor moldings, and grafting It is possible to suppress the discoloration of the cyclic hindered amine compound monomer before polymerization.

[Step (S3)]
The resulting modified polyolefin resin for outdoor molded bodies may be solid, fluid, etc., preferably solid, and may be obtained in various forms such as pellets.

[Outdoor molded body]
In this invention, the outdoor molded object comprised from the modified polyolefin resin for outdoor molded objects can be proposed.
The outdoor molded body may be any form such as a sheet, a film, a tube / tube (polygon, circle, ellipse, various forms such as a gear type, a hollow form, etc.) or a covering material. It may be used for specific purposes such as for forestry, forestry and civil engineering.
Moreover, the outdoor molded body may be formed as a multi-layer laminate. In this case, the plurality of layers may be formed, for example, as layers each including the above-mentioned “additive”.
When it is molded as a sheet or film, its thickness can be determined appropriately according to its intended use, but if it is a film or sheet for agriculture, horticulture, fishery forestry, and civil engineering, it is 0.02 mm. It may be about 10 mm or less.

[Production method of outdoor molding]
In the present invention, a method for producing an outdoor molded body,
Prepare modified polyolefin resin for outdoor moldings,
Melt molding the resin for outdoor molding,
Proposed is a production method comprising obtaining the outdoor molded body.

(Preparation of outdoor molding)
After preparing and preparing a modified polyolefin resin for outdoor molding, an outdoor molding (film, sheet, tube / tube or covering material) is molded.

  As the molding method, for example, a melt extrusion molding method such as an inflation method and a T-die method, a co-extrusion method such as a calendar method, an inflation method and a T-die method, a multilayer processing method, a lamination method, an internal / external heating method, etc. are used. Thus, a desired outdoor molded body can be manufactured.

  For example, when using the inflation molding method, the modified polyolefin resin (pellet) for outdoor molding is supplied to each extruder of the inflation molding machine, and the melt extruded from the die is blown to form the desired outdoor molding. It is possible to produce a body.

  The pressure is about 0.1 MPa to 100 MPa, preferably about 0.5 MPa to 10 MPa. The heating (extrusion) temperature is about the melting point of the resin + 0 ° C. or more and about 50 ° C. or less, and preferably about the melting point of the resin + 10 ° C. or more and 30 ° C. or less.

  The present invention will be described in detail with reference to the following examples and comparative examples, but these merely disclose one embodiment of the present invention, and the scope of the present invention is limited to the contents of these examples. Is not to be done. In addition, by the following examples, those skilled in the art can easily implement all the invention modes included in the scope of the present invention.

(Modified polyolefin resin for outdoor molding)
The following are prepared as a cyclic hindered amine compound, a polyolefin resin, and a radical initiator, mixed according to the composition as shown in Table 1, and a twin-screw extruder (trade name: TEX28V-42CW-4V: Nippon Steel Works, Ltd.) (Manufactured by Hiroshima Seisakusho Co., Ltd.) and extruded at 190 ° C. and 300 rpm and pelletized.

<material>
As raw materials, “A”, “B”, “C1” and “C2” described in Table 1 below mean the following substances.
A: Linear low density polyethylene Prime Polymer Co., Ltd .: SP1520
[Density 0.913g / cm3, MFR 2.0g / 10min]
B: Radical generator 1,1-bis (tert-amylperoxy) cyclohexanate [manufactured by NOF Corporation: Perhexa HC]
C1: Vinyl group-containing cyclic amino compound 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate [manufactured by ADEKA: ADK STAB LA-82]
C2: Vinyl group-containing cyclic amino compound 2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate [manufactured by ADEKA: ADK STAB LA-87]

(Preparation of outdoor molding)
As a next step, pellets of modified polyolefin resin for outdoor moldings are used as a single-screw extruder (trade name “Lab Plast Mill D20-20” manufactured by Toyo Seiki Co., Ltd.), 150 mm wide T-die, 190 ° C., 30 rpm. It was made into a sheet.

(Evaluation test)
The outdoor molded bodies (sheets) prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were subjected to the following evaluation tests, and the evaluation results are shown in Table 1.

<1: Bleed property evaluation test>
After the sheet is placed in a dry oven maintained at a temperature of 60 ° C. and stored for 30 days, the surface state of the sheet is observed with a microscope, and a standardized sheet (reference) using only a polyolefin resin, a molded sheet, Was evaluated according to the following criteria.
<Evaluation criteria>
Evaluation A: Bleed was hardly confirmed, the sheet was less sticky than the reference, and the sheets were slippery without being caught when they were stacked.
Evaluation ○: Although some bleed was present, it was transparent, not sticky, and the function as an outdoor sheet was not lost.
Evaluation (triangle | delta): Bleed exists and it has adhesiveness, and there were many adhesions of a fingerprint and dust.
Evaluation x: Many bleeds existed, there was no transparency, stickiness was seen on the sheet surface, and there was a sound when the stacked sheets were peeled off.

<2: Light resistance evaluation test>
About the prepared sheet, using iSuper UV Tester SUV-W261 (Iwasaki Electric Co., Ltd.), punching for 100 hours with No. 3 dumbbell, and using Autograph AG-X plus (Shimadzu Corporation) A tensile test was performed at 5 kN and a tensile speed of 200 mm / min. The residual strength at break when compared with the sheet before the light resistance test was evaluated according to the following evaluation criteria.
<Evaluation criteria>
Evaluation A: The residual strength at break was 90% or more.
Evaluation 0: The residual strength at break was 70% or more and less than 90%.
Evaluation Δ: The residual strength at break was 50% or more and less than 70%.
Evaluation x: The residual strength at break was less than 50%.

<3: Appearance evaluation test>
After the sheet was stored at 23 ° C. for one month, the appearance of the sheet was visually observed and evaluated according to the following criteria.
<Evaluation criteria>
Evaluation A: There was no change in appearance.
Evaluation ◯: Although there was a slight change in haze and hue on the appearance, it was difficult to distinguish visually.
Evaluation (triangle | delta): The change of the haze and hue over the whole was recognized visually. Alternatively, partial cloudiness, streaks, and surface irregularities partially occurred.
Evaluation x: It was clearly understood that there were many cloudiness, streaks, surface irregularities, etc. on the appearance, and the function as an outdoor sheet was not exhibited.

<4. Other evaluations>
In Comparative Example 1 and Comparative Example 2, there was an unreacted product of a cyclic hindered amine compound monomer. In Comparative Example 3, since the radical initiator was excessive, the crosslinking component of the resin increased, and the film appearance deteriorated. In Comparative Example 4, HALS was insufficient, and the functions of light resistance and weather resistance were not exhibited as an outdoor molded body.

Claims (17)

A modified polyolefin resin for outdoor moldings,
A cyclic hindered amine compound represented by the following chemical formula (I):
Comprising a polyolefin resin,
A modified polyolefin resin for outdoor moldings, wherein the cyclic hindered amine compound is substantially graft-polymerized and fixed to a polyolefin resin.
[Chemical Formula (I)]
[In the above chemical formula (I),
R ₁ is a hydrogen atom, or a linear or branched alkyl group or alkoxyl group,
R ₂ is a (meth) acryloyl group or a vinyl group. ]   The outdoor molded object of Claim 1 whose abundance of an unreacted cyclic hindered amine compound (monomer) is 0 to 0.3 mass% on the basis of the total mass of the modified polyolefin resin for outdoor molded articles. Modified polyolefin resin.   The modified polyolefin resin for outdoor moldings according to claim 1 or 2, wherein the cyclic hindered amine compound has a weight average molecular weight of 200 or more and 5000 or less.   4. The content of the cyclic hindered amine compound according to claim 1, wherein the content of the cyclic hindered amine compound is 0.01% by mass or more and 15% by mass or less based on the total mass of the modified polyolefin resin for outdoor molded bodies. Modified polyolefin resin for outdoor moldings.   The modified polyolefin resin for outdoor moldings according to any one of claims 1 to 4, wherein the polyolefin resin is linear low-density polyethylene.   The modified polyolefin resin for outdoor molded articles according to any one of claims 1 to 5, further comprising a radical initiator.   The content of the radical initiator is 0.01% by mass or more and 10% by mass or less based on the total mass of the cyclic hindered amine compound, the polyolefin resin, and the radical initiator. Modified polyolefin resin for outdoor moldings as described.   The modified polyolefin resin for outdoor molded articles according to claim 6 or 7, wherein an addition ratio (molar ratio) of the radical initiator and the cyclic hindered amine compound is 10: 1 or more and 1:10 or less.   The modified polyolefin resin for outdoor molded articles according to any one of claims 1 to 8, wherein the outdoor molded article is a film, a sheet, a tube, or a covering material. A method for producing a modified polyolefin resin for outdoor moldings,
(S1) A cyclic hindered amine compound represented by the following chemical formula (I), a polyolefin resin, and a radical initiator are prepared,

[Chemical Formula (I)]
[In the above chemical formula (I),
R ₁ is a hydrogen atom, or a linear or branched alkyl group or alkoxyl group,
R ₂ is a (meth) acryloyl group or a vinyl group. ]
(S2) Under the radical initiator, the cyclic hindered amine compound and the polyolefin resin are graft-polymerized, and the cyclic hindered amine compound is substantially graft-polymerized and fixed to the polyolefin resin.
(S3) A method for producing a modified polyolefin resin for outdoor molded articles, comprising obtaining a modified polyolefin resin for outdoor molded articles.   The production method according to claim 10, wherein the radical initiator is an organic peroxide.   The manufacturing method according to claim 10 or 11, comprising mixing the radical initiator, the cyclic hindered amine compound, and the polyolefin resin, and extruding, pressing, and / or heating.   The manufacturing method according to claim 12, wherein the pressurization is performed at a pressure of 0.1 MPa to 100 MPa. An outdoor molded body,
Sheets, films, tubes / tubes or covering materials used outdoors,
The outdoor molded object comprised by the modified polyolefin resin for outdoor molded objects as described in any one of Claims 1-9.   The outdoor molded body according to claim 14, wherein the outdoor molded body is used for agriculture, horticulture, fishery forestry, or civil engineering. A method for manufacturing an outdoor molded body,
Preparing a modified polyolefin resin for outdoor moldings according to any one of claims 1 to 9,
Melt molding the resin for outdoor molding,
The manufacturing method which comprises obtaining the said outdoor molded object.   The manufacturing method according to claim 16, wherein the melt molding is performed on the outdoor molded body resin by an inflation method and a T-die method.