WO2015056655A1 - Controlled-release resin composition - Google Patents

Abstract

Provided is a pellet-shaped controlled-release resin composition which exhibits a strong blocking effect and excellent long-term storage stability. The controlled-release resin composition is configured so as to include at least a base resin and a functional additive. The controlled-release resin composition is molded into a pellet shape, and an antiblocking agent having an oil absorption level of 100ml/100mg or higher is adhered to the surface thereof.

Description

Sustained release resin composition

The present invention relates to a sustained release resin composition in which a functional additive such as a chemical solution, a fragrance, and a lubricating oil is kneaded in a base resin, and the functional additive is continuously released from the base resin in small amounts. The present invention relates to a means for preventing blocking of a sustained-release resin composition formed into a pellet.

In recent years, resin materials for molding are generally supplied to the market in the form of pellets because they can be easily taken out from storage locations, supplied to molding apparatuses, transported between storage locations, and measured. . In this case, when the blocking (a phenomenon in which the pellets adhere to each other) occurs in the resin material molded into a pellet shape, the above-described various advantages are lost, and thus the molded pellet is subjected to a blocking prevention treatment. (See the claims of Patent Document 1.) The anti-blocking treatment is performed by attaching an anti-blocking agent to the surface of the pellet.

In Patent Document 1, inorganic powder, organic powder, fatty acid powder, fatty acid derivative powder, and the like are used as an antiblocking agent, and silica, talc, calcium carbonate, and mica are particularly preferable as the inorganic powder, and an antiblocking agent. It is described that the average particle size of is particularly preferably from 0.1 to 50 μm.

JP 2012-040719 A

By the way, a sustained-release resin composition obtained by kneading functional additives such as chemicals, fragrances, and lubricating oils in a base resin is also shipped in the form of pellets and molded into a desired shape by a molding apparatus. . The sustained-release resin composition, because of its characteristics, is a functional additive that exudes from the base resin because it exhibits the required functions and effects by continuously releasing the functional additive from the base resin minutely. Therefore, blocking is more likely to occur than other general resin materials.

Therefore, for the sustained-release resin composition, the general anti-blocking agent listed in Patent Document 1, that is, inorganic powder, organic powder, fatty acid powder, fatty acid derivative having an average particle size of 0.1 to 50 μm It is difficult to obtain a sufficient blocking effect only by performing a blocking treatment using the above powder or the like.

The present invention has been made in view of the actual situation of the prior art, and an object thereof is to provide a pellet-like sustained release resin composition having a high anti-blocking effect and excellent long-term storage stability. It is in.

In order to solve such problems, the present invention includes a base resin, a functional additive, and a sustained-release aid for the functional additive, and is formed into pellets. An anti-blocking agent having an oil absorption of 100 ml / 100 mg or more is attached to the surface of

As described above, since the functional additive oozes out from the base resin, the sustained-release resin composition obtains the required blocking effect by using an anti-blocking agent for other general resin materials. I can't. On the other hand, the content of the functional additive contained in the base resin is naturally limited. Therefore, the present invention pays attention to the content of the functional additive and the oil absorption amount of the anti-blocking agent, and applies an anti-blocking agent having an oil absorption amount of 100 ml / 100 mg or more to the surface of the pellet-like sustained release resin composition. It was found that if it adheres, the sustained-release resin composition can have the required anti-blocking effect.

The present invention is also characterized in that, in the sustained-release resin composition having the above-described configuration, the antiblocking agent is a granule having an average particle diameter of 1 to 100 μm.

The outer shape and average particle diameter of the anti-blocking agent are closely related to the amount of anti-blocking agent adhering to the pellet surface, the uniformity of the adhesion, and thus the anti-blocking effect. According to experiments, when an anti-blocking agent for granules having an average particle size of 1 to 100 μm is used, a large amount of anti-blocking agent can be uniformly attached to the pellet surface, thus preventing blocking of the sustained-release resin composition. The effect is enhanced.

In the sustained-release resin composition having the above-described configuration, the anti-blocking agent has a specific surface area of 100 m ² or more and 1000 m ² or less.

The more the anti-blocking agent is porous and the higher the specific surface area is, the more functional additives can be adsorbed. On the other hand, if the specific surface area of the antiblocking agent is too high, the sustained release of the functional additive is impaired. According to experiments, when the specific surface area of the antiblocking agent is 100 m ² or more and 1000 m ² or less, it is possible to achieve both the antiblocking effect of the sustained release resin composition and the sustained release of the functional additive.

According to the present invention, the anti-blocking agent having an oil absorption of 100 ml / 100 mg or more is attached to the surface of the sustained-release resin composition formed into pellets, so that the functional additive is generally released gradually. A sustained-release resin composition that is more likely to cause blocking than a typical resin material can be provided with a required anti-blocking effect.

Hereinafter, the configuration of the sustained-release resin composition according to the embodiment will be described. The sustained-release resin composition according to the embodiment includes a base resin, a functional additive, a sustained-release aid for the functional additive, an organic weathering agent, an inorganic weathering agent, and an inorganic filler, It is formed into pellets. An antiblocking agent is attached to the surface of the pellet.

[Base resin]
The base resin is not particularly limited as long as it satisfies the moldability and mechanical strength required for the sustained-release resin molding. Examples include polyamide resin, polyacetal resin, polyethylene resin, polypropylene resin, polystyrene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polyarylate resin, polyphenylene ether resin, thermoplastic polyurethane resin, liquid crystalline polyester resin, etc. Can be mentioned.

Specific examples of the polyamide resin include polyamide resins such as polyamide 6, polyamide 66, polyamide 11 and polyamide 12 resin, and aromatic polyamide resins such as polyamide MXD and polyamide 6T resin.

Specific examples of the polyacetal resin include, in addition to a homopolymer consisting only of oxymethylene units, copolymers having oxymethylene units as main components and other copolymer units such as oxyethylene units as subcomponents thereof, these Examples thereof include a cross-linked polymer obtained by cross-linking and a graft copolymer formed by graft copolymerization.

Specific examples of the polyethylene resin include high density polyethylene, low density polyethylene, ultra low density polyethylene, and linear low density polyethylene.

Specific examples of the polypropylene resin include a polypropylene homopolymer, a random copolymer of ethylene and propylene, and a block copolymer.

Specific examples of polystyrene resins include styrene homopolymers, styrene-acrylic acid copolymers based on styrene, styrene-methyl acrylate copolymers, styrene-ethyl acrylate copolymers, styrene-methacrylic copolymers. Acid copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene-polyphenylene ether copolymer, styrene-butadiene copolymer, styrene-acrylonitrile Examples include copolymers, acrylonitrile-butadiene-styrene copolymers, styrene-methylstyrene copolymers, styrene-dimethylstyrene copolymers, styrene-ethylstyrene copolymers, styrene-diethylstyrene copolymers, and the like. The styrene component content in the styrene-based copolymer is preferably 50 mol% or more, particularly preferably 80 mol% or more.

As the polyethylene terephthalate resin, a polymer obtained by polycondensation using terephthalic acid as an acid component and ethylene glycol as a glycol component can be used. In addition, as an acid component, isophthalic acid, naphthalenedicarboxylic acid, adipic acid, Sebacic acid, dodecanedioic acid, oxalic acid, etc. as glycol components, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol , Cyclohexanediol, or the like, or a long chain glycol having a molecular weight of 400 to 6000, that is, a copolymer of 20 mol% or less of polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. It is also possible to.

The polybutylene terephthalate resin has a structure in which terephthalic acid units and 1,4-butanediol units are ester-bonded, 50 mol% or more of dicarboxylic acid units are composed of terephthalic acid units, and 50 mol% or more of diol components are A polymer composed of 1,4-butanediol units can be preferably used.

If there are too few terephthalic acid units or 1,4-butanediol units, for example, less than 50 mol%, the crystallization rate of the PBT resin may decrease, and the moldability of the resulting polybutylene terephthalate resin may decrease. Therefore, the proportion of terephthalic acid units in all dicarboxylic acid units is usually 70 mol% or more, preferably 80 mol% or more, more preferably 95 mol% or more, and particularly preferably 98 mol% or more. The proportion of 1,4 butanediol units is usually 70 mol% or more, preferably 80 mol% or more, more preferably 95 mol% or more, and particularly preferably 98 mol% or more.

In the dicarboxylic acid component that is a raw material of the polybutylene terephthalate resin, there is no particular limitation as a dicarboxylic acid component other than terephthalic acid. Specifically, for example, phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenylsulfone dicarboxylic acid and 2,6-naphthalenedicarboxylic acid; fats such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Cyclic dicarboxylic acids; aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid; These dicarboxylic acid components can be introduced into the polymer skeleton as dicarboxylic acids, or using dicarboxylic acid derivatives such as dicarboxylic acid esters and dicarboxylic acid halides as raw materials.

The diol component that is a raw material of the polybutylene terephthalate resin is not particularly limited as a diol component other than 1,4-butanediol. Specifically, for example, ethylene glycol, diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1,5-pentanediol, neopentyl glycol Aliphatic diols such as 1,6-hexanediol and 1,8-octanediol; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexanedimethylol Alicyclic diols such as xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone and the like; Cited That.

Furthermore, the polybutylene terephthalate resin may be a copolymer of any conventionally known monomer unit. Specific examples of the monomer component include hydroxy such as lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-β-hydroxyethoxybenzoic acid and the like. Carboxylic acids; monofunctional components such as alkoxycarboxylic acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid; tricarbaric acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid And trifunctional or higher polyfunctional components such as acid, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, and the like.

Examples of the polycarbonate resin include polymers obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted or a transesterification method in which a dihydroxydiaryl compound and a carbonic ester such as diphenyl carbonate are reacted. A typical example is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A).

Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane 1,1-bis (4-hydroxy-3- Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4 Bis (hydroxyaryl) alkanes such as -hydroxy-3,5-dichlorophenyl) propane, 1,1- Bis (hydroxyaryl) cycloalkanes such as 1,4-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3′-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3 ′ Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone Sulfone, and the like.

These are used singly or in combination of two or more, but in addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, etc. may be used in combination. Furthermore, the dihydroxyaryl compound and a trivalent or higher valent phenol compound as shown below may be used in combination. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4′-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

The viscosity average molecular weight of the polycarbonate resin is not particularly limited, but is usually from 10,000 to 100,000, more preferably from 15,000 to 30,000, and even more preferably from 17,000 to 26,000 in terms of moldability and strength. Moreover, when manufacturing this polycarbonate resin, a molecular weight modifier, a catalyst, etc. can be used as needed.

As the polyarylate resin, a resin having an aromatic dicarboxylic acid residue and a bisphenol residue as repeating units can be used. Polyarylate raw materials for introducing bisphenol residues are bisphenols, and specific examples thereof include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5- Dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 4,4'-dihydroxydiphenylsulfone 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, etc. It is done. These compounds may be used alone or in combination of two or more. In particular, 2,2-bis (4-hydroxyphenyl) propane is economically preferable, and it is optimal to use the compound alone.

On the other hand, as raw materials for introducing an aromatic dicarboxylic acid residue into a polyarylate resin, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenic acid, Examples include 4,4′-dicarboxydiphenyl ether, bis (p-carboxyphenyl) alkane, 4,4′-dicarboxydiphenyl sulfone, and terephthalic acid and isophthalic acid are particularly preferable. In the present invention, a polyarylate resin composition obtained by mixing and using both is particularly preferable in terms of melt processability and mechanical properties. The mixing ratio (terephthalic acid / isophthalic acid) can be arbitrarily selected, but is preferably in the range of 90/10 to 10/90 in terms of molar fraction, more preferably 70/30 to 30/70, The optimum is 50/50. Even if the mixed mole fraction of terephthalic acid is less than 10 mol% or more than 90 mol%, it may be difficult to obtain a sufficient degree of polymerization by the interfacial polymerization method. The polyarylate resin desirably has an intrinsic viscosity of 0.4 to 1.0, preferably 0.4 to 0.8, more preferably 0.5 to 0.7, from the viewpoint of mechanical properties and fluidity. .

The polyphenylene ether resin has a repeating unit structure of the following formula (1) and has a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) in the range of 0.15 to 1.0 dl / g. Homopolymers and / or copolymers can be used. A more preferred reduced viscosity is in the range of 0.20 to 0.70 dl / g, most preferably in the range of 0.40 to 0.60.

(R1 and R4 each independently represent hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl or hydrocarbonoxy. R2 and R3 each independently represent hydrogen, primary or Or secondary lower alkyl, phenyl.)
Specific examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl- 6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), etc., and 2,6-dimethylphenol and other phenols (for example, 2, And polyphenylene ether copolymers such as copolymers with 3,6-trimethylphenol and 2-methyl-6-butylphenol). Of these, poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1) is more preferable. , 4-phenylene ether).

As an example of a method for producing the polyphenylene ether resin, there is a method of oxidative polymerization of 2,6-xylenol using a complex of cuprous salt and amine described in US Pat. No. 3,306,874 as a catalyst. The specifications of US Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, Japanese Patent Publication No. 52-17880, Japanese Unexamined Patent Publication No. 50-51197 and Japanese Unexamined Patent Publication No. 63-152628 are also disclosed. The methods described in these publications are also preferable as a method for producing a polyphenylene ether resin. The polyphenylene ether resin may be used as it is after the polymerization step, or melt kneaded using an extruder or the like under a nitrogen gas atmosphere or a non-nitrogen gas atmosphere, devolatilization or non-devolatilization. It may be used as a pellet.

The polyphenylene ether resin includes polyphenylene ether functionalized with various dienophile compounds. Examples of various dienophile compounds include maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, itaconic acid, acrylic acid, methacrylic acid, methyl allylate, methyl methacrylate, glycidyl acrylate, glycidyl methacrylate, stearyl acrylate and styrene. In order to functionalize polyphenylene ether with these dienophile compounds, an extruder may be used in the presence or absence of a radical generator, which may be functionalized in a molten state under devolatilization or non-devolatilization. The functionalization may be performed in the non-molten state, that is, in the temperature range from room temperature to the melting point in the presence or absence of the agent. The melting point of the functionalized polyphenylene ether is the peak top temperature of the peak observed in the temperature-heat flow graph obtained when the temperature is raised at 20 ° C./min in the differential thermal scanning calorimeter (DSC) measurement. If there are multiple peak top temperatures, the highest temperature is defined.

The polyphenylene ether resin may contain a resin component other than polyphenylene ether, such as an aromatic vinyl polymer. Examples of the aromatic vinyl polymer include atactic polystyrene, high impact polystyrene, syndiotactic polystyrene, and acrylonitrile-styrene copolymer. When the polyphenylene ether resin contains a polyphenylene ether resin and an aromatic vinyl polymer, the polyphenylene ether resin is 70 wt% or more, preferably 80 wt%, based on the total amount of the polyphenylene ether resin and the aromatic vinyl polymer. % Or more.

As the thermoplastic polyurethane resin, a thermoplastic polyurethane resin containing polyisocyanate and polyol as starting materials can be used. Among them, the content of oxyethylene groups in the thermoplastic polyurethane resin is 40% by mass or more and 65% by mass or less. A film having a softening temperature of 160 ° C. or higher by thermomechanical analysis (TMA) when a film having a thickness of 20 μm is suitable.

As the liquid crystalline polyester resin, a liquid crystalline polyester resin that forms an anisotropic molten phase called a thermotropic liquid crystalline polyester can be used. The property of the anisotropic molten phase of the liquid crystal polyester resin can be confirmed by a normal deflection inspection method using an orthogonal deflector, that is, by observing a sample placed on a hot stage in a nitrogen atmosphere. And as liquid crystalline polyester resin used for this invention, it contains the repeating unit represented by following formula (2) and / or the repeating unit represented by Formula (3), and is represented by Formula (2). A blend of two or more liquid crystal polyester resins in which the amount of the repeating unit is less than 40 mol% in all repeating units can also be used.

The liquid crystal polyester resin may be either a semi-aromatic liquid crystal polyester resin having an aliphatic group in the molecular chain, or a wholly aromatic liquid crystal polyester resin in which the molecular chains are all composed of aromatic groups. Among these liquid crystal polyester resins, it is preferable to use a wholly aromatic liquid crystal polyester resin because of its good flame retardancy and mechanical properties. Examples of the repeating unit constituting the liquid crystal polyester resin include an aromatic oxycarbonyl repeating unit, an aromatic dicarbonyl repeating unit, an aromatic dioxy repeating unit, an aromatic oxydicarbonyl repeating unit, and an aliphatic dioxy repeating unit. . Among these repeating units, the liquid crystalline polyester resin is, as an aromatic oxycarbonyl repeating unit, a 6-oxy-2-naphthoyl repeating unit represented by the formula (2) and / or a formula (3). The paraoxybenzoyl repeating unit is essential.

In the liquid crystal polyester resin, the amount of the repeating unit represented by the formula (2) in all repeating units is less than 40 mol% in order that the obtained liquid crystal polyester resin composition exhibits high toughness (impact strength). Yes, it is preferably 35 mol% or less, and particularly preferably 30 mol% or less. In the liquid crystal polyester resin, the amount of the repeating unit represented by the formula (3) in all the repeating units is achieved by the purpose of the present invention, and the repeating unit represented by the formula (2) in all the repeating units. As long as the amount is less than 40 mol%, it is not particularly limited, but it is preferably 80 mol% or less, and particularly preferably 75 mol% or less.

Examples of the monomer that gives the repeating unit of the formula (2) include 6-hydroxy-2-naphthoic acid, and examples of the monomer that gives the repeating unit of the formula (3) include parahydroxybenzoic acid. These monomers may be used as ester-forming derivatives such as acylated products, ester derivatives and acid halides.

When the liquid crystalline polyester resin is composed of only repeating units represented by the formulas (2) and (3), the repeating unit represented by the formula (2) in all the repeating units of the liquid crystal polyester resin. The content of is preferably 15 to 30 mol%, particularly preferably 20 to 30 mol%.

The liquid crystal polyester resin may contain an aromatic oxycarbonyl repeating unit other than the formula (2) and the formula (3). Specific examples of monomers that give aromatic oxycarbonyl repeating units other than those represented by formulas (2) and (3) include, for example, metahydroxybenzoic acid, orthohydroxybenzoic acid, 5-hydroxy-2-naphthoic acid, 3- Hydroxy-2-naphthoic acid, 4′-hydroxyphenyl-4-benzoic acid, 3′-hydroxyphenyl-4-benzoic acid, 4′-hydroxyphenyl-3-benzoic acid, alkyl, alkoxy or halogen substituents thereof, And alkyl, alkoxy or halogen substituted products of 6-hydroxy-2-naphthoic acid and parahydroxybenzoic acid. These monomers may be used as ester-forming derivatives such as acylated products, ester derivatives and acid halides.

In the present invention, preferred wholly aromatic liquid crystal polyester resins include the repeating unit represented by the formula (2) and / or the repeating unit represented by the formula (3), the aromatic dicarbonyl repeating unit and the aromatic dioxy. It consists of repeating units. A more preferred wholly aromatic liquid crystal polyester resin has a total amount of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) of 50 to 90 mol% in all repeating units, and The content of the aromatic dioxy repeating unit and the aromatic dicarbonyl repeating unit is substantially equimolar. When the liquid crystal polyester resin includes an aromatic dicarbonyl repeating unit and an aromatic dioxy repeating unit as described above, the content of both repeating units in all the repeating units of the liquid crystal polyester resin is substantially equal. Mole is preferred. Here, the content of the aromatic dicarbonyl repeating unit and the aromatic dioxy repeating unit is substantially equimolar means that the ratio (mol%) of both repeating units in the liquid crystal polyester resin is 95 /%. It means 100 to 100/95.

In the liquid crystal polyester resin, specific examples of the monomer giving the aromatic dicarbonyl repeating unit include, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7- Ester formation of aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, alkyl, alkoxy or halogen substituted products thereof, and ester derivatives and acid halides thereof Sex derivatives. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable because the liquid crystal polyester from which terephthalic acid and 2,6-naphthalenedicarboxylic acid are obtained can be easily adjusted to appropriate levels of mechanical properties, heat resistance, melting point temperature, and moldability.

In the liquid crystal polyester resin, specific examples of the monomer giving the aromatic dioxy repeating unit include, for example, hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1, Aromatic diols such as 4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, alkyls and alkoxys thereof Alternatively, halogen-substituted products and ester-forming derivatives such as acylated products thereof can be mentioned. Among these, hydroquinone, resorcin, and 4,4'-dihydroxybiphenyl are preferable from the viewpoint of reactivity during polymerization, characteristics of the obtained liquid crystal polyester resin, and the like.

Specific examples of monomers that give aromatic oxydicarbonyl repeating units in the liquid crystalline polyester resin include 3-hydroxy-2,7-naphthalenedicarboxylic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, and the like. Hydroxy aromatic dicarboxylic acids, their alkyl, alkoxy or halogen-substituted products, and ester-forming derivatives thereof such as acylated products, ester derivatives and acid halides thereof.

In the liquid crystal polyester resin used in the present invention, specific examples of the monomer giving the aliphatic dioxy repeating unit include aliphatic diols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Of the acylated product. In addition, polyesters containing aliphatic dioxy repeating units such as polyethylene terephthalate and polybutylene terephthalate are converted into the above aromatic oxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, acylated products, ester derivatives, and acid halides thereof. A liquid crystal polyester resin containing an aliphatic dioxy repeating unit can also be obtained by reacting with the above.

The liquid crystal polyester resin may contain an amide bond or a thioester bond as long as the object of the present invention is not impaired. Monomers that give such bonds include hydroxy aromatic amines, aromatic diamines, aromatic amino carboxylic acids, mercapto aromatic carboxylic acids, and aromatic dithiols and hydroxy aromatic thiols. The amount of these monomers used is that of the monomer giving the aromatic oxycarbonyl repeating unit, aromatic dicarbonyl repeating unit, aromatic dioxy repeating unit, aromatic oxydicarbonyl repeating unit, and aliphatic dioxy repeating unit. It is preferable that it is 10 mol% or less with respect to the total amount. Depending on the composition and composition ratio of the monomer and the sequence distribution of each repeating unit in the polymer, liquid crystalline polyester resins combining these repeating units may or may not form an anisotropic melt phase. The liquid crystalline polyester resin used in the invention is limited to those forming an anisotropic molten phase.

Specific examples of preferable liquid crystal polyester resins include those composed of the following monomer structural units.

(1) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid copolymer (2) 4-hydroxybenzoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl copolymer (3) 4-hydroxybenzoic acid / Terephthalic acid / isophthalic acid / 4,4'-dihydroxybiphenyl copolymer (4) 4-hydroxybenzoic acid / terephthalic acid / isophthalic acid / 4,4'-dihydroxybiphenyl / hydroquinone copolymer (5) 4-hydroxy Benzoic acid / terephthalic acid / hydroquinone copolymer (6) 2-hydroxy-6-naphthoic acid / terephthalic acid / hydroquinone copolymer (7) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer (8) 2-hydroxy-6-naphthoic acid / terephthalic acid / 4,4 ' -Dihydroxybiphenyl copolymer (9) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / hydroquinone copolymer (10) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / 4, 4'-dihydroxybiphenyl copolymer (11) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer (12) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone Copolymer (13) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer (14) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalene Dicarboxylic acid / hydroquinone / 4,4′-dihydroxybiphenyl copolymer (15 4-hydroxybenzoic acid / terephthalic acid / ethylene glycol copolymer (16) 4-hydroxybenzoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl / ethylene glycol copolymer (17) 4-hydroxybenzoic acid / 2- Hydroxy-6-naphthoic acid / terephthalic acid / ethylene glycol copolymer (18) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl / ethylene glycol copolymer ( 19) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / 4,4-dihydroxybiphenyl copolymer.

Among these, it is preferable to use a copolymer selected from the above (1), (13), or (19) as a liquid crystal polyester resin because it is excellent in heat resistance and mechanical properties. The crystal melting temperature (Tm) of the liquid crystalline polyester resin measured by a differential operation calorimeter is not particularly limited, but is preferably 320 to 380 ° C. from the viewpoint of heat resistance, and is preferably 325 to 380 ° C. More preferably, it is 330 to 380 ° C. The crystal melting temperature (Tm) is measured by the method described below.

<Method for measuring crystal melting temperature>
Exstar 6000 manufactured by Seiko Instruments Inc. is used as a differential scanning calorimeter. After measuring the endothermic peak temperature (Tm1) observed when the liquid crystal polyester resin sample is measured at room temperature to 20 ° C./min, the sample is held at a temperature 20 to 50 ° C. higher than Tm1 for 10 minutes. Next, the sample was cooled to room temperature under a temperature lowering condition of 20 ° C./min, and an endothermic peak when measured again under a temperature rising condition of 20 ° C./min was observed, and the temperature showing the peak top of the liquid crystal polyester resin was observed. The crystal melting temperature (Tm) is used. In addition, the load deflection temperature of the liquid crystal polyester resin used in the present invention, measured according to ASTM D648, is preferably 270 to 340 ° C, more preferably 280 to 340 ° C, and 290 to 340 ° C. Most preferably.

<Load deflection temperature measurement method>
The deflection temperature under load is a strip test piece 127 mm long and 3.2 mm thick using an injection molding machine (UH1000-100 manufactured by Nissei Plastic Industry Co., Ltd.), and this test piece conforms to ASTM D648. And measured under conditions of a load of 1.82 MPa and a heating rate of 2 ° C./min.

Further, the melt viscosity of the liquid crystalline polyester resin used in the present invention measured by a capillary rheometer is preferably 10 to 100 Pa · s, more preferably 10 to 80 Pa · s, and more preferably 10 to 60 Pa · s. Most preferably it is.

<Measuring method of melt viscosity>
Melt viscosity is measured using a melt viscosity measuring device (Capillograph 1D manufactured by Toyo Seiki Co., Ltd.), and a capillary having a diameter of 0.7 mm and a length of 10 mm is sheared at a crystal melting temperature (Tm) + 30 ° C. It is determined by measuring the viscosity at 10 ³ s ⁻¹ .

As the base resin, any one of the above-described resins can be used alone, or a mixture of two or more resins selected from these can be used.

[Functional additives]
The functional additive is an additive that imparts a required function to the sustained-release resin composition, such as a small animal control agent, an antibacterial agent, an antifungal agent, a fragrance, a disinfectant, a deodorant, a cleaning agent, a fertilizer, There are lubricants.

The small animal control agent is a drug having a control activity of small animals such as various agricultural pests, sanitary pests and other insects, mosses, mites, moths, etc., a compound having a small animal repellent activity, insecticidal activity, acaricidal activity, Examples of the killing activity include compounds having a killing activity such as killing activity, compounds having a feeding inhibitory activity for small animals, compounds having a growth control activity for small animals, and the like.

Specific examples of small animal control agents include chloronicotinyl insecticides such as imidacloprid, compounds composed of neophyll radicals having a silicon atom such as silafluophene, benfuracarb, alanicarb, methoxydiazone, carbosphane, fenocarb, carbaryl, Carbamate compounds such as mesomil, propoxer, phenoxycarb, pyrethrin, allethrin, d1, d-T80-arethrin, d-T80-resmethrin, bioareslin, d-T80-phthalthrin, phthalthrin, resmethrin, flamethrin, propraslin, permethrin, acrinatrin , Etofenprox, tralomethrin, phenothrin, d-phenothrin, fenvalerate, empentrin, praretrin, tefluthrin, benfurthuri Pyrethroid compounds such as dichloroboss, fenitrothion, diazinon, marathon, promophos, fenthion, trichlorphone, nared, temefos, fencrofos, chlorpyrifosmethyl, siaphos, calclofos, azamethiphos, pyridafenthion, propetanephos, chlorpyrifos and the like Examples include isomers, derivatives, and analogs. In addition, compounds having an activity of controlling the growth of small animals such as metoprene, pyriproxyfen, quinoprene, hydroprene, deoenolan, NC-170, flufenoloxuron, diflubenzuron, lufenuron, chlorazuron, and the like can be mentioned. Kelsen, chlorfenavir, debufenpyradopyridaben, milbemectin, fenpyroximate as acaricides, silyloside, norbomide, zinc chloride, thallium sulfate, precious neighbors, anto, warfarin, endside, coumarin, bear tetralin , Promadiolone, diffetialone and the like.

In addition, Hinoki thiol contained in Taiwan Hinoki, Asunaro, Hinoki Asunaro (Aomori Hiba), herbs and casinoal derivatives (α-Cabinal, T-Cabinal) contained in Cypress, perfume oil such as clove, nutmeg, coriander, cumin Naturally-derived drugs such as geraniol, pinene, caryophyllene, borneol, eugenol, etc., which are abundant in plants, as well as known perfume oils having small animal control properties such as cedar, can also be used as the small animal control agents in the present invention. it can.

[Sustained release aid for functional additives]
The functional additive sustained release aid is intended to impart sustained release of the functional additive to the base resin, and is not particularly limited as long as it can impart plastic performance to the base resin. In particular, at least one compound selected from sulfonamide derivatives, sulfonic acid ester derivatives, carboxylic acid amide derivatives, and carboxylic acid ester derivatives is preferred. These compounds are considered to have an action of dissolving and holding the functional additive and imparting sustained release properties.

Among the above-mentioned sustained-release aids for functional additives, examples of the carboxylic acid ester derivatives include alkyl esters and aromatic esters of various carboxylic acids that may be substituted with a hydroxyl group, a nitro group, an amino group, an epoxy group, a halogen, or the like. And those having a hydroxyl group or an epoxy group are preferred because of their good compatibility with polyamides.

Specific examples of the carboxylic acid ester derivative include, for example, dimethyl phthalate, diethyl phthalate, di-n-octyl phthalate, diphenyl phthalate, benzyl phthalate, dimethoxyethyl phthalate, 4,5-epoxyhexahydrophthalic acid di (2-ethylhexyl), 4,5-epoxycyclohexahydrophthalic acid di (7,8-epoxy-2-octenyl), 4,5-epoxycyclohexahydrophthalic acid di (9,10-epoxyoctadecyl), 4,5-epoxycyclohexa Phthalate derivatives such as di (10,11-epoxyundecyl) hydrophthalate, di (tetrahydrofurfuroxylethyl) phthalate, various phthalic acid mixed esters and ethylene oxide adducts of phthalic acid mixed esters, isophthalic acid ester derivatives Tetrahydrophthalic acid ester derivatives, butoxyethyl parahydroxybenzoate, cyclohexyloxyethoxyethoxyethyl parahydroxybenzoate, 2-ethylhexyl parahydroxybenzoate, hydroxybenzoic acid ester of ω-alkyl oligoethylene oxide, parahydroxybenzoic acid of undecyl glycidyl ether Benzoic acid ester derivatives such as acid adducts, propionic acid ester derivatives such as di (tetrahydrofurfuroxylethyl) thiodipropionic acid, adipic acid ester derivatives, azelaic acid ester derivatives, sebacic acid ester derivatives, dodecane-2-acid ester derivatives , Maleic acid ester derivatives, fumaric acid ester derivatives, trimetic acid ester derivatives, tri (butoxyethoxyethyl) citrate, di-n-octyl citrate Citric acid ester derivatives such as til-mono (nonylphenoxyethyl), tri-n-octyl citrate, dioctyl citrate (tetrahydrofurfuroxylethyl) citrate, trimyristyl citrate, triethyl citrate, itaconic acid ester derivatives, tetrahydrofuric acid oleate Oleic acid ester derivatives such as furyl, ricinoleic acid ester derivatives, lactic acid (n-butyl), lactic acid (2-ethylhexyl), lactic acid (n-butoxyethoxyethyl), lactic acid (n-octoxyethoxyethyl), lactic acid (n- Lactic acid ester derivatives such as decyloxyethoxyethyl), tartrate derivatives such as di (octoxyethoxyethyl) tartrate, n-octyl (nonylphenoxyethyl) tartrate, di (octoxyethoxyethyl) tartrate, dibutoxy malate ethyl Apples di (n- butoxyethoxyethyl), distearyl malate, malic acid ester derivatives such as malic acid octadecenyl isononyl, salicylic acid ester derivatives of salicylic acid adduct of benzyl glycidyl ether and the like. The phosphoric acid ester derivatives include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri- (2-ethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, isodecyl -Diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (chloroethyl) phosphate, xylenyl diphenyl phosphate, tetrakis (2,4-ditertiarybutylphenyl) 4,4'-biphenylene diphosphate, etc. .

Specific examples of the phosphazene derivative include the following general formula (4): wherein m represents an integer of 3 to 25. R ¹ and R ² are the same or different and each represents a phenyl group which may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms and / or an allyl group. The cyclic phosphazene compound represented by this can be mentioned.

Further, the following general formula (5) [wherein n represents an integer of 3 to 1000. R ³ and R ⁴ are the same or different and represent a phenyl group which may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms and / or an allyl group. X represents a group -N = P (OR ³ ) ₃ , a group -N = P (OR ⁴ ) ₃ , a group -N = P (O) (OR ³ ) or a group -N = P (O) (OR ⁴ ). Show. Y represents a group —P (OR ³ ) ₄ , a group —P (OR ⁴ ) ₄ , a group —P (O) (OR ³ ) ₂ or a group —P (O) (OR ⁴ ) ₂ . And those in which at least one phosphazene compound selected from these phosphazene compounds is an o-, m- or p-phenylene group or a biphenylene group.

Furthermore, the following general formula (6) [wherein r represents 0 or 1, and A represents a group —SO ₂ —, —S—, —O— or —C (CH ₃ ) ₂ —. And at least one bridging group selected from the group consisting of the groups represented by the above formulas, the ^two oxygen atoms from which the alkyl groups and the like are removed from the substituents R ¹ , R ² , R ³ and R ⁴ are bridged. Phosphazene compounds.

Specific examples of the cyclic phosphazene compound represented by the general formula (4) include hexaphenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decaffenoxycyclopentaphosphazene, hexapropoxycyclotriphosphazene, octapropoxycyclotetraphosphazene, decapropoxy And cyclic phosphazene compounds such as cyclopentaphosphazene.

Further, specific examples of the linear phosphazene compound represented by the general formula (5) include a linear phosphazene compound in which a propoxy group and / or a phenoxy group are substituted on a linear dichlorophosphazene.

Specific examples of the crosslinked structure represented by the general formula (6) include, for example, 4,4′-sulfonyldiphenylene (bisphenol-S residue), 4,4′-oxydiphenylene group, 4,4′-thio. A diphenylene group, a 4,4'-diphenylene group, etc. can be mentioned.

These phosphazene derivatives may be substituted with an amino group and / or a phenylamino group at an arbitrary position. These phosphazene derivatives may be used alone or in a mixture of two or more. Further, it may be a mixture of cyclic phosphazene and linear phosphazene.

Further, examples of the carboxylic acid amide derivative include N-cyclohexylbenzoic acid amide.

Examples of the sulfonamide derivatives include N-methyl-benzenesulfonamide, N-ethyl-benzenesulfonamide, N-butyl-benzenesulfonamide, N-cyclohexyl-benzenesulfonamide, N-ethyl-P-toluenesulfonamide, Examples thereof include N-butyl-toluenesulfonamide and N-cyclohexyl-toluenesulfonamide.

Further, examples of the sulfonate ester derivative include ethyl benzenesulfonate. As the component B, one kind selected from a sulfonamide derivative, a sulfonic acid ester derivative, a carboxylic acid amide derivative, and a carboxylic acid ester derivative can be used alone, or a mixture of two or more kinds selected from these can be used.

[Inorganic filler]
In addition, a predetermined amount of an inorganic filler can be added to the sustained-release resin composition according to the embodiment in order to increase the mechanical strength of the sustained-release resin molding. As the machine filler, a particulate inorganic filler, a fibrous inorganic filler, or a scaly inorganic filler can be applied.

Examples of the particulate inorganic filler include potassium titanate particles, titania particles, monoclinic titania particles, silica particles, calcium phosphate and the like, and these can be used alone or in combination. Among the particulate inorganic fillers, potassium titanate particles are particularly preferable.

Examples of the fibrous inorganic filler include fibrous fibers having a shape with an average fiber diameter of 0.05 to 10 μm and an average fiber length of 3 to 150 μm, preferably an average fiber diameter of 0.1 to 7 μm and an average fiber length of 5 to 50 μm. An inorganic filler can be preferably used. Examples of the fibrous inorganic filler include potassium tetratitanate fiber, potassium 6 titanate fiber, potassium potassium titanate fiber, titania fiber, and monoclinic titania fiber. Silica fiber, wollastonite, zonotlite, etc. can be exemplified, and these can be used alone or in combination. Of these fibrous inorganic fillers, 8 potassium titanate fibers are particularly preferred.

Examples of scale-like inorganic fillers include potassium titanate, lithium potassium titanate, potassium magnesium titanate, talc, synthetic mica, natural mica, sericite, plate-like alumina, boron nitride, etc., and these can be used alone or in combination. Can be used. Among the scaly inorganic fillers, potassium titanate is particularly preferable. When these inorganic fillers are blended, sustained release can be maintained over a long period of time. In addition, the blending of the inorganic filler can contribute to the improvement of mechanical properties.

Inorganic fillers can be used as they are, but silane coupling agents or titanate coupling agents such as aminosilane, epoxy silane, and acrylic silane in order to improve the interfacial adhesion with the resin and further improve the mechanical properties. A surface treatment agent such as a surface treatment agent may be used.

[Organic weathering agent]
In order to further improve the weather resistance, an organic weathering agent can be further added to the sustained-release resin composition of the present invention. As an organic weathering agent, one or more selected from the group consisting of hindered phenolic antioxidants, phosphorus antioxidants, UV-absorbing light stabilizers, hindered amine light stabilizers, and carbon are used. Can be mentioned.

Examples of hindered phenolic antioxidants include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamido)], bis- [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) -butanoic acid]- Glycol ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl- 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,3 ', 3``, 5,5', 5 ''-hexa-tert-butyl-a, a ', a ''-(Methylene-2,4,6-triyl) tri-p-cresol, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Lax [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, hinders such as methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate Mention may be made of dophenol antioxidants.

Phosphorous antioxidants include tris (2,4-di-tert-butylphenyl) phosphite, tris [2-[[2,4,8,10-tetra-tert-butylbenzo [d, f] [1 , 3,2] Dioxaphosphine-6-yl] oxy] ethyl] amine, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphos Phonite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol phosphite, bis (2,6-di-tert-butyl-4-phenyl) pentaerythritol phosphite, Examples thereof include phosphorus antioxidants such as bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite.

UV absorbers include 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -4 , 6-di-tert-pentylphenol, propanedioic acid, [(4-methoxyphenyl) -methylene] -dimethyl ester, and the like.

As a hindered amine light stabilizer, N, N ', N' ', N' ''-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine- 4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, poly [(6- (1,1,3,3-tetramethylbutyl) amino-1,3, 5-Triazine-2,4-diyl) (2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)) Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-dispiro- [5.1.11.2] -heneicosane -21-one, propanedioic acid, [(4-methoxyphenyl) -methylene]-, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 1,3-benzenedicarboxamide, Hinders such as N, N-bis (2,2,6,6-tetramethyl-4-piperidinyl), 2-ethyl, 2'-ethoxy-oxalanilide It may be mentioned amine-based light stabilizer.

The organic weathering agent described above can be used alone or in combination. Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′- from the viewpoint of compatibility with the base resin and excellent film formation inhibition Hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, Tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, bis ( 2,4-di-tert-butylphenyl) pentaerythritol phosphite, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2-ethyl, 2'-Ethoxy-oxalanilide, N, N ', N' ', N' ''-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethyl Peridin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, poly [(6- (1,1,3,3-tetramethylbutyl) amino-1, 3,5-triazine-2,4-diyl) (2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino )), 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) can be preferably used.

In the sustained-release resin composition of the present invention, it is desirable that the content of the functional additive with respect to the total amount of the sustained-release resin composition be 1% by weight or more and 50% by weight or less. This is because if the content is less than 1% by weight, the sufficient function cannot be exhibited and the continuity of the effect is lowered. On the other hand, when the content exceeds 50% by weight, it becomes difficult to produce a sustained-release resin composition.

The sustained-release resin composition of the present invention can be produced, for example, by blending each component and melt-kneading. Each component can be blended in advance by dry mixing using a tumbler, blender, mixer, or the like, or can be performed by supplying each component from the same or different hoppers of the kneader. The obtained sustained-release resin composition is pelletized by a pelletizer after extrusion molding. An antiblocking agent is attached to the surface of the pelletized sustained release resin composition.

[Anti-blocking agent]
Antiblocking agents include inorganic powders, organic powders, fatty acid powders, fatty acid derivative powders, and the like. These antiblocking agents can be used alone or in combination of two or more. The amount of the antiblocking agent added is preferably 0.001 to 0.03 parts by mass with respect to 100 parts by mass of the raw material pellets. By setting the amount of the anti-blocking agent within the above range, it is possible to obtain resin pellets that are excellent in blocking resistance and have little influence on the physical properties of the molded article. Further, the sustained release resin composition of the present invention comprises an antiblocking agent having an oil absorption of 100 ml / 100 mg or more, an average particle diameter of 1 to 100 μm, and a specific surface area of 100 m ² or more and 1000 m ² or less. Are preferably used.

Since the sustained-release resin composition according to the present invention exhibits a desired effect by gradually releasing the functional additive from the base resin, blocking due to the functional additive is likely to occur. However, since the content of the functional additive contained in the base resin is naturally limited, if an anti-blocking agent having an oil absorption amount corresponding to the content of the functional additive in the base resin is used, it will be gradually reduced. Since the exudation of the functional additive from the release resin composition can be prevented, blocking of the sustained release resin composition can be prevented. According to experiments, blocking of the sustained-release resin composition could be prevented by using an anti-blocking agent having an oil absorption of 100 ml / 100 mg or more. In addition, when a granule having an average particle diameter of 1 to 100 μm is used as an anti-blocking agent, the anti-blocking agent can be uniformly attached to the surface of the pellet, and the anti-blocking effect of the sustained-release resin composition is enhanced. It is done. Furthermore, by using an anti-blocking agent having a specific surface area of 100 m ² or more and 1000 m ² or less, it is possible to achieve both the anti-blocking effect of the sustained-release resin composition and the sustained-release property of the functional additive.

As inorganic powder, silica, silica alumina, diatomaceous earth, alumina, calcium carbonate, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, boron hydroxide, basic magnesium carbonate, dolomite, Examples include calcium sulfate, potassium titanate, barium carbonate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide and the like.

Examples of the organic powder include powder of crystalline polyolefin such as polyethylene and polypropylene.

As the fatty acid powder, a saturated or unsaturated higher fatty acid having 12 to 30 carbon atoms is used. Specific examples of such higher fatty acids include lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, behenic acid, oleic acid, linolenic acid, α-eleostearic acid, β-eleostearic acid, α -Linolenic acid and the like can be mentioned. Of these, stearic acid is preferred.

Examples of the fatty acid derivative powder include metal salts such as sodium salts, potassium salts, magnesium salts, calcium salts, zinc salts, aluminum salts, iron salts, and lithium salts of the above higher fatty acids. Of these, stearates are preferable. Specific examples of higher fatty acid salt derivatives include higher fatty acid amides and esters. Of these, amides or esters of stearic acid, erucic acid, oleic acid, itaconic acid, or montanic acid are preferred.

Among the various anti-blocking agents described above, inorganic powder, fatty acid powder and fatty acid derivative powder are preferable, and among inorganic powder, silica, talc, calcium carbonate and mica are particularly preferable.

[Anti-blocking agent binder]
The anti-blocking agent can be directly attached to the surface of the sustained-release resin composition formed into a pellet, but the binder is used to enhance the adhesion of the anti-blocking agent to the sustained-release resin composition. It is particularly preferable that the binding is carried out via.

Examples of the binder include polyether polyol, aliphatic hydrocarbon oil, alkane having a total carbon number of 7 to 18 which may have a hydroxyl group, a carboxyl group or an ester group, a hydroxyl group, a carboxyl group or an ester group. Examples thereof include alkenes having a total carbon number of 7 to 18, natural oils, naphthenic oils, paraffin oils, aromatic oils, and silicone oils. Among these, silicone oils, polyether polyols having 2 to 20 carbon atoms (such as ethylene glycol), mineral oils, and alcohols having 7 to 18 carbon atoms are preferable, and silicone oils are more preferable. These binders can be used individually by 1 type or in combination of 2 or more types.

The application of the binder to the pellet surface can be performed by spraying the binder into the processing apparatus while stirring the raw material pellets supplied into the processing apparatus through the hopper. According to this method, the binder can be efficiently applied to the pellet surface.

In addition, when molding the sustained-release resin composition, for example, an appropriate molding method such as injection molding, extrusion molding, press molding, blow molding, machining molding, or the like can be applied. There is no particular limitation on the shape of the small animal control resin molded product, which is a product, and any shape such as a flat plate shape, a rod shape, a cylindrical shape, a comb shape, a spherical shape, and a net shape can be used. In addition to molding the sustained-release resin composition alone, two-color or multicolor molding in combination with metal or the like can also be performed.

<Experimental example>
Hereinafter, an experimental example will be given to determine the relationship between the oil absorption amount of the antiblocking agent, the particle diameter, the specific surface area, and the feeder dropping speed, and the effect of the sustained release resin composition according to the present invention will be clarified.

The sustained-release resin composition used as the basis of the sample is 100 parts by weight of polyamide-12 (Daiamide L1901 manufactured by Daicel Huls) as a base resin, 10 parts by weight of etofenblox as a small animal control agent, and controls small animals. 10 parts by weight of N-butylbenzenesulfonamide as a sustained release aid, 5 parts by weight of fibrous potassium titanate (Tismo D102 manufactured by Otsuka Chemical Co., Ltd.) as an inorganic filler, and Tris as a first organic weathering agent 0.25 parts by weight of (2,4-di-tert-butylphenyl) phosphite (Irgaphos TFS manufactured by Ciba Specialty Chemicals), N, N'-hexane-1,6 as the second organic weathering agent -Diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)] (Irgaphos 168 manufactured by Ciba Specialty Chemicals) 0.25 layer Part, 1,3-benzenedicarboxamide, N, N-bis (2,2,6,6-tetramethyl-4-piperidinyl) (Nylostap S-EED manufactured by Clariant) as a third organic weathering agent And a mixture containing 5 parts by weight of titanium oxide having a particle diameter of 20 nm as an inorganic weathering agent was used. From this mixture, a pellet as a sample was prepared.

The test was performed by measuring the pellet feeder falling speed immediately after the antiblocking agent was attached (external addition) and the pellet feeder falling speed after heating at 60 ° C. for 48 hours. The feeder falling speed is a dropping speed of pellets from a feeder formed in a hopper shape, and its unit is g / s. Tables 1 and 2 below show the test results.

It is determined that pellets not externally added with an anti-blocking agent have a feeder drop rate of 19 g / s even immediately after production, and do not have feeder supply necessary for the production of small animal control resin moldings. Is done. After leaving at 60 ° C. for 48 hours, the feeder drop speed of the pellet is further reduced.

The pellets externally added with a calcium carbonate blocking agent having an oil absorption of 10 ml / 100 g, a particle diameter of 2 μm, and a specific surface area of 1.5 m ² / g have a feeder drop rate of 16 g / s immediately after the external addition, and control of small animals It is determined that it does not have the feeder supply capability necessary for the production of the resin molded body. In addition, pellets externally added with a silica blocking agent having an oil absorption of 30 ml / 100 g, a particle size of 4 μm, and a specific surface area of 40 m ² / g have a feeder drop rate of 15 g / s immediately after the external addition, and are small animal control resins. It is determined that it does not have the feeder supply capability necessary for the production of the molded body. It is considered that each of these blocking agents could hardly exhibit the blocking effect because the oil absorption amount and the specific surface area were too small.

The pellets externally added with a calcium carbonate blocking agent having an oil absorption of 35 ml / 100 g, a particle diameter of 1.1 μm, and a specific surface area of 3 m ² / g have a feeder drop rate of 61 g / s immediately after the external addition, and are small animal controllable. Although it is determined that it has the feeder supply capability necessary for the production of the resin molded product, the feeder fall speed is reduced to 0 g / s after heating at 60 ° C. for 48 hours, so that the small animal control resin molded product can be produced. It is determined that there is no.

Also, pellets externally added with a calcium phosphate blocking agent having an oil absorption of 92 ml / 100 g, a particle diameter of 5 μm, and a specific surface area of 93 m ² / g have a feeder drop rate of 90 g / s immediately after the external addition, and a small animal control resin. Although it is determined that it has the feeder supply capability necessary for the production of the molded product, the feeder falling speed decreases to 2 g / s after heating at 60 ° C. for 48 hours, and thus the small animal control resin molded product cannot be produced. It is determined.

In addition, pellets externally added with a talc blocking agent having an oil absorption of 41 ml / 100 g, a particle diameter of 5 μm, and a specific surface area of 8.5 m ² / g have a feeder drop rate of 78 g / s immediately after the external addition, and control of small animals Although it is determined that it has the feeder supply capability necessary for the production of the functional resin molded product, the feeder falling speed decreases to 2 g / s after heating at 60 ° C. for 48 hours. It is determined that it cannot be performed.

In addition, pellets externally added with a talc blocking agent having an oil absorption of 54 ml / 100 g, a particle diameter of 1 μm, and a specific surface area of 20 m ² / g have a feeder drop rate of 81 g / s immediately after external addition, and are small animal control resins. Although it is determined that the feeder supply property necessary for the production of the molded product is obtained, the feeder drop rate is reduced to 10 g / s after heating at 60 ° C. for 48 hours, and thus the small animal control resin molded product cannot be produced. It is determined.

In addition, pellets externally added with a silica blocking agent having an oil absorption of 100 ml / 100 g, a particle size of 5 μm, and a specific surface area of 200 m ² / g have a feeder drop rate of 84 g / s immediately after the external addition, and are small animal control resins. Although it is determined that the feeder supply property necessary for the production of the molded product is obtained, the feeder drop rate decreases to 12 g / s after heating at 60 ° C. for 48 hours, and thus the small animal control resin molded product cannot be produced. It is determined.

Of course, these anti-blocking agents can also be used for the purpose of producing a small animal controllable resin molding immediately after the production of the pellets.

In contrast, pellets externally added with a calcium phosphate / calcium carbonate blocking agent having an oil absorption of 155 ml / 100 g, a particle size of 5.5 μm, and a specific surface area of 89 m ² / g have a feeder drop rate of 101 g / s, and the feeder dropping speed after heating at 60 ° C. for 48 hours is also maintained at 43 g / s, so it is determined that there is no practical problem. In addition, if it has the feeder fall speed of 40 g / s or more, a small animal controllable resin molding can be manufactured with target manufacturing efficiency.

In addition, the pellets externally added with a silica blocking agent having an oil absorption of 300 ml / 100 g, a particle diameter of 0.3 μm, and a specific surface area of 300 m ² / g have a feeder dropping speed of 97 g / s immediately after the external addition, and 60 ° C. Since the feeder falling speed after heating for 48 hours is maintained at 60 g / s, it is determined that there is no practical problem.

Furthermore, pellets externally added with a silica blocking agent having an oil absorption of 400 ml / 100 g, a particle diameter of 5 μm, and a specific surface area of 700 m ² / g have a feeder drop rate of 106 g / s immediately after the external addition and are 48 at 60 ° C. Since the feeder falling speed after heating for a certain time is maintained at 76 g / s, it is determined that there is no practical problem.

The present invention includes small animal control agent-containing resin molded products, antibacterial agent-containing resin molded products, antifungal agent-containing resin molded products, fragrance-containing resin molded products, bactericidal agent-containing resin molded products, deodorant-containing resin molded products, and fertilizer-containing resins. It can be used for the production of molded products and lubricating oil-containing resin molded products.

Claims (8)

1. A sustained-release resin composition comprising at least a base resin and a functional additive, formed into a pellet, and having an anti-blocking agent having an oil absorption of 100 ml / 100 mg or more attached to the surface thereof.
2. 2. The sustained release resin composition according to claim 1, wherein the antiblocking agent is a granule having an average particle diameter of 1 to 100 μm.
3. ^2. The sustained-release resin composition according to claim 1, wherein the anti-blocking agent has a specific surface area of 100 m ² or more and 1000 m ² or less.
4. The functional additive is any one or more selected from small animal control agents, antibacterial agents, fungicides, fragrances, bactericides, deodorants, fertilizers and lubricating oils. 2. The sustained release resin composition according to 1.
5. The sustained-release resin composition according to claim 1, wherein the antiblocking agent is a granule having an average particle diameter of 1 to 100 µm and a specific surface area of 100 m ² or more and 1000 m ² or less.
6. The antiblocking agent is a granule having an average particle diameter of 1 to 100 μm,
   The functional additive is any one or more selected from small animal control agents, antibacterial agents, fungicides, fragrances, bactericides, deodorants, fertilizers and lubricating oils. 2. The sustained release resin composition according to 1.
7. The antiblocking agent is a granule having an average particle diameter of 1 to 100 μm, a specific surface area of 100 m ² or more and 1000 m ² or less,
   The functional additive is any one or more selected from small animal control agents, antibacterial agents, fungicides, fragrances, bactericides, deodorants, fertilizers and lubricating oils. 2. The sustained release resin composition according to 1.
8. The anti-blocking agent has a specific surface area of 100 m ² or more and 1000 m ² or less,
   The functional additive is any one or more selected from small animal control agents, antibacterial agents, fungicides, fragrances, bactericides, deodorants, fertilizers and lubricating oils. 2. The sustained release resin composition according to 1.