JP5286683B2 - Phosphite-containing granular composition and method for producing the same - Google Patents

Description

  The present invention relates to a composition suitable as a deterioration preventing agent for thermoplastic resins such as polyolefins.

It is known in Patent Document 1 that the phosphite represented by the formula (1) is useful as an anti-degradation agent for thermoplastic resins such as polyolefin. Specifically, a phosphite is added to polypropylene. It is disclosed that a melt-kneaded thermoplastic resin composition is small in coloration by NOx gas, that is, excellent in coloration resistance.

[Wherein R ¹ , R ² , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkyl having 6 to 12 carbon atoms. A cycloalkyl group, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X represents a single bond, a sulfur atom or a —CHR ⁶ — group. , R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms,
A represents an alkylene group having 2 to 8 carbon atoms or * —C (═O) R ⁷ — group, R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and “*” represents> PO -Represents a bond with the oxygen atom side of the moiety,
Y and Z each represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
When Y is a hydroxyl group, any one of R ⁴ and R ⁵ is an alkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, carbon Represents an aralkyl group or a phenyl group of formula 7 to 12, and two R ^{1 s} in formula (1) may be the same or different from each other, and ^two R ^{2 s} in formula (1) may be the same as each other The two R ³ in the formula (1) may be the same as or different from each other. ]

The phosphite described in Patent Document 1 is usually a powder having an average particle size of about 20 to 60 μm, and there is a problem that dust is generated when added to a thermoplastic resin.
On the other hand, Patent Document 2 discloses that a phosphoric acid ester metal salt different from a phosphite ester as a main component and a composition containing metal soap produces dust, which is lower than metal soap as a binder. It is disclosed that when an organic compound having a melting point (specifically, glycerin monostearate) is further added, the composition becomes granular and hardly generates dust.

JP-A-10-273494 ([Claim 1], Examples 14 [0110] to [0115]) JP 2001-81236 A ([Claims], [0004], [0005], [0059] Example 6)

The present inventor examined a thermoplastic resin composition obtained by adding a composition containing glycerin monostearate and containing phosphite as a main component to polypropylene, and a composition with less glycerin monostearate. However, the composition containing glycerin monostearate in such an amount that dust does not occur is less dust, but the resulting thermoplastic resin composition has insufficient color resistance. The problem of not being revealed.
An object of the present invention is to provide a composition containing a phosphite ester as a main component and a method for producing the same, which gives a thermoplastic resin composition that hardly generates dust and has excellent coloration resistance.

Under such circumstances, the present inventor has found that a composition obtained by mixing a specific compound with the phosphite ester (1) can solve all of these problems, and has completed the present invention.
That is, the invention according to the composition of the present invention is a composition comprising a phosphite ester represented by the formula (1) and a compound represented by the formula (2), It is a granular composition containing 30 to 99.5 parts by weight of the phosphite ester (1) and 0.5 to 20 parts by weight of the compound (2).

［式中、Ｒ^１、Ｒ^２、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子、炭素数１〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表し、Ｒ^３は水素原子又は炭素数１〜８のアルキル基を表し、Ｘは単結合、硫黄原子又は−ＣＨＲ⁶−基を表し、Ｒ⁶は水素原子、炭素数１〜８のアルキル基又は炭素数５〜８のシクロアルキル基を表し、
Ａは炭素数２〜８のアルキレン基又は＊−Ｃ（＝Ｏ）Ｒ⁷−基を表し、Ｒ⁷は単結合又は炭素数１〜８のアルキレン基を表し、＊印は、＞Ｐ−Ｏ−部分の酸素原子側との結合手であることを表し、
Ｙ及びＺは、いずれか一方がヒドロキシル基、炭素数１〜８のアルコキシ基又は炭素数７〜１２のアラルキルオキシ基を表し、他方が水素原子又は炭素数１〜８のアルキル基を表すが、
Ｙがヒドロキシル基であるときは、Ｒ^４及びＲ^５のいずれか一方は炭素数３〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表し、また、式（１）における２個のＲ^１は互いに同一でもよく、異なってもよく、式（１）における２個のＲ^２は互いに同一でもよく、異なってもよく、式（１）における２個のＲ^３は互いに同一でもよく、異なってもよい。］

[Wherein R ¹ , R ² , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkyl having 6 to 12 carbon atoms. A cycloalkyl group, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X represents a single bond, a sulfur atom or a —CHR ⁶ — group. , R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms,
A represents an alkylene group having 2 to 8 carbon atoms or * —C (═O) R ⁷ — group, R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and “*” represents> PO -Represents a bond with the oxygen atom side of the moiety,
Y and Z each represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
When Y is a hydroxyl group, any one of R ⁴ and R ⁵ is an alkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, carbon Represents an aralkyl group or a phenyl group of formula 7 to 12, and two R ^{1 s} in formula (1) may be the same or different from each other, and ^two R ^{2 s} in formula (1) may be the same as each other The two R ³ in the formula (1) may be the same as or different from each other. ]

^{(R 8 -B-S-C} 2 H 4 CO 2) n -D (2)
[Wherein R ⁸ represents an alkyl group having 12 to 18 carbon atoms. B represents a single bond or a —C ₂ H ₄ CO ₂ — group. D represents an n-valent alcohol residue having 5 to 18 carbon atoms. n represents an integer of 1 to 4. ]

  In the invention according to the production method of the present invention, 30 to 99.5 parts by weight of a phosphite represented by the formula (1) and 0.5 to 20 parts by weight of a compound represented by the formula (2) are mixed. And granulating in a temperature range of 40 to 70 ° C., a method for producing a granular composition.

In the granular composition of the present invention, generation of dust during handling such as when a phosphite is added to a thermoplastic resin is reduced, and the phosphite contained in the granular composition is sufficiently dispersed in the thermoplastic resin. Is done. In addition, the thermoplastic resin composition containing the composition of the present invention has improved color resistance.
Furthermore, the production method of the present invention can easily produce a granular composition containing phosphite as a main component with reduced generation of dust.

Hereinafter, the present invention will be described in detail.
The phosphite ester (1) used in the present invention is a compound represented by the above formula (1).
In the phosphite (1), R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a carbon number. A 6-12 alkylcycloalkyl group, a C7-12 aralkyl group, or a phenyl group is represented.
Here, examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, a t-butyl group, a t-pentyl group, and a t-octyl group.
Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group, a cyclohexyl group, and a cyclopentyl group.
Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include a methylcyclopentyl group, a methylcyclohexyl group, and a dimethylcyclohexyl group.
Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group.

In the phosphite (1), R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include the same groups as described above.
R ³ is preferably a hydrogen atom or a methyl group.
In the phosphite (1), X represents a single bond, a sulfur atom or a —CHR ⁶ — group, and R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms. Represent. Examples of the alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 5 to 8 carbon atoms include the same groups as described above.
Examples of the —CHR ⁶ — group include a methylene group, an ethylidene group, a propylidene group, and a 1-cyclohexylmethyl group. X is preferably a single bond, a methylene group or an ethylidene group. In phosphorus-based antioxidant (I), A is an alkylene group, or * -C (= O) -R ⁷ 2 to 8 carbon atoms - group, R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms The * mark represents a bond with the oxygen atom side of the> PO- moiety. Examples of the alkylene group having 1 to 8 carbon atoms include a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group. A is preferably an alkylene group having 2 to 4 carbon atoms or the above-described * —C (═O) —R ⁷ — group.
In the alkylene group having 2 to 4 carbon atoms, the carbon-carbon bond may be interrupted by a group containing a hetero atom. Examples of the group containing a hetero atom in this case include —O—C (═O) — or —C (═O) —O— group. R ⁷ is preferably an alkylene group having 1 to 4 carbon atoms.

Y and Z each represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. When Y is a hydroxyl group, any one of R ⁴ and R ⁵ is an alkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, carbon It is preferably an aralkyl group or a phenyl group of several 7 to 12. Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, and a t-butoxy group. Examples of the aralkyloxy group having 7 to 12 carbon atoms include a benzyloxy group.
When Y in Formula (1) is a hydroxyl group, Z is more preferably a hydrogen atom or a methyl group, one of R ⁴ and R ⁵ is a t-butyl group, and the other is a hydrogen atom or a methyl group. It is more preferable that
Also, when Z in the formula (1) is a hydroxyl group, R ⁵ is a methyl group, Y is a hydrogen atom, it is preferred that R ⁴ is a t- butyl group.
In addition, R ¹ , R ² and R ³ in the formula (1) may be the same as or different from each other.

Of the phosphite ester (1), particularly preferred compounds are exemplified below.
6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] Dioxaphosphepine, 6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenzo [d, f] [ 1,3,2] dioxaphosphine, 6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -4,8-di-t-butyl-2,10- Dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -4,8 -Di-t-butyl-2,10-dimethyl-12H-dibenzo [d, g] [1, , 2] dioxaphosphosine like.

  The phosphite ester (1) used in the present invention is in a powder form and usually contains 10% by weight or more of a component of 45 μm or less, and the weight-based average particle size of (1) is 20 to 60 μm. Degree.

The composition of the present invention contains 30 to 99.5 parts by weight, preferably 92 to 99 parts by weight, particularly preferably 94 to 98 parts by weight of the phosphite ester (1) with respect to 100 parts by weight of the present composition.
If the phosphite ester (1) is 30 parts by weight or more, it is preferable because it tends to give a thermoplastic resin composition having excellent color resistance. If it is 99 parts by weight or less, granulation and melting are easy. It is preferable because it tends to progress and suppress fine powder.

The composition of the present invention contains 0.5 to 20 parts by weight, preferably 1 to 8 parts by weight, particularly preferably 2 to 6 parts by weight of the compound (2) with respect to 100 parts by weight of the present composition.
When the amount of compound (2) is 0.5 parts by weight or more, granulation and melting easily proceed and fine powder tends to be suppressed, and when it is 20 parts by weight or less, when granulating Granules having a large particle size are preferably reduced, and the concentration of phosphite (1) in the granules tends to increase.

Here, R ⁸ in the compound (2) is preferably a dodecyl group, a tetradecyl group or an octadecyl group.
D is an n-valent alcohol residue having 5 to 18 carbon atoms, and n is an integer of 1 to 4. Here, the alcohol residue means a portion other than the hydrogen atom of the hydroxyl group of the alcohol. Examples of suitable alcohol residues D include alcohols such as dodecyl alcohol, tetradecyl alcohol, octadecyl alcohol, and pentaerythritol. In particular, when B in the compound (2) is a single bond, a compound in which R ⁸ is a dodecyl group, n is 4, and D is a pentaerythritol residue is preferable. When B is a —C ₂ H ₄ CO ₂ — group, R ⁸ is a dodecyl group, a tetradecyl group or an octadecyl group, n is 1, and D has 12 carbon atoms corresponding to R ⁸ above. It is preferably 14 or 18 alcohol residues.
Incidentally, B is _{-C 2 H} 4 CO 2 - is a group is _usually a -C ₂ H 4 _{CO 2} -D.

Specific examples of the compound (2) that can be used in the present invention include the following.
3,3′-thiodipropionic acid di-n-dodecyl ester,
3,3′-thiodipropionic acid di-n-tetradecyl ester,
3,3′-thiodipropionic acid di-n-octadecyl ester,
Tetrakis (3-dodecylthiopropionic acid) pentaerythrityl ester

The composition of the present invention may further contain at least one additive selected from the following additive group as long as the thermoplastic resin is not adversely affected such as coloring of the thermoplastic resin when blended with the thermoplastic resin.
The weight-based average particle diameter of the additive used in the present invention is preferably in the range of 0.1 to 100 μm, particularly preferably in the range of 0.5 to 70 μm.
When using a commercially available additive as it is, it is preferable to use it after adjusting to a preferable weight-based average particle diameter by a known method in advance.
[Additives: neutralizers, lubricants, hindered amine light stabilizers, UV absorbers, metal soaps, antistatic agents, antiblocking agents, pigments, flame retardants, fillers, and phenolic antioxidants Antioxidants other than phosphate ester (1) and compound (2)]

Examples of the additive include the following compounds.
Neutralizing agents such as hydrotalcite, calcium hydroxide, aluminum hydroxide;
Lubricants such as oleic acid amide and erucic acid amide;
Tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) Phosphorous antioxidants such as pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphonite;

  Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly [{6- (1,1,3,3, -tetramethylbutyl) amino-1,3,5-triazine-2, 4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} -1,6-hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] Hindered amine light stabilizers such as

  2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2,4-di-tert-butylphenyl UV absorbers such as 3,5-di-t-butyl-4-hydroxybenzoate;

Synthetic hydrotalcite, natural hydrotalcite, neutralizing agents such as calcium hydroxide;
Fillers such as calcium carbonate, silicate, glass fiber, talc, kaolin, mica, barium sulfate, carbon black, carbon fiber, zeolite, metal powder, metal oxide;

  Stearic acid lithium salt, magnesium salt, sodium salt, calcium salt, barium salt, aluminum salt, zinc salt, or iron salt, lithium palmitate, magnesium salt, sodium salt, calcium salt, barium salt, aluminum salt, zinc Salt or iron salt, lithium salt of lauric acid, magnesium salt, sodium salt, calcium salt, barium salt, aluminum salt, zinc salt or iron salt, calcium salt or zinc salt of behenic acid, calcium of 12-hydroxystearic acid Metal soap containing a fatty acid metal salt having 4 to 18 carbon atoms such as a salt, magnesium salt or zinc salt;

The following antistatic agents;
Quaternary ammonium salt type cationic surfactant, betaine type amphoteric surfactant, alkyl phosphate type anionic surfactant, primary amine salt, secondary amine salt, tertiary amine salt, quaternary Cationic surfactants such as amine salts and pyridine derivatives,
Sulfated oil, soap, sulfated ester oil, sulfated amide oil, sulfated olefin salt of olefin, fatty alcohol sulfate, alkyl sulfate, fatty acid ethyl sulfonate, alkyl naphthalene sulfonate, alkyl benzene sulfonate , Anionic surfactants such as oxalate ester sulfonate and phosphate ester salt,
Partial fatty acid ester of polyhydric alcohol, ethylene oxide adduct of aliphatic alcohol, ethylene oxide adduct of fatty acid, ethylene oxide adduct of aliphatic amino or fatty acid amide, ethylene oxide adduct of alkylphenol, partial polyhydric alcohol An antistatic agent such as an ethylene oxide adduct of a fatty acid ester, a nonionic surfactant such as polyethylene glycol, an amphoteric surfactant such as a carboxylic acid derivative or an imidazoline derivative, or an antistatic agent having a melting point exceeding 70 ° C. among these;

  Inorganic antiblocking agents such as aluminum silicate, synthetic silica, natural silica, zeolite, kaolin and diatomaceous earth, or organic antiblocking agents such as cross-linked polymethylmethacrylic acid;

  Carbon black, titanium oxide, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, perylene or perine pigment, quinophthalone pigment, diketopyrrolo-pyrrole pigment, dioxazine pigment, disazo condensation pigment and benzimidazolone pigment Pigments such as

  Flame retardants such as decabromobiphenyl, antimony trioxide, phosphorus flame retardant, aluminum hydroxide;

  2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentyl) Phenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, Tris (3,5-di-tert-butyl 4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5 -Triazine-2,4,6- (1H, 3H, 5H) -trione, 2,2'-methylenebis (6-t-butyl-4-methylphenol), 4,4'-butylidenebis (6-t-butyl) -3-methyl Phenol), 4,4'-thiobis (6-t-butyl-3-phenolic antioxidant other than the phenol-based antioxidant (1), such as methyl phenol);

In the composition of the present invention, the content of the additive is usually 100 parts by weight or less, preferably 70 parts by weight or less, based on 100 parts by weight of the phosphite (1), excluding the metal soap described later. Preferably, 40 parts by weight or less may be contained.
The total content of the above additives with respect to 100 parts by weight of the granular composition is about 0 to 69.5 parts by weight.

  The composition of the present invention preferably contains a metal soap. A preferable blending ratio of the metal soap is 0.1 to 100 parts by weight, particularly preferably 0.1 to 40 parts by weight, based on 100 parts by weight of the phosphite (1).

Examples of the shape of the composition of the present invention include pellets formed by melt-kneading and then extruding, etc., but it is easy to produce a granular granular composition and has excellent dispersibility in a thermoplastic resin. The resulting thermoplastic resin composition is preferred because it tends to improve the color resistance.
Hereinafter, the granular granular composition will be described.
In addition, granular form means the granule aggregate of the irregular shape as described in JIS-Z 8841 (1993) 10 description table 1 shape and name of granulated material.

In the granular granular composition, a component having a particle size of 45 μm or less by a sieve is usually 10% by weight or less based on the granular composition. Thereby, generation | occurrence | production of the dust of this composition is suppressed significantly.
As a method for reducing the component having a particle size of 45 μm or less, for example, the time for mixing and granulating 30 to 99.5 parts by weight of phosphite (1) and 0.5 to 20 parts by weight of compound (2) For example, a method of increasing the temperature for mixing and granulating 30 to 99.5 parts by weight of phosphite (1) and 0.5 to 20 parts by weight of compound (2). .

The average particle size of the granular composition of the present invention is usually 80 to 2000 μm.
When the average particle size is 80 μm or more, it is preferable because generation of dust tends to be suppressed, and when it is 2000 μm or less, it is preferable because dispersibility of the phosphite ester in the thermoplastic resin tends to be excellent. . In particular, the average particle diameter is preferably 90 to 1000 μm.
In the present invention, the average particle size is obtained by using a Seishin company robot shifter equipped with a standard sieve of JIS Z 8801, and sieving about 5 g of the sample at a vibration level of 8, shift time of 3 minutes, and pulse interval of 1 second. The average particle diameter based on the weight is obtained from the opening of the particles and the weight of the particles remaining on the sieve.

  Here, in the present invention, it does not mean that one particle contains the phosphite ester (1) and the compound (2) in the above-mentioned weight ratio, but 100 parts by weight of the whole granular composition contains It means that 30 to 99.5 parts by weight of the phosphite (1) and 0.5 to 20 parts by weight of the compound (2) are contained. It means that the granular composition contains the phosphite ester (1) and the compound (2) in the above weight ratio.

As a manufacturing method of a granular granular composition, for example, 30 to 99.5 parts by weight of phosphite (1) and 0.5 of compound (2) are added to 100 parts by weight of the present granular composition. -20 parts by weight, preferably 1-8 parts by weight, particularly preferably 2-6 parts by weight, and a method in which additives are mixed as necessary and granulated in a temperature range of 40-70 ° C.
The granulation temperature in the present invention is a temperature of a mixture comprising a phosphite ester (1), a compound (2) and, if necessary, an additive which is further added.
Although it varies depending on the melting point and amount of the compound (2), the preferred granulation temperature is preferably in the range of 40 ° C. to 60 ° C. because the operation of granulation tends to be easy.

As a granulation method, usually, an apparatus that can be mixed with the phosphite ester (1) and the compound (2) is used, and the temperature of the mixture at the time of mixing is 40 to 70 ° C, preferably 40 to 60 ° C. It is the method of granulating in the temperature range.
Examples of such devices include high-speed rotating devices such as Henschel mixers, super mixers, and high-speed mixers, stirring and mixing granulators such as vertical granulators, and rolling fluid coating devices.

As a specific granulation method, for example, a method of stirring and mixing at a high speed after charging a phosphite ester (1), a compound (2) and an additive added as necessary into a mixer such as a Henschel mixer, For example, a method of spray-mixing the phosphorous acid ester (1) and the compound (2) heated and melted to the additive added as necessary and cooling it with stirring is exemplified.
As a method of setting the granulation temperature to 40 to 70 ° C., for example, a method of heating by attaching a hot water jacket to a Henschel mixer, for example, a method of raising the temperature using shear heat generated by high-speed stirring, etc. Is mentioned.
Among the above methods, the method of stirring and mixing at a high speed after the phosphite ester (1), the compound (2) and additives to be added as needed are charged into a mixer such as a Henschel mixer is simple in operation. Is particularly preferred.

  Since the granular granular composition thus obtained has few fine powders, the amount of dust scattering is small and the fluidity is good. Fine powder may be removed from the obtained granular granular composition by a sieving operation. However, since the granular granular composition of the present invention has a small amount of fine powder, the sieving step can be omitted.

  The composition of the present invention is suitable as an anti-degradation agent for thermoplastic resins that are easily deteriorated by heat or light. Examples of the thermoplastic resin used in the present invention include: Polyethylene resins such as polypropylene resin, high density polyethylene (HD-PE), low density polyethylene (LD-PE), linear low density polyethylene (LLDPE), methylpentene polymer, ethylene / ethyl acrylate copolymer resin, Ethylene / vinyl acetate copolymer resin, polystyrenes such as poly (p-methylstyrene), poly (α-methylstyrene) polystyrene, acrylonitrile / styrene copolymer resin, acrylonitrile / butadiene / styrene copolymer resin, special acrylic rubber / Acrylonitrile / styrene copolymer resin, acrylonitrile / chlorinated polyethylene / styrene copolymer resin, chlorinated polyethylene, polychloroprene, chlorinated rubber, polyvinyl chloride, polyvinylidene chloride, methacrylic resin, ethylene / vinyl alcohol Copolymer resin, fluororesin, polyacetal, grafted polyphenylene ether resin, polyphenylene sulfide resin, polyurethane, polyamide, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyacrylate, polysulfone, polyetheretherketone, polyethersulfone , Aromatic polyester resin, diallyl phthalate prepolymer, silicone resin, 1,2-polybutadiene, polyisoprene, styrene / butadiene copolymer, butadiene / acrylonitrile copolymer, ethylene / propylene copolymer, ethylene / methyl methacrylate copolymer Examples include coalescence, among which polyethylene-based resins and polypropylene-based resins are preferable because of good moldability. Riwake, polypropylene resin is preferred.

Here, the polypropylene-based resin means a polyolefin containing a structural unit derived from propylene. Specifically, a crystalline propylene homopolymer, a propylene-ethylene random copolymer, a propylene-α-olefin random copolymer. Polypropylene block comprising a polymer, a propylene-ethylene-α-olefin copolymer, a propylene homopolymer component or a copolymer component mainly composed of propylene, and a copolymer component of propylene and ethylene and / or α-olefin A copolymer etc. are mentioned.
When a polypropylene resin is used as the thermoplastic resin used in the present invention, one type of polypropylene resin may be used, or two or more types may be blended and used.

  The α-olefin is usually an α-olefin having 4 to 12 carbon atoms. For example, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-octene, Examples include decene, and more preferred are 1-butene, 1-hexene, and 1-octene.

  Examples of the propylene-α-olefin random copolymer include a propylene-1-butene random copolymer, a propylene-1-hexene random copolymer, and a propylene-1-octene random copolymer.

  Examples of the propylene-ethylene-α-olefin copolymer include propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, and propylene-ethylene-1-octene copolymer. It is done.

  As a copolymer component mainly composed of propylene in a propylene homopolymer component or a copolymer component mainly composed of propylene and a polypropylene block copolymer composed of a copolymer component of propylene and ethylene and / or α-olefin Examples thereof include a propylene-ethylene copolymer component, a propylene-1-butene copolymer component, a propylene-1-hexene copolymer component, and the like, and a copolymer component of propylene and ethylene and / or an α-olefin. As, for example, propylene-ethylene copolymer component, propylene-ethylene-1-butene copolymer component, propylene-ethylene-1-hexene copolymer component, propylene-ethylene-1-octene copolymer component, propylene -1-butene copolymer component, propylene-1-hex Examples thereof include a cene copolymer component and a propylene-1-octene copolymer component. The content of ethylene and / or α-olefin having 4 to 12 carbon atoms in the copolymer component of propylene and ethylene and / or α-olefin is usually 0.01 to 20% by weight.

  Examples of the polypropylene block copolymer comprising a propylene homopolymer component or a copolymer component mainly composed of propylene and a copolymer component of propylene and ethylene and / or α-olefin include, for example, a propylene-ethylene block Copolymer, (propylene)-(propylene-ethylene) block copolymer, (propylene)-(propylene-ethylene-1-butene) block copolymer, (propylene)-(propylene-ethylene-1-hexene) block Copolymer, (propylene)-(propylene-1-butene) block copolymer, (propylene)-(propylene-1-hexene) block copolymer, (propylene-ethylene)-(propylene-ethylene-1-butene) ) Block copolymer, (propylene-ethylene)-(pro Len-ethylene-1-hexene) block copolymer, (propylene-ethylene)-(propylene-1-butene) block copolymer, (propylene-ethylene)-(propylene-1-hexene) block copolymer, ( Propylene-1-butene)-(propylene-ethylene) block copolymer, (propylene-1-butene)-(propylene-ethylene-1-butene) block copolymer, (propylene-1-butene)-(propylene- (Ethylene-1-hexene) block copolymer, (propylene-1-butene)-(propylene-1-butene) block copolymer, (propylene-1-butene)-(propylene-1-hexene) block copolymer Etc.

  Further, when a polypropylene resin is used as the thermoplastic resin used in the present invention, preferably, a crystalline propylene homopolymer, a propylene homopolymer component or a copolymer component mainly composed of propylene, propylene and ethylene and / or Or it is a polypropylene-type block copolymer which consists of a C4-C12 alpha olefin copolymer component. More preferably, a polypropylene block copolymer comprising a propylene homopolymer component or a copolymer component mainly composed of propylene, and a copolymer component of propylene and ethylene and / or an α-olefin having 4 to 12 carbon atoms. It is.

  The crystallinity of the polypropylene resin is preferably high from the viewpoint of rigidity and scratch resistance. As a polypropylene resin having high crystallinity, A.A. Fraction of propylene monomer units at the center of a chain in which five propylene monomer units in the polypropylene molecule are determined in accordance with the method published by Zambelli et al. (Macromolecules 6, 925, 1973) and meso-bonded in succession (Pendat) It is called a fraction and is expressed in [mmmm].

  The method for producing the thermoplastic resin used in the present invention is not particularly limited, and a thermoplastic resin produced by a known polymerization method can be used using a conventionally known appropriate polymerization catalyst. Moreover, you may use a commercially available thermoplastic resin.

  When a polypropylene resin is used as the thermoplastic resin used in the present invention, examples of the polymerization catalyst include Ziegler type catalysts, Ziegler-Natta type catalysts, Group IV transition metals having a cyclopentadienyl ring. Examples include a catalyst system comprising a compound and an alkylaluminoxane, or a catalyst system comprising an organoaluminum compound and a compound that reacts with a transition metal compound of Group IV of the periodic table having a cyclopentadienyl ring to form an ionic complex. It is done.

  When the thermoplastic resin used in the present invention is a polypropylene resin, the polymerization method includes, for example, a slurry polymerization method using an inert hydrocarbon solvent, a solvent polymerization method, a liquid phase polymerization method using no solvent, and a gas phase. Examples thereof include a polymerization method, or a liquid phase-gas phase polymerization method in which they are continuously performed. These polymerization methods may be a batch method or a continuous method. Moreover, the method of manufacturing a polypropylene resin in one step may be used, and the method of manufacturing in two or more steps may be used. In particular, production of a polypropylene block copolymer comprising a propylene homopolymer component or a copolymer component mainly composed of propylene, and a copolymer component of propylene and ethylene and / or an α-olefin having 4 to 12 carbon atoms. As a method, preferably, a step of producing a propylene homopolymer component or a copolymer component mainly composed of propylene and a copolymer component of propylene and ethylene and / or an α-olefin having 4 to 12 carbon atoms are produced. A multi-stage production method comprising at least two stages consisting of stages may be mentioned.

  The melt index (MI) of the thermoplastic resin used in the present invention is preferably in the range of 0.01 to 100 g / 10 minutes from the viewpoint of molding processability in the case of a polypropylene resin, for example.

  The addition amount of the granular composition of the present invention is usually in the range of 0.02 to 1 part by weight, preferably in the range of 0.04 to 0.5 part by weight, with respect to 100 parts by weight of the thermoplastic resin. Especially preferably, it is the range of 0.08-0.2 weight part. It is preferable that the amount of the composition of the present invention added is 0.02 parts by weight or more because the processing stability tends to be improved. Even if added in excess of 1 part by weight, no improvement in stability commensurate with the addition is observed, which is economically disadvantageous.

As a method of blending the composition of the present invention into a thermoplastic resin, for example, after mixing the composition and a thermoplastic resin, a method of melt-kneading with a single-screw or multi-screw extruder, for example, polymerizing a thermoplastic resin. For example, there may be mentioned a method in which a solution obtained by dissolving or suspending the composition in a solvent in advance is fed into the solution after the removal, and then the solvent is removed by a method such as evaporation.
The thermoplastic resin thus obtained can be processed into products such as films, molding materials and pipes.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.

The following compounds were used in the following examples.
Phosphite ester (abbreviated as 1-1): 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t- Butyldibenzo [d, f] [1,3,2] dioxaphosphepine (Sumitomo Chemical Co., Ltd., Sumitizer GP)
Compound (2-1): 3,3′-thiodipropionic acid di-n-tetradecyl ester (Sumilyzer TPM, manufactured by Sumitomo Chemical Co., Ltd.)
Glycerin monostearate (abbreviated as 2 ')
Metal soap (abbreviated as 3,): calcium stearate

Example 1
<Production example of granular composition>
1 kg of phosphite ester (1-1) and 50 g of compound (2-1) were charged into a mixing tank of a 10 L Henschel mixer equipped with a temperature sensor and a hot water jacket inside the mixing tank. Subsequently, the hot water jacket was passed through 50 ° C., and mixed at a high speed of 950 rpm for granulation. At 4 minutes 00 seconds from the start of mixing, the temperature sensor inside the mixing tank reached 51 ° C. (end point temperature), and stirring was stopped, and 1 kg of granular granular composition A was taken out from the outlet.

(Examples 2 to 4 and Comparative Examples 1 to 3)
Using the compounds and amounts shown in Table 1, except that the jacket temperature and the end point temperature of mixing are granulated under the conditions shown in Table 1, the same procedure as in Example 1 was carried out. G> was manufactured.
In Example 2, metal soap (3) as an additive was put into a 200 g mixing tank and granulated.

  The particle sizes of the granular compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were measured. The results are shown in Table 2. The particle size was measured by using a robot shifter manufactured by Seishin Corporation, about 5 g of a sample at a vibration level of 8, a shift time of 3 minutes, and a pulse interval of 1 second. It means that there are few fine powders and there are few powdering at the time of handling, so that there are few contents of particle size 45 micrometers or less.

(Example 5)
<Manufacture of a thermoplastic resin composition and coloring resistance of the obtained thermoplastic resin composition>
1 kg of polypropylene (MI (230 ° C., 2.16 kg): 3 g / 10 min), 0.5 g of calcium stearate and 1 g of granular composition A are dry blended and extruded at an extrusion temperature of 230 ° C. using a 30 mmφ single screw extruder. A pellet was obtained. This pellet was injection molded at 230 ° C. to obtain a polypropylene sheet (40 × 60 × 1 mm). The color resistance (ΔYI) before and after the polypropylene sheet was exposed to 650 ppm NOx gas was 0.62.

<Evaluation method of coloring resistance (ΔYI)>
The polypropylene sheet was exposed to 650 ppm NOx gas at about 25 ° C. for 7 days. The yellowness index (YI) of the sheet before and after exposure was measured, and the color resistance of the polypropylene composition was evaluated by the difference (ΔYI) between YI after exposure and YI before exposure.

(Examples 6 to 8, Comparative Example 4, Reference Example 1)
Examples 6 to 8, Comparative Example 4 and Reference Example 1 were carried out in the same manner as in Example 5 except that the granular composition shown in Table 3 was used. The results are shown in Table 3 together with Example 5. A smaller ΔYI means better coloration resistance.

Example 9
[Production of polyethylene composition and processing stability of the obtained polyethylene composition]
1 kg of linear low density polyethylene (MI (190 ° C., 2.16 kg): 1 g / 10 min) and 1.0 g of antioxidant composition B were dry blended and extruded at a temperature of 210 ° C. using a 30 mmφ single screw extruder. And pellets were obtained (the MFR (190 ° C., 5 kg) of the pellets was measured and used as the initial MFR). The pellet was extruded three times at 250 ° C. The MFR (190 ° C., 5 kg) of the pellet after extrusion three times was measured, and the processing stability of the polyethylene composition was evaluated.

<Method for evaluating processing stability (MFR (g / 10 min))>
JIS K 7210 (1976) (Method A) However, the temperature was 190 ° C. and the load was 5 kg.

(Examples 10-11, Comparative Examples 5-6)
Examples 10 to 11 and Comparative Examples 5 to 6 were carried out in the same manner as in Example 9 except that the granular composition shown in Table 4 was used. The results are shown in Table 4 together with Example 9. The closer the MFR after repeated extrusion is to the initial MFR, the better the processing stability.

Claims (6)

A composition comprising a phosphite represented by the formula (1) and a compound represented by the formula (2), the phosphite (1) being 80 to 98.100 parts by weight with respect to 100 parts by weight of the composition. A granular composition containing 04 parts by weight and containing 1 to 8 parts by weight of the compound (2).

[Wherein R ¹ , R ² , R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkyl having 6 to 12 carbon atoms. A cycloalkyl group, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X represents a single bond, a sulfur atom or a —CHR ⁶ — group. , R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms,
A represents an alkylene group having 2 to 8 carbon atoms or * —C (═O) R ⁷ — group, R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and “*” represents> PO -Represents a bond with the oxygen atom side of the moiety,
Y and Z each represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
When Y is a hydroxyl group, any one of R ⁴ and R ⁵ is an alkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, carbon Represents an aralkyl group or a phenyl group of formula 7 to 12, and two R ^{1 s} in formula (1) may be the same or different from each other, and ^two R ^{2 s} in formula (1) may be the same as each other The two R ³ in the formula (1) may be the same as or different from each other. ]
^{(R 8 -B-S-C} 2 H 4 CO 2) n -D (2)
[Wherein R ⁸ represents an alkyl group having 12 to 18 carbon atoms. B represents a single bond or a —C ₂ H ₄ CO ₂ — group. D represents an n-valent alcohol residue having 5 to 18 carbon atoms. n represents an integer of 1 to 4. ]   Compound (2) is 3,3′-thiodipropionic acid di-n-dodecyl ester, 3,3′-thiodipropionic acid di-n-tetradecyl ester, 3,3′-thiodipropionic acid di-n. The granular composition according to claim 1, which is at least one compound selected from the group consisting of -octadecyl ester and tetrakis (3-dodecylthiopropionic acid) pentaerythrityl ester.   The granular composition according to claim 1 or 2, wherein the average particle size is 90 to 1000 µm.   The granular composition according to any one of claims 1 to 3, wherein the content of a component having a particle size of 45 µm or less in the granular composition is 10 wt% or less.   A method for stabilizing a thermoplastic resin, comprising 0.02 to 1 part by weight of the composition according to any one of claims 1 to 4 in 100 parts by weight of a thermoplastic resin. The stabilization method according to claim 5 , wherein the thermoplastic resin is a polyolefin.