Patent Application
20130035427
The present invention relates to a thermoplastic polymer composition superior in the processing stability. Moreover, the present invention also relates to a processing stabilizer.
Since thermoplastic polymers are superior in transparency and show good impact resistance, they are widely used for food packaging containers, convenience goods and the like. For the production of such products, thermoplastic polymers are used as compositions containing additives. As additives for thermoplastic polymers, 2,4-di-t-pentyl-6-[1-(3,5-di-t-pentyl-2-hydroxyphenyl)ethyl]phenyl acrylate, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepine (which is also called 6-t-butyl-4-[3-[(2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl]-2-methylphenol), octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris(2,4-di-t-butylphenyl)phosphite and the like are known (patent documents 1-6).
There is a demand for a thermoplastic polymer composition showing further improved processing stability.
The present inventors have conducted intensive studies in an attempt to solve the aforementioned problems and found that a thermoplastic polymer composition containing
the following compound represented by the formula (1),
the following compound represented by the formula (2),
at least one selected from the group consisting of the following compounds represented by the formulas (3)-(7), or
the following compound represented by the formula (8),
glucose, and
a thermoplastic polymer
shows superior processing stability. They have reached the following invention based on such findings.
[1] A thermoplastic polymer composition comprising a compound represented by the formula (1):
wherein in the formula (1),
each R1 and/or each R2 are/is independently a C1-6 alkyl group, a C6-12 aryl group or a C7-18 aralkyl group,
R3 is a hydrogen atom or a C1-3 alkyl group, and
R4 is a hydrogen atom or a methyl group,
glucose and a thermoplastic polymer.
[2] The thermoplastic polymer composition of the above-mentioned [1], wherein the total amount of the compound represented by the formula (1) and glucose is 0.001-3 parts by weight relative to 100 parts by weight of the thermoplastic polymer.
[3] A processing stabilizer comprising a compound represented by the formula (1) and glucose.
[4] The processing stabilizer of the above-mentioned [3],
wherein the compound represented by the formula (1) is at least one selected from the group consisting of 2,4-di-t-pentyl-6-[1-(3,5-di-t-pentyl-2-hydroxyphenyl)ethyl]phenyl acrylate and 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate.
[5] The processing stabilizer of the above-mentioned [3] or [4], wherein the content of glucose is 0.1-95 wt % of the total of the compound represented by the formula (1) and glucose.
[6] The processing stabilizer of any one of the above-mentioned [3]-[5], further comprising a compound represented by the formula (2):
wherein in the formula (2),
each R5 and/or each R6 are/is independently a hydrogen atom or a C1-6 alkyl group,
L1 is an n-valent C1-24 alcohol residue optionally containing a hetero atom,
n is an integer of 1-4, and
the alcohol residue here is a residue obtained by removing a hydrogen atom from the hydroxy group of the alcohol.
[7] The processing stabilizer of any one of the above-mentioned [3]-[6], further comprising at least one selected from the group consisting of the compounds represented by the formulas (3)-(7):
wherein in the formula (3), each R7 and/or each R8 are/is independently a hydrogen atom, a C1-9 alkyl group, a C5-8 cycloalkyl group, a C6-12 alkylcycloalkyl group, a C7-12 aralkyl group or a phenyl group,
wherein in the formula (4), each R9 is independently a hydrogen atom, a C1-9 alkyl group, a C5-8 cycloalkyl group, a C6-12 alkylcycloalkyl group, a C7-12 aralkyl group or a phenyl group,
wherein in the formula (5), each R10 is independently a C1-18 alkyl group or a phenyl group optionally substituted by at least one selected from the group consisting of a C1-9 alkyl group, a C5-8 cycloalkyl group, a C6-12 alkylcycloalkyl group and a C7-12 aralkyl group,
wherein in the formula (6),
each R11 and/or each R12 are/is independently a hydrogen atom, a C1-9 alkyl group, a C5-8 cycloalkyl group, a C6-12 alkylcycloalkyl group, a C7-12 aralkyl group or a phenyl group,
each L2 is independently a single bond, a sulfur atom or a divalent group represented by the formula (6a):
wherein in the formula (6a), R13 and R14 are each independently a hydrogen atom or a C1-7 alkyl group, and the total carbon number of R13 and R14 is not more than 7, and
each L3 is independently a C2-9 alkylene group,
wherein in the formula (7),
each R15 and/or each R16 are/is independently a hydrogen atom, a C1-9 alkyl group, a C5-8 cycloalkyl group, a C6-12 alkylcycloalkyl group, a C7-12 aralkyl group or a phenyl group,
R17 is a C1-8 alkyl group or a phenyl group optionally substituted by at least one selected from the group consisting of a C1-9 alkyl group, a C5-8 cycloalkyl group, a C6-12 alkylcycloalkyl group and a C7-12 aralkyl group, and
L4 is a single bond, a sulfur atom or a divalent group represented by the formula (7a):
wherein in the formula (7a), R18 and R19 are each independently a hydrogen atom or a C1-7 alkyl group, and the total carbon number of R18 and R19 is not more than 7.
[8] The processing stabilizer of any one of the above-mentioned [3]-[6], further comprising a compound represented by the formula (3).
[9] A method of producing a thermoplastic polymer composition comprising mixing the processing stabilizer of any one of the above-mentioned [3]-[8] and a thermoplastic polymer.
[10] Use of the processing stabilizer of any one of the above-mentioned [3]-[8] for improving the processing stability of a thermoplastic polymer composition.
[11] A thermoplastic polymer composition comprising a compound represented by the formula (8):
wherein in the formula (8),
each R20 and/or each R21 are/is independently a hydrogen atom, a C1-3 alkyl group, a C5-8 cycloalkyl group, a C6-12 alkylcycloalkyl group, a C7-12 aralkyl group or a phenyl group,
R23 and R24 are each independently a hydrogen atom, a C1-8 alkyl group, a C5-8 cycloalkyl group, a C6-12 alkylcycloalkyl group, a C7-12 aralkyl group or a phenyl group,
each R22 is independently a hydrogen atom or a C1-8 alkyl group,
L5 is a single bond, a sulfur atom or a divalent group represented by the formula (8a):
wherein in the formula (8a), R25 is a hydrogen atom, a C1-8 alkyl group or a C5-8 cycloalkyl group,
L6 is a C2-8 alkylene group or a divalent group represented by the formula (8b):
wherein in the formula (8b), L7 is a single bond or a C1-8 alkylene group, and * shows bonding to the oxygen atom side, and
one of Z1 and Z2 is a hydroxy group, a C1-8 alkyl group, a C1-8 alkoxy group or a C7-12 aralkyloxy group, and the other is a hydrogen atom or a C1-8 alkyl group, glucose and a thermoplastic polymer.
[12] The thermoplastic polymer composition of the above-mentioned [11], wherein the total amount of the compound represented by the formula (8) and glucose is 0.001-3 parts by weight relative to 100 parts by weight of the thermoplastic polymer.
[13] A processing stabilizer comprising a compound represented by the formula (8) and glucose.
[14] The processing stabilizer of the above-mentioned [13], wherein the compound represented by the formula (8) is 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepine.
[15] The processing stabilizer of the above-mentioned [13] or [14], wherein the content of glucose is 0.1-95 wt % of the total of the compound represented by the formula (8) and glucose.
[16] The processing stabilizer of any one of the above-mentioned [13]-[15], further comprising a compound represented by the formula (2).
[17] The processing stabilizer of any one of the above-mentioned [13]-[16], further comprising at least one selected from the group consisting of the compounds represented by the formulas (3)-(7).
[18] The processing stabilizer of any one of the above-mentioned [13]-[16], further comprising a compound represented by the formula (3).
[19] A method of producing a thermoplastic polymer composition comprising mixing the processing stabilizer of any one of the above-mentioned [13]-[18] and a thermoplastic polymer.
[20] Use of the processing stabilizer of any one of the above-mentioned [13]-[18] for improving the processing stability of a thermoplastic polymer composition.
[21] A thermoplastic polymer composition comprising a compound represented by the formula (2), glucose and a thermoplastic polymer.
[22] The thermoplastic polymer composition of the above-mentioned [21], wherein the total amount of the compound represented by the formula (2) and glucose is 0.001-3 parts by weight relative to 100 parts by weight of the thermoplastic polymer.
[23] The thermoplastic polymer composition of the above-mentioned [21] or [22], wherein the thermoplastic polymer is a styrene-butadiene block copolymer.
[24] A processing stabilizer comprising a compound represented by the formula (2) and glucose.
[25] A processing stabilizer consisting of a compound represented by the formula (2) and glucose.
[26] The processing stabilizer of the above-mentioned [24] or [25], wherein the compound represented by the formula (2) is at least one selected from the group consisting of octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane and pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].
[27] The processing stabilizer of any one of the above-mentioned [24]-[26], wherein the content of glucose is 0.1-95 wt % of the total of the compound represented by the formula (2) and glucose.
[28] A method of producing a thermoplastic polymer composition comprising mixing the processing stabilizer of any one of the above-mentioned [24]-[27] and a thermoplastic polymer.
[29] Use of the processing stabilizer of any one of the above-mentioned [24]-[27] for improving the processing stability of a thermoplastic polymer composition.
[30] A thermoplastic polymer composition comprising glucose, a thermoplastic polymer and at least one selected from the group consisting of the compounds represented by the formulas (3)-(7).
[31] The thermoplastic polymer composition of the above-mentioned [30], wherein the total amount of glucose and the compound selected from the group consisting of the compounds represented by the formulas (3)-(7) is 0.001-3 parts by weight relative to 100 parts by weight of the thermoplastic polymer.
[32] The thermoplastic polymer composition of the above-mentioned [30] or [31], wherein the thermoplastic polymer is a styrene-butadiene block copolymer.
[33] A processing stabilizer comprising glucose and at least one selected from the group consisting of the compounds represented by the formulas (3)-(7).
[34] A processing stabilizer consisting of glucose and at least one selected from the group consisting of the compounds represented by the formulas (3)-(7).
[35] The processing stabilizer of the above-mentioned [33] or [34], wherein at least one selected from the group consisting of the compounds represented by the formulas (3)-(7) is the compound represented by the formula (3).
[36] The processing stabilizer of the above-mentioned [35], wherein the compound represented by the formula (3) is tris(2,4-di-t-butylphenyl)phosphite.
[37] A method of producing a thermoplastic polymer composition comprising mixing the processing stabilizer of any one of the above-mentioned [33]-[36] and a thermoplastic polymer.
[38] Use of the processing stabilizer of any one of the above-mentioned [33]-[36] for improving the processing stability of a thermoplastic polymer composition.
In the present invention, the “Ca-b” means that the carbon number is not less than a and not more than b. In the following, the “compound represented by the formula (1)” and the like are sometimes abbreviated as “compound (1)” and the like. Similarly, the “divalent group represented by the formula (6a)” and the like are sometimes abbreviated as “divalent group (6a)” and the like.
By using compound (1), compound (2), at least one selected from the group consisting of compounds (3)-(7) or compound (8) in combination with glucose, the processing stability of a thermoplastic polymer composition can be improved.
The present invention is explained successively in the following. In the following, the thermoplastic polymer composition of the present invention and the processing stabilizer of the present invention, which contain compound (1) and glucose as essential components, are sometimes referred to as “the first thermoplastic polymer composition” and “the first processing stabilizer”, respectively.
In addition, the thermoplastic polymer composition of the present invention and the processing stabilizer of the present invention, which contain compound (8) and glucose as essential components, are sometimes referred to as “the second thermoplastic polymer composition” and “the second processing stabilizer”, respectively.
Furthermore, the thermoplastic polymer composition of the present invention and the processing stabilizer of the present invention, which contain compound (2) and glucose as essential components, are sometimes referred to as “the third thermoplastic polymer composition” and “the third processing stabilizer”, respectively.
Moreover, the thermoplastic polymer composition of the present invention and the processing stabilizer of the present invention, which contain glucose and at least one selected from the group consisting of compounds (3)-(7) as essential components, are sometimes referred to as “the fourth thermoplastic polymer composition” and “the fourth processing stabilizer”, respectively.
Here, the “processing stabilizer” means an agent used for improving the processing stability of the thermoplastic polymer composition. The processing stability of the thermoplastic polymer composition can be evaluated by the method described in the below-mentioned Examples.
The thermoplastic polymer composition of the present invention characteristically contains the processing stabilizer of the present invention (i.e., compound (1), compound (2), at least one selected from the group consisting of the compounds represented by the formulas (3)-(7), or compound (8), and glucose). The processing stabilizer of the present invention is explained in the following.
The first processing stabilizer contains compound (1) as one of the characteristics. Only one kind of compound (1) may be used or two or more kinds thereof may be used in combination. In the following, compound (1) is explained successively.
Each R1 and/or each R2 in the formula (1) are/is independently a C1-8 alkyl group, a C6-12 aryl group or a C7-18 aralkyl group. While there are two R1, they may be the same or different, and they are preferably the same. The same applies to R2.
The C1-8 alkyl group may be a chain or a cyclic group, preferably a chain (linear or branched chain), more preferably a branched chain. The C1-8 alkyl group includes a linear C1-8 alkyl group (e.g., a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group (to be also referred to as an amyl group) and the like), a branched chain C2-6 alkyl group (e.g., an isopropyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a t-pentyl group, a 2-ethylhexyl group and the like), and a cyclic C2-6 alkyl group (i.e., a C3-6 cycloalkyl group, for example, a cyclopentyl group, a cyclohexyl group and the like). Examples of the C6-12 aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like. Examples of the C7-18 aralkyl group include a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group and the like.
Preferably, each R1 and/or each R2 are/is independently a branched chain C3-8 alkyl group, more preferably a C4-8 alkyl group having a tertiary carbon atom, still more preferably a t-butyl group or a t-pentyl group, particularly preferably a t-pentyl group.
R3 in the formula (1) is a hydrogen atom or a C1-3 alkyl group. The C1-3 alkyl group may be a linear or branched chain. Examples of the C1-3 alkyl group include a methyl group, an ethyl group, a propyl group and an isopropyl group. R3 is preferably a hydrogen atom or a methyl group.
R4 in the formula (1) is a hydrogen atom or a methyl group, preferably a hydrogen atom.
Examples of compound (1) include 2,4-di-t-butyl-6-[1-(3,5-di-t-butyl-2-hydroxyphenyl)ethyl]phenyl(meth)acrylate, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl(meth)acrylate, 2,4-di-t-pentyl-6-[1-(3,5-di-t-pentyl-2-hydroxyphenyl)ethyl]phenyl(meth)acrylate, 2,4-di-t-butyl-6-(3,5-di-t-butyl-2-hydroxy-benzyl)phenyl(meth)acrylate, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-ethylphenyl(meth)acrylate, 2-t-pentyl-6-(3-t-pentyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl(meth)acrylate and the like. Here, the “(meth)acrylate” means “acrylate and methacrylate”.
Preferable compound (1) is 2,4-di-t-pentyl-6-[1-(3,5-di-t-pentyl-2-hydroxyphenyl)ethyl]phenyl acrylate (hereinafter sometimes to be abbreviated as “compound (1-1)”), and 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (hereinafter sometimes to be abbreviated as “compound (1-2)”). Compound (1-1) is commercially available as Sumilizer (registered trade mark) GS(F) (manufactured by Sumitomo Chemical Company, Limited), and compound (1-2) is commercially available as Sumilizer (registered trade mark) GM (manufactured by Sumitomo Chemical Company, Limited).
As compound (1), a commercially available product can be used, or it can be produced according to a known method (e.g., the method described in JP-A-1-168643 or JP-A-58-84835).
The first processing stabilizer contains glucose as one of the characteristics. Glucose may be D-glucose or L-glucose or a mixture thereof, preferably D-glucose (dextrose). Glucose may be α-form or β-form or a mixture thereof. Glucose may be of a pyranose type or a furanose type or a mixture thereof, preferably pyranose type. Glucose may be an anhydride or a hydrate, or a mixture thereof. Glucose is commercially available, and a commercially available product can be directly used.
The content of glucose in the first processing stabilizer is preferably not less than 0.1 wt % (more preferably not less than 1 wt %, still more preferably not less than 2 wt %, particularly preferably not less than 5 wt %), preferably not more than 95 wt % (more preferably not more than 90 wt %, still more preferably not more than 75 wt %, particularly preferably not more than 50 wt %), of the total of compound (1) and glucose.
The first processing stabilizer may consist of compound (1) and glucose, or may contain other component. For example, the first processing stabilizer may contain compound (2). Only one kind of compound (2) may be used or two or more kinds thereof may be used in combination. In the following, compound (2) is explained successively.
Each R5 and/or each R6 in the formula (2) are/is independently a hydrogen atom or a C1-6 alkyl group. When n is two or more, R5 may be the same as or different from each other, and they are preferably the same. The same applies to R6. The C1-6 alkyl group may be a chain or a cyclic group, and the chain may be a linear or branched chain. The C1-6 alkyl group includes a linear C1-6 alkyl group (a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group), a branched chain C3-6 alkyl group (e.g., an isopropyl group, an isobutyl group, a t-butyl group, an isopentyl group, a t-pentyl group, a t-hexyl group), and a cyclic C3-6 alkyl group (i.e., a C3-6 cycloalkyl group, for example, a cyclopentyl group, a cyclohexyl group). Preferably, each R5 and/or each R6 are/is independently a linear C1-6 alkyl group or branched chain C3-6 alkyl group, more preferably a methyl group or a t-butyl group. Still more preferably, each R5 and each R6 are t-butyl groups.
L1 in the formula (2) is an n-valent C1-24 alcohol residue optionally containing a hetero atom, and n is an integer of 1-4. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like. These hetero atoms may be replaced with the carbon atom of the n-valent C1-24 alcohol residue. That is, the n-valent C1-24 alcohol residue may have —O—, —S—, —NR— wherein R is a hydrogen atom or other substituent (e.g., a C1-6 alkyl group)) and the like. As the hetero atom, an oxygen atom is preferable.
The n-valent C1-24 alcohol residue (n=1-4) may be a chain or a cyclic residue, or a combination of these. The chain may be a linear or branched chain.
Examples of the monovalent C1-24 alcohol residue include the residues of methanol, ethanol, propanol, isopropanol, butanol, t-butanol, hexanol, octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol and the like.
Examples of the divalent C1-24 alcohol residue include the residues of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, diethylene glycol, triethylene glycol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane and the like.
Examples of the trivalent C1-24 alcohol residue include the residues of glycerol and the like.
Examples of the tetravalent C1-24 alcohol residue include the residues of erythritol, pentaerythritol and the like.
Examples of compound (2) include ester of 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid, 3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionic acid or 3-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid and a monovalent or polyvalent alcohol. Examples of the aforementioned monovalent or polyvalent alcohol include methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentylglycol, diethylene glycol, thioethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, a mixture thereof and the like.
Preferable compound (2) is octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (hereinafter sometimes to be abbreviated as “compound (2-1)”), 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (hereinafter sometimes to be abbreviated as “compound (2-2)”) and pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (hereinafter sometimes to be abbreviated as “compound (2-3)”). Compound (2-1) is commercially available as “Irganox (registered trade mark) 1076” (manufactured by BASF), compound (2-2) is commercially available as “Sumilizer (registered trade mark) GA-80” (manufactured by Sumitomo Chemical Company, Limited), and compound (2-3) is commercially available as “Irganox (registered trade mark) 1010” (manufactured by BASF).
As compound (2), a commercially available product can be used, or it can be produced according to a known method (e.g., the method described in U.S. Pat. No. 3,330,859, U.S. Pat. No. 3,644,482 or JP-A-59-25826).
The first processing stabilizer may further contain at least one selected from the group consisting of compounds (3)-(7). Only one kind of compounds (3)-(7) may be used or two or more kinds thereof may be used in combination. In the following, compounds (3)-(7) are explained successively.
Each R7 and/or each R8 in the formula (3) are/is independently a hydrogen atom, a C1-6 alkyl group, a C5-8 cycloalkyl group, a C6-12 alkylcycloalkyl group, a C7-12 aralkyl group or a phenyl group. While there are three R7, they may be the same as or different from each other, and they are preferably the same. The same applies to R8. The positions of R7 and R8 are preferably the 2-position and the 4-position.
The C1-6 alkyl group may be a linear or branched chain. The carbon number of the C1-6 alkyl group is preferably not less than 3 and not more than 5. Examples of the C1-6 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a t-pentyl group, a 2-ethylhexyl group, a nonyl group and the like.
The C5-8 cycloalkyl group includes a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
Examples of the C6-12 alkylcycloalkyl group include a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 1-methylcyclohexyl group, a 2-methylcyclohexyl group, a 1-methyl-4-isopropylcyclohexyl group and the like.
Examples of the C7-12 aralkyl group include a benzyl group, an α-methylbenzyl group (also to be referred to as a 1-phenylethyl group), an α,α-dimethylbenzyl group (also to be referred to as a 1-methyl-1-phenylethyl group or a cumyl group) and the like.
Preferably, each R7 and/or each R8 are/is independently a hydrogen atom or a C1-9 alkyl group, more preferably a hydrogen atom, a t-butyl group or a nonyl group, still more preferably a t-butyl group.
Examples of compound (3) include tris(2,4-di-t-butylphenyl)phosphite (hereinafter sometimes to be abbreviated as “compound (3-1)”), triphenyl phosphite, tris(4-nonylphenyl)phosphite, tris(2,4-dinonylphenyl)phosphite and the like. Of these, compound (3-1) is preferable. Compound (3-1) is commercially available as “Irgafos (registered trade mark) 168” (manufactured by BASF).
Each R9 in the formula (4) is independently a hydrogen atom, a C1-9 alkyl group, a C5-8 cycloalkyl group, a C6-12 alkylcycloalkyl group, a C7-12 aralkyl group or a phenyl group. While there are four R9, they may be the same as or different from each other, and they are preferably the same. Examples of the C1-9 alkyl group, C5-8 cycloalkyl group, C6-12 alkylcycloalkyl group and C7-12 aralkyl group for R9 include those mentioned above. Each R9 is preferably independently a hydrogen atom or a C1-9 alkyl group, more preferably a hydrogen atom.
Examples of compound (4) include tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylene diphoshonite (hereinafter sometimes to be abbreviated as “compound (4-1)”), tetrakis(2,4-di-t-butyl-5-methylphenyl)-4,4-biphenylene diphoshonite (hereinafter sometimes to be abbreviated as “compound (4-2)”) and the like. Of these, compound (4-1) is preferable. Compound (4-1) is commercially available as “Sandostab (registered trade mark) P-EPQ” (manufactured by Clariant), and compound (4-2) is commercially available as “Yoshinox (registered trade mark) GSY-P101” (manufactured by API).
Each R10 in the formula (5) is independently a C1-18 alkyl group or a phenyl group. The phenyl group for R10 may have, as a substituent, at least one selected from the group consisting of a C1-9 alkyl group, a C5-8 cycloalkyl group, a C6-12 alkylcycloalkyl group and a C7-12 aralkyl group. Examples of these substituents for phenyl group include those mentioned above. In addition, while there are two R10, they may be the same as or different from each other, and they are preferably the same.
The C1-18 alkyl group may be a linear or branched chain. The carbon number of the C1-18 alkyl group is preferably not less than 12 and not more than 18. Examples of the C1-18 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group and the like.
Examples of the phenyl group substituted by a C1-9 alkyl group include a 2-methylphenyl group, a 4-methylphenyl group, a 2-t-butylphenyl group, a 4-t-butylphenyl group, a 2-nonylphenyl group, a 4-nonylphenyl group, a 2,4-di-t-butylphenyl group, a 2,4-di-nonylphenyl group, a 2,6-di-t-butylphenyl group, a 2-t-butyl-4-methylphenyl group, a 2-t-butyl-4-ethylphenyl group, a 2,5-di-t-butylphenyl group, a 2,6-di-t-butyl-4-methylphenyl group and the like.
Examples of the phenyl group substituted by a C5-8 cycloalkyl group include a 2-cyclopentylphenyl group, a 2-cyclohexylphenyl group, a 4-cyclohexylphenyl group, a 2,4-dicyclohexylphenyl group and the like.
Examples of the phenyl group substituted by a C6-12 alkylcycloalkyl group include a 2-(2-methylcyclohexyl)phenyl group, a 4-(2-methylcyclohexyl)phenyl group, a 2,4-di-(2-methylcyclohexyl)phenyl group and the like.
Examples of the phenyl group substituted by a C7-12 aralkyl group include a 2-benzylphenyl group, a 2-cumylphenyl group, a 4-cumylphenyl group, a 2,4-dicumylphenyl group and the like.
Examples of the phenyl group substituted by a C1-9 alkyl group and a C5-8 cycloalkyl group include a 2-methyl-4-cyclohexylphenyl group and the like. Examples of the phenyl group substituted by a C1-9 alkyl group and a C6-12 alkylcycloalkyl group include a 2-methyl-4-(2-methylcyclohexyl)phenyl group and the like. Examples of the phenyl group substituted by a C1-9 alkyl group and a C7-12 aralkyl group include a 2-benzyl-4-methylphenyl group and the like.
Each R10 is preferably independently an octadecyl group (also to be referred to as a stearyl group), a 2,6-di-t-butyl-4-methylphenyl group, a 2,4-di-t-butylphenyl group or a 2,4-dicumylphenyl group.
Examples of compound (5) include bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite (hereinafter sometimes to be abbreviated as “compound (5-1)”), bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite (hereinafter sometimes to be abbreviated as “compound (5-2)”), bis(2,4-dicumylphenyl)pentaerythritol diphosphite (hereinafter sometimes to be abbreviated as “compound (5-3)”), distearylpentaerythritol diphosphite (hereinafter sometimes to be abbreviated as “compound (5-4)”), diisodecylpentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-t-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-t-butylphenyl)pentaerythritol diphosphite and the like. Of these, compound (5-1), compound (5-2) and compound (5-3) are preferable. Compound (5-1) is commercially available as “Adekastab (registered trade mark) PEP-36” (manufactured by ADEKA), compound (5-2) is commercially available as “Ultranox (registered trade mark) 626” (manufactured by GE Plastics), compound (5-3) is commercially available as “Doverphos S9228T” (manufactured by Dover Chemical Corporation), and compound (5-4) is commercially available as “Adekastab (registered trade mark) PEP-8” (manufactured by ADEKA).
Each R11 and/or each R12 in the formula (6) are/is independently a hydrogen atom, a C1-9 alkyl group, a C5-8 cycloalkyl group, a C6-12 alkylcycloalkyl group, a C7-12 aralkyl group or a phenyl group. Examples of the C1-9 alkyl group, C5-8 cycloalkyl group, C6-12 alkylcycloalkyl group and C7-12 aralkyl group for R11 or R12 include those mentioned above. While there are six R11, they may be the same as or different from each other, and they are preferably the same. The same applies to R12. The positions of R11 and R12 are preferably the 3-position and the 5-position, when the position of the carbon atom on the benzene ring to which L2 is bonded is the 1-position. Preferably, each R11 and/or each R12 are/is independently a C1-9 alkyl group, more preferably a t-butyl group.
Each L2 in the formula (6) is independently a single bond, a sulfur atom or a divalent group represented by the formula (6a). The total carbon number of R13 and R14 in the formula (6a) is not more than 7, and R13 and R14 are each independently a hydrogen atom or a C1-7 alkyl group. While there are three L2, they may be the same as or different from each other, and they are preferably the same.
The C1-7 alkyl group may be a linear or branched chain. The carbon number of the C1-7 alkyl group is preferably not less than 1 and not more than 3. The total carbon number of R13 and R14 is preferably not more than 3. Examples of the C1-7 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a t-pentyl group, a hexyl group, a heptyl group and the like.
Examples of the divalent group (6a) include —CH2—, —CH(CH3)—, —CH(C2H5)—, —C(CH3)2—, —CH(n-C3H7)— and the like.
Each L2 is preferably —CH2— or a single bond, more preferably a single bond.
Each L3 in the formula (6) is independently a C2-8 alkylene group. While there are three L3, they may be the same as or different from each other, and they are preferably the same.
Examples of the C2-8 alkylene group include an ethylene group, a propylene group (—CH(CH3)CH2—, —CH2CH(CH3)—), a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a 2,2-dimethyl-1,3-propylene group and the like.
Each L3 is preferably independently an ethylene group or a trimethylene group, more preferably an ethylene group. % As compound (6), 6,6′,6″-[nitrilotris(ethyleneoxy)]tris(2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepine) (hereinafter sometimes to be abbreviated as “compound (6-1)”) is preferable. Compound (6-1) is commercially available as “Irgafos (registered trade mark) 12” (manufactured by BASF).
Each R15 and/or each R16 in the formula (7) are/is independently a hydrogen atom, a C1-9 alkyl group, a C5-8 cycloalkyl group, a C6-12 alkylcycloalkyl group, a C7-12 aralkyl group or a phenyl group. Examples of the C1-9 alkyl group, C5-8 cycloalkyl group, C6-12 alkylcycloalkyl group and C7-12 aralkyl group for R15 or R16 include those mentioned above. While there are two R15, they may be the same as or different from each other, and they are preferably the same. The same applies to R16. The positions of R15 and R16 are preferably the 3-position and the 5-position, when the position of the carbon atom on the benzene ring to which L4 is bonded is the 1-position. That is, when the position of the carbon atom on the benzene ring to which O is bonded is the 1-position, respectively, the 2-position and the 4-position are preferable. Preferably, each R15 and/or each R16 are/is independently a C1-9 alkyl group, more preferably a t-butyl group.
R17 in the formula (7) is a C1-8 alkyl group or a phenyl group. The phenyl group for R17 may have, as a substituent, at least one selected from the group consisting of a C1-9 alkyl group, a C5-8 cycloalkyl group, a C6-12 alkylcycloalkyl group and a C7-12 aralkyl group. Examples of the C1-6 alkyl group and the phenyl group having a substituent for R17 include those mentioned above. The carbon number of the C1-8 alkyl group for R17 is preferably not less than 4 and not more than 8. R17 is preferably a C1-8 alkyl group, more preferably an octyl group.
L4 in the formula (7) is a single bond, a sulfur atom or a divalent group represented by the formula (7a). The total carbon number of R18 and R18 in the formula (7a) is not more than 7, and R18 and R19 are each independently a hydrogen atom or a C1-7 alkyl group. Examples of the alkyl group for R18 or R19 include those mentioned above. The total carbon number for R18 or R19 is preferably not more than 3. Specific examples of the divalent group (7a) include those recited for the divalent group (6a). L4 is preferably —CH2— or a single bond, more preferably —CH2—.
Examples of compound (7) include 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite (hereinafter sometimes to be abbreviated as “compound (7-1)”) and 2,2′-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite. Of these, compound (7-1) is preferable. Compound (7-1) is commercially available as “Adekastab (registered trade mark) HP-10” (manufactured by ADEKA).
Among compounds (3)-(7), compound (3) is preferable, and compound (3-1) is more preferable.
When the first processing stabilizer contains at least one of compound (2)-compound (7), the content of each of compound (2)-compound (7) is preferably not less than 0.1 part by weight (more preferably not less than 10 parts by weight, still more preferably not less than 20 parts by weight), preferably not more than 200 parts by weight (more preferably not more than 90 parts by weight, still more preferably not more than 80 parts by weight), relative to 100 parts by weight of the total of compound (1) and glucose.
Next, the second processing stabilizer is explained. The second processing stabilizer contains compound (8) as one of the characteristics. Only one kind of compound (8) may be used or two or more kinds thereof may be used in combination. In the following, compound (8) is explained successively.
Each R20 and/or each R21 in the formula (8) are/is independently a hydrogen atom, a C1-8 alkyl group, a C5-8 cycloalkyl group, a C6-12 alkylcycloalkyl group, a C7-12 aralkyl group or a phenyl group. R23 and R24 in the formula (8) are each independently a hydrogen atom, a C1-6 alkyl group, a C5-8 cycloalkyl group, a C6-12 alkylcycloalkyl group, a C7-12 aralkyl group or a phenyl group. While there are two R20, they may be the same as or different from each other, and they are preferably the same. The same applies to R21.
The C1-8 alkyl group may be a linear or branched chain. The carbon number of the C1-8 alkyl group is preferably not less than 1 and not more than 5. Examples of the C1-6 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a t-pentyl group, an isooctyl group (also to be referred to as a 6-methylheptyl group), a t-octyl group (also to be referred to as a 1,1,3,3-tetramethylbutyl group), a 2-ethylhexyl group and the like.
The C5-8 cycloalkyl group includes a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
Examples of the C6-12 alkylcycloalkyl group include a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 1-methylcyclohexyl group, a 2-methylcyclohexyl group, a 1-methyl-4-isopropylcyclohexyl group and the like.
Examples of the C7-12 aralkyl group include a benzyl group, α-methylbenzyl group (also to be referred to as a 1-phenylethyl group), an α,α-dimethylbenzyl group (also to be referred to as a 1-methyl-1-phenylethyl group or a cumyl group) and the like.
Preferably, each R20 and/or R23 are/is independently a C1-8 alkyl group (more preferably a C4-8 alkyl group having a tertiary carbon atom), a C5-8 cycloalkyl group (more preferably a cyclohexyl group) or a C6-12 alkylcycloalkyl group (more preferably a 1-methylcyclohexyl group). As the C4-8 alkyl group having a tertiary carbon atom, a t-butyl group, a t-pentyl group and a t-octyl group are still more preferable.
Each R21 is preferably independently a C1-8 alkyl group, a C5-8 cycloalkyl group or a C6-12 alkylcycloalkyl group, more preferably a C1-5 alkyl group. The C1-5 alkyl group may be a linear or branched chain. Examples of the C1-5 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a t-pentyl group and the like. More preferably, each R21 is independently a methyl group, a t-butyl group or a t-pentyl group.
R24 is preferably a hydrogen atom or a C1-5 alkyl group, more preferably a hydrogen atom or a methyl group. Examples of the C1-5 alkyl group for R24 include those mentioned above.
Each R22 in the formula (8) is independently a hydrogen atom or a C1-8 alkyl group. While there are two R22, they may be the same as or different from each other, and they are preferably the same. Each R22 is preferably a hydrogen atom or a C1-8 alkyl group, more preferably a methyl group or a hydrogen atom. Examples of the C1-8 alkyl group and C1-5 alkyl group for R22 include those mentioned above.
L5 in the formula (8) is a single bond, a sulfur atom or a divalent group represented by the formula (8a). R25 in the formula (8a) is a hydrogen atom, a C1-8 alkyl group or a C5-8 cycloalkyl group. R25 is preferably a hydrogen atom or a C1-5 alkyl group. Examples of the C1-8 alkyl group, C1-5 alkyl group and C5-8 cycloalkyl group for R25 include those mentioned above. L5 is preferably a single bond or the divalent group (8a), more preferably a single bond.
L6 in the formula (8) is a C2-8 alkylene group or a divalent group represented by the formula (8b). L7 in the formula (8b) is a single bond or a C1-8 alkylene group. The C2-8 alkylene group and C1-8 alkylene group may be each a linear or branched chain. Examples of the C2-8 alkylene group include an ethylene group, a propylene group (—CH(CH3)CH2—, —CH2CH(CH3)—), a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a 2,2-dimethyl-1,3-propylene group and the like. Examples of the C1-8 alkylene group include a methylene group, the aforementioned C2-8 alkylene group and the like.
L6 is preferably a C2-8 alkylene group, the divalent group (8b) wherein L7 is a single bond (i.e., a carbonyl group), or the divalent group (8b) wherein L7 is an ethylene group; more preferably a C2-8 alkylene group; and still more preferably a trimethylene group.
One of Z1 and Z2 in the formula (8) is a hydroxy group, a C1-8 alkyl group, a C1-8 alkoxy group or a C7-12 aralkyloxy group, and the other is a hydrogen atom or a C1-8 alkyl group. Examples of the C1-8 alkyl group for Z1 and Z2 include those mentioned above.
The C1-8 alkoxy group may be a linear or branched chain. Examples of the C1-8 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a t-pentyloxy group, an isooctyloxy group (also to be referred to as a 6-methylheptyloxy group), a t-octyloxy group (also to be referred to as a 1,1,3,3-tetramethylbutyloxy group), a 2-ethylhexyloxy group and the like.
Examples of the C7-12 aralkyloxy group include a benzyloxy group, an α-methylbenzyloxy group, an α,α-dimethylbenzyloxy group and the like.
Preferably, one of Z1 and Z2 is a hydroxy group, and the other is a hydrogen atom.
A preferable combination of the substituents is a combination wherein each R20 and/or R23 are/is independently a C4-8 alkyl group having a tertiary carbon atom, cyclohexyl or a 1-methylcyclohexyl group, each R21 is independently a C1-5 alkyl group, each R22 is independently a hydrogen atom or a C1-5 alkyl group, R24 is a hydrogen atom or a C1-5 alkyl group, L5 is a single bond, L6 is a C2-8 alkylene group, and one of Z1 and Z2 is a hydroxy group and the other is a hydrogen atom. In this preferable combination, each R20 is more preferably the same. The same applies to each R21 and each R22. In addition, in this preferable combination, each R20, each R22 and R23 are all still more preferably t-butyl groups or t-pentyl groups (particularly t-butyl groups).
Examples of compound (8) include 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepine, 2,10-dimethyl-4,8-di-t-butyl-6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine, 2,4,8,10-tetra-t-pentyl-6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]-12-methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, 2,4,8,10-tetra-t-pentyl-6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-12-methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-dibenzo[d,f][1,3,2]dioxaphosphepine, 2,10-dimethyl-4,8-di-t-butyl-6-(3,5-di-t-butyl-4-hydroxybenzoyloxy)-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6-(3,5-di-t-butyl-4-hydroxybenzoyloxy)-12-methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, 2,10-diethyl-4,8-di-t-butyl-6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6-[2,2-dimethyl-3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-dibenzo[d,f][1,3,2]dioxaphosphepine and the like.
Of compound (8), 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepine (hereinafter sometimes to be abbreviated as “compound (8-1)”) is preferable. Compound (8-1) is commercially available as “Sumilizer (registered trade mark) GP” (manufactured by Sumitomo Chemical Company, Limited).
As compound (8), a commercially available product can be used, or it can be produced according to a known method (e.g., the method described in JP-A-10-273494).
The second processing stabilizer contains glucose as one of the characteristics. Explanations of glucose are the same as those mentioned above.
The content of glucose in the second processing stabilizer is preferably not less than 0.1 wt % (more preferably not less than 1 wt %, still more preferably not less than 2 wt %, particularly preferably not less than 5 wt %), preferably not more than 95 wt % (more preferably not more than 90 wt %, still more preferably not more than 75 wt %, particularly preferably not more than 50 wt %), of the total of compound (8) and glucose.
The second processing stabilizer may consist of compound (8) and glucose, or may contain other component. For example, the second processing stabilizer may further contain compound (2). Only one kind of compound (2) may be used or two or more kinds thereof may be used in combination. Explanations of compound (2) are the same as those mentioned above.
The second processing stabilizer may further contain at least one selected from the group consisting of compounds (3)-(7). Only one kind of compounds (3)-(7) may be used or two or more kinds thereof may be used in combination. Explanations of compounds (3)-(7) are the same as those mentioned above.
When the second processing stabilizer contains at least one of compound (2)-compound (7), the content of each of compound (2)-compound (7) is preferably not less than 0.1 part by weight (more preferably not less than 10 parts by weight, still more preferably not less than 20 parts by weight), preferably not more than 200 parts by weight (more preferably not more than 90 parts by weight, still more preferably not more than 80 parts by weight), relative to 100 parts by weight of the total of compound (8) and glucose.
Next, the third processing stabilizer is explained. The third processing stabilizer contains compound (2) as one of the characteristics. Only one kind of compound (2) may be used or two or more kinds thereof may be used in combination. Explanations of compound (2) are the same as those mentioned above.
The third processing stabilizer contains glucose as one of the characteristics. Explanations of glucose are the same as those mentioned above.
The content of glucose in the third processing stabilizer is preferably not less than 0.1 wt % (more preferably not less than 1 wt %, still more preferably not less than 2 wt %, particularly preferably not less than 5 wt %), preferably not more than 95 wt % (more preferably not more than 90 wt %, still more preferably not more than 75 wt %, particularly preferably not more than 50 wt %), of the total of compound (2) and glucose.
The third processing stabilizer may consist of compound (2) and glucose, or may contain other component. For example, the third processing stabilizer may contain compound (1). Only one kind of compound (1) may be used or two or more kinds thereof may be used in combination. Explanations of compound (1) are the same as those mentioned above.
The third processing stabilizer may further contain at least one selected from the group consisting of compounds (3)-(7). Only one kind of compounds (3)-(7) may be used or two or more kinds thereof may be used in combination. Explanations of compounds (3)-(7) are the same as those mentioned above.
The third processing stabilizer may further contain compound (8). Only one kind of compound (8) may be used or two or more kinds thereof may be used in combination. Explanations of compound (8) are the same as those mentioned above.
Of compound (1) and compounds (3)-(8) usable for the third processing stabilizer, compound (1), compound (3) and compound (8) are preferable, compound (1) and compound (8) are more preferable, and compound (1) is still more preferable.
When the third processing stabilizer contains at least one of compound (1), compound (3)-compound (8), the content of each of compound (1), compound (3)-compound (8) is preferably not less than 0.1 part by weight (more preferably not less than 10 parts by weight, still more preferably not less than 20 parts by weight), preferably not more than 200 parts by weight (more preferably not more than 90 parts by weight, still more preferably not more than 80 parts by weight), relative to 100 parts by weight of the total of compound (2) and glucose.
Next, the fourth processing stabilizer is explained. The fourth processing stabilizer contains at least one selected from the group consisting of compounds (3)-(7) (i.e., organic phosphorous compound) as one of the characteristics. Only one kind of compounds (3)-(7) may be used or two or more kinds thereof may be used in combination. Explanations of compounds (3)-(7) are the same as those mentioned above.
The fourth processing stabilizer contains glucose as one of the characteristics. Explanations of glucose are the same as those mentioned above.
The weight ratio of the compound selected from the group consisting of compounds (3)-(7) and glucose in the fourth processing stabilizer (i.e., compound selected from the group consisting of compounds (3)-(7):glucose) is preferably 1000:1-0.05:1. The compound selected from the group consisting of compounds (3)-(7):glucose is more preferably 1000:1-0.1:1 from the aspect of processing stability of a thermoplastic polymer composition, and still more preferably 1000:1-0.5:1, particularly preferably 1000:1-1:1, from the aspect of suppression of color change of a thermoplastic polymer composition.
The fourth processing stabilizer may consist of glucose and at least one selected from the group consisting of compounds represented by the formulas (3)-(7), or may contain other component. Here, “the fourth processing stabilizer consist of glucose and at least one selected from the group consisting of the compounds represented by the formulas (3)-(7)” means “the total amount of glucose and the compound selected from the group consisting of compound (3)-compound (7) is not less than 99 wt % of the fourth processing stabilizer”.
The fourth processing stabilizer may further contain at least one selected from the group consisting of compound (1), compound (2) and compound (8). Only one kind of each of compound (1), compound (2) and compound (8) may be used or two or more kinds thereof may be used in combination. Explanations of compound (1), compound (2) and compound (8) are the same as those mentioned above.
The content of each of compound (1), compound (2) and compound (8), which can be used in combination in the fourth processing stabilizer is preferably 0-90 wt %, more preferably 0.1-80 wt %, of the fourth processing stabilizer.
The processing stabilizer of the present invention (i.e., the first-fourth processing stabilizers) may contain additives other than the above-mentioned components (hereinafter to be abbreviated as “other additives”). Only one kind of other additives may be used or two or more kinds thereof may be used in combination. Examples of other additive include antioxidant, UV absorber, light stabilizer, stabilizer, lubricant, metal deactivator, nucleating agent, antistatic agent, flame-retardant, filler, pigment, inorganic filler and the like.
Examples of the antioxidant include phenol antioxidant (excluding compound (1) and compound (2)), sulfur antioxidant, phosphorus antioxidant (excluding compounds (3)-(8)), hydroquinone antioxidant and the like.
Examples of the phenol antioxidant include those described in the following [1]-[16] and the like.
[1] alkylated monophenol such as 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,6-di-t-butylphenol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1′-methylundecyl-1′-yl)phenol, 2,4-dimethyl-6-(1′-methylheptadecyl-1′-yl)phenol, 2,4-dimethyl-6-(1′-methyltridecyl-1′-yl)phenol and the like.
[2] alkylthiomethylphenol such as 2,4-bis(octylthiomethyl)-6-t-butylphenol, 2,4-bis(octylthiomethyl)-6-methylphenol, 2,4-bis(octylthiomethyl)-6-ethylphenol, 2,6-bis(dodecylthiomethyl)-4-nonylphenol and the like.
[3] alkylidene bisphenol and derivatives thereof such as 2,2-r-methylenebis(4-methyl-6-t-butylphenol), 2,2′-methylenebis(4-ethyl-6-t-butylphenol), 2,2′-methylenebis[4-methyl-6-α-methylcyclohexyl)phenol], 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,2′-methylenebis(4-methyl-6-nonylphenol), 2,2′-methylenebis(4,6-di-t-butylphenol), 2,2′-ethylidenebis(4,6-di-t-butylphenol), 2,2′-ethylidenebis(4-isobutyl-6-t-butylphenol), 2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4′-methylenebis(6-t-butyl-2-methylphenol), 4,4′-methylenebis(2,6-di-t-butylphenol), 4,4′-butylidenebis(3-methyl-6-t-butylphenol), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3′-t-butyl-4′-hydroxyphenyl)butyrate], bis(3-t-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3′-t-butyl-2′-hydroxy-5′-methylbenzyl)-6-t-butyl-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-t-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra(5-t-butyl-4-hydroxy-2-methylphenyl)pentane and the like.
[4] acylaminophenol derivative such as 4-hydroxylauryl anilide, 4-hydroxystearic anilide, octyl-N-(3,5-di-t-butyl-4-hydroxyphenyl)carbamate and the like.
[5] ester of β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid and a monovalent or polyvalent alcohol (e.g., methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentylglycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane or a mixture thereof and the like).
[6] bis(hydroxyphenyl)sulfide such as 2,2′-thiobis(6-t-butylphenol), 2,2′-thiobis(4-methyl-6-t-butylphenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(2-methyl-6-t-butylphenol), 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)sulfide and the like.
[7] O-benzyl derivative, N-benzyl derivative and S-benzyl derivative such as 3,5,3′,5′-tetra-t-butyl-4,4′-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tris(3,5-di-t-butyl-4-hydroxybenzyl)amine, bis(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide, isooctyl 3,5-di-t-butyl-4-hydroxybenzylmercaptoacetate and the like.
[8] triazine derivative such as 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2-n-octylthio-4,6-bis(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2-n-octylthio-4,6-bis(4-hydroxy-3,5-di-t-butylphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-t-butyl-4-phenoxy)-1,3,5-triazine, tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 2,4,6-tris(3,5-di-t-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 2,4,6-tris(3,5-di-t-butyl-4-hydroxyphenylpropyl)-1,3,5-triazine, tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, tris[2-(3′,5′-di-t-butyl-4′-hydroxycinnamoyloxy)ethyl]isocyanurate and the like.
[9] hydroxybenzylated malonate derivative such as dioctadecyl 2,2-bis(3,5-di-t-butyl-2-hydroxybenzyl)malonate, dioctadecyl 2-(3-t-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecylmercaptoethyl 2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate and the like.
[10] aromatic hydroxybenzyl derivative such as 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,4-bis(3,5-di-t-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)phenol and the like.
[11] benzylphosphonate derivative such as dimethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl 5-t-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoester and the like.
[12] ester of β-(5-t-butyl-4-hydroxy-3-methylphenyl)propionic acid and a monovalent or polyvalent alcohol (e.g., methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentylglycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane or a mixture thereof and the like).
[13] ester of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid and a monovalent or polyvalent alcohol (e.g., methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentylglycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane or a mixture thereof and the like).
[14] ester of 3,5-di-t-butyl-4-hydroxyphenylacetic acid and a monovalent or polyvalent alcohol (e.g., methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentylglycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane or a mixture thereof).
[15] amide of β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid such as N,N′-bis[3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionyl]hydrazine, N,N′-bis[3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionyl]hexamethylenediamine, N,N′-bis[3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionyl]trimethylenediamine and the like.
[16] tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and the like.
Examples of the sulfur antioxidant include dilauryl 3,3′-thiodipropionate, tridecyl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, lauryl stearyl 3,3′-thiodipropionate, neopentanetetrakis(3-lauryl thiopropionate) and the like.
Examples of the phosphorus antioxidant include trilauryl phosphite, trioctadecyl phosphite, tristearylsorbitol triphosphite, 2,2′-ethylidenebis(4,6-di-t-butylphenyl)fluorophosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite, bis(2,4-di-t-butyl-6-methylphenyl)methyl phosphite, 2-(2,4,6-tri-t-butylphenyl)-5-ethyl-5-butyl-1,3,2-oxaphosphorinan and the like.
Examples of the hydroquinone antioxidant include 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, 2,5-di-t-pentylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyphenyl stearate, bis(3,5-di-t-butyl-4-hydroxyphenyl) adipate and the like.
Examples of the UV absorber include those described in the following [1]-[3] and the like.
[1] salicylate derivative such as phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3′,5′-di-t-butyl-4′-hydroxybenzoate, 4-t-octylphenyl salicylate, bis(4-t-butylbenzoyl)resorcinol, benzoylresorcinol, hexadecyl 3′,5′-di-t-butyl-4′-hydroxybenzoate, octadecyl 3′,5′-di-t-butyl-4′-hydroxybenzoate, 2-methyl-4,6-di-t-butylphenyl 3′,5′-di-t-butyl-4′-hydroxybenzoate and the like.
[2] 2-hydroxybenzophenone derivative such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2′,4,4′-tetrahydroxybenzophenone and the like.
[3] 2-(2′-hydroxyphenyl)benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(3′,5′-di-t-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-t-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-t-octylphenyl)benzotriazole, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(3′-sec-butyl-2′-hydroxy-5′-t-butylphenyl)benzotriazole, 2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole, 2-(3′,5′-di-t-pentyl-2′-hydroxyphenyl)benzotriazole, 2-[2′-hydroxy-3′,5′-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-[(3′-t-butyl-2′-hydroxyphenyl)-5′-(2-octyloxycarbonylethyl)phenyl]-5-chlorobenzotriazole, 2-[3′-t-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl]-5-chlorobenzotriazole, 2-[3′-t-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl]-5-chlorobenzotriazole, 2-[3′-t-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl]benzotriazole, 2-[3′-t-butyl-2′-hydroxy-5-(2-octyloxycarbonylethyl)phenyl]benzotriazole, 2-[3′-t-butyl-2′-hydroxy-5′-[2-(2-ethylhexyloxy)carbonylethyl]phenyl]benzotriazole, 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, mixture of 2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole and 2-[3′-t-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenyl]benzotriazole, 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2,2′-methylenebis[4-t-butyl-6-(2H-benzotriazol-2-yl)phenol], condensate of poly(3-11) (ethylene glycol) and 2-[3′-t-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl]benzotriazole, condensate of poly(3-11) (ethylene glycol) and methyl 3-[3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl]propionate, 2-ethylhexyl 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, octyl 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, methyl 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionic acid and the like.
Examples of the light stabilizer include those described in the following [1]-[5] and the like.
[1] hindered amine light stabilizer, for example, those described in the following [a]-[c].
[a] bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(N-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl)2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)decanedioate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-1-[2-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)ethyl]-2,2,6,6-tetramethylpiperidine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate.
[b] mixed ester of 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol, mixed ester of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, mixed ester of 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, mixed ester of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane.
[c] polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[(6-morpholino-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)], poly[(6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)], polycondensate of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 1,2-dibromoethane, N,N′,4,7-tetrakis[4,6-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, N,N′,4-tris[4,6-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, N,N′,4,7-tetrakis[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, N,N′,4-tris[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine.
[2] acrylate light stabilizer such as ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline and the like.
[3] nickel light stabilizer such as nickel complex of 2,2′-thiobis-[4-(1,1,3,3-tetramethylbutyl)phenol], nickel dibutyldithiocarbamate, nickel salt of monoalkylester, nickel complex of ketoxime and the like.
[4] oxamide light stabilizer such as 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-t-butylanilide, 2,2′-didodecyloxy-5,5′-di-t-butylanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-t-butyl-2′-ethoxyanilide, 2-ethoxy-5,4′-di-t-butyl-2′-ethyloxanilide and the like.
[5] 2-(2-hydroxyphenyl)-1,3,5-triazine light stabilizer such as 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and the like.
Examples of the stabilizer include hydroxyamines such as N,N-dibenzylhydroxyamine, N,N-diethylhydroxyamine, N,N-dioctylhydroxyamine, N,N-dilauryl hydroxyamine, N,N-ditetradecylhydroxyamine, N,N-dihexadecylhydroxyamine, N,N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl-N-octadecylhydroxyamine and the like, and the like.
Examples of the lubricant include aliphatic hydrocarbon such as paraffin, wax and the like, C8-22 higher fatty acid, metal (Al, Ca, Mg, Zn) salt of C8-22 higher fatty acid, C8-22 aliphatic alcohol, polyglycol, ester of C4-22 fatty acid and C4-18 aliphatic monovalent alcohol, C8-22 higher aliphatic amide, silicone oil, rosin derivative and the like.
Of the aforementioned other additives, phenol antioxidant, phosphorus antioxidant, sulfur antioxidant, UV absorber and hindered amine light stabilizer are preferable, and phenol antioxidant is more preferable.
Examples of particularly preferable phenol antioxidant include those described below: 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,4-bis(octylthiomethyl)-6-t-butylphenol, 2,2′-thiobis(6-t-butylphenol), 2,2′-methylenebis(4-methyl-6-t-butylphenol), 2,2′-methylenebis(4-ethyl-6-t-butylphenol), 2,2′-methylenebis[4-methyl-6-α-methylcyclohexyl)phenol], 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,2′-methylenebis(4,6-di-t-butylphenol), 2,2′-ethylidenebis(4,6-di-t-butylphenol), 4,4′-methylenebis(6-t-butyl-2-methylphenol), 4,4′-methylenebis(2,6-di-t-butylphenol), 4,4′-butylidenebis(3-methyl-6-t-butylphenol), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 1,1,3-tris(5-t-butyl-4-hydroxy-2-methylphenyl)butane, ethylene glycol bis[3,3-bis(3′-t-butyl-4′-hydroxyphenyl)butyrate], 2,4,6-tris(3,5-di-t-butyl-4-phenoxy)-1,3,5-triazine, tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, bis(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, tris[2-(3′,5′-di-t-butyl-4′-hydroxycinnamoyloxy)ethyl]isocyanurate, diethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate, di-n-octadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoester, neopentanetetrayl tetrakis(3,5-di-t-butyl-4-hydroxycinnamate), thiodiethylene bis(3,5-di-t-butyl-4-hydroxycinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 3,6-dioxaoctamethylene bis(3,5-di-t-butyl-4-hydroxycinnamate), hexamethylene bis(3,5-di-t-butyl-4-hydroxycinnamate), triethylene glycol bis(5-t-butyl-4-hydroxy-3-methylcinnamate), 3,9-bis[2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, N,N′-bis[3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionyl]hydrazine, N,N′-bis[3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionyl]hexamethylenediamine.
Examples of particularly preferable phosphorus antioxidant include those described below: 2,2′-ethylidenebis(4,6-di-t-butylphenyl)fluorophosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite, 2-(2,4,6-tri-t-butylphenyl)-5-ethyl-5-butyl-1,3,2-oxaphosphorinan.
Examples of particularly preferable UV absorber include those described below: phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3′,5′-di-t-butyl-4′-hydroxybenzoate, 4-t-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2′,4,4′-tetrahydroxybenzophenone, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(3′,5′-di-t-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-t-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-t-octylphenyl)benzotriazole, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(3′-sec-butyl-2′-hydroxy-5′-t-butylphenyl)benzotriazole, 2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole, 2-(3′,5′-di-t-pentyl-2′-hydroxyphenyl)benzotriazole, 2-[2′-hydroxy-3′,5′-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole.
Examples of particularly preferable hindered amine light stabilizer include those described below: bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(N-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) 2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-1-[2-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)ethyl]-2,2,6,6-tetramethylpiperidine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, mixed ester of 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol, mixed ester of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, mixed ester of 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, mixed ester of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[(6-morpholino-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)], poly[(6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)].
Examples of the production method of the processing stabilizer of the present invention include a method including mixing the essential components and optional components used as necessary (i.e., compounds (1)-(8), glucose and other additives) of the first-fourth processing stabilizers in a blending machine such as Henschel mixer, super mixer, high speed mixer and the like and the like. The thus-obtained mixture (processing stabilizer) may be further subjected to extrusion molding or agitation granulation.
Next, the thermoplastic polymer composition of the present invention is explained. The thermoplastic polymer composition of the present invention contains respective essential components of the first-fourth processing stabilizers (i.e., compound (1), compound (2), at least one selected from the group consisting of compounds represented by the formulas (3)-(7) or compound (8), and glucose) and a thermoplastic polymer. The thermoplastic polymer composition of the present invention may contain each optional component of the first-fourth processing stabilizers (i.e., compound (1)-compound (8), which are not essential components, and the aforementioned other additives). Only one kind of thermoplastic polymers may be used or two or more kinds thereof may be used in combination.
Examples of the thermoplastic polymer include polyethylene resin (high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-vinyl alcohol copolymer (EVOH), ethylene-ethyl acrylate copolymer (EEA), ethylene-vinyl acetate copolymer (EVA) and the like), polypropylene resin (crystalline propylene homopolymer, propylene-ethylene random copolymer, propylene-α-olefin random copolymer, propylene-ethylene-α-olefin copolymer, polypropylene block copolymer comprised of a block of propylene homopolymer or copolymer containing propylene as a main component and a block of copolymer of propylene and ethylene and/or other α-olefin, and the like), methylpentene polymer, polystyrene resin (polystyrenes such as polystyrene (PS), poly(p-methylstyrene), poly(α-methylstyrene) and the like, acrylonitrile-styrene copolymer (SAN), acrylonitrile-butadiene-styrene copolymer (ABS), special acrylic rubber-acrylonitrile-styrene copolymer, acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS) and the like), polybutadiene resin (polybutadiene; polybutadiene rubber (BR); styrene-butadiene copolymer (SB); styrene-butadiene block copolymer (SBS); impact resistance polystyrene (HI-PS) modified by polybutadiene, styrene-butadiene copolymer or SBS and the like), chlorinated polyethylene (CPE), polychloroprene, chlorinated rubber, poly(vinyl chloride) thermoplastic elastomer, poly(vinyl chloride) (PVC), poly(vinylidene chloride) (PVDC), methacrylate resin, fluororesin, polyacetal (POM), grafted poly(phenylene ether) resin, poly(phenylene sulfide) resin (PPS), polyurethane (PU), polyamide (PA), polyester resin (e.g., poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT) and the like), poly(lactic acid) (PLA), polycarbonate (PC), polyacrylate, polysulfone (PPSU), poly(ether ether ketone) (PEEK), poly(ether sulfone) (PES), aromatic polyester, diallyl phthalate prepolymer, silicone resin (SI), 1,2-polybutadiene, polyisoprene, butadiene-acrylonitrile copolymer (NBR), ethylene-methyl methacrylate copolymer (EMMA) and the like.
Of these, due to good molding processability, polyethylene resin, polypropylene resin, polystyrene resin and polybutadiene resin are preferable, polyethylene resin and polybutadiene resin are more preferable. In the first-third thermoplastic polymer compositions, ethylene-vinyl alcohol copolymer (EVOH) and styrene-butadiene block copolymer (SBS) are more preferable, and in the fourth thermoplastic polymer composition, a styrene-butadiene block copolymer (SBS) is still more preferable.
While the weight average molecular weight (Mw) of the thermoplastic polymer to be used is not particularly limited, it is generally not less than 1000 and not more than 300,000. Mw can be measured by, for example, gel permeation chromatography (GPC) using polystyrene as a standard.
The content of the first processing stabilizer in the first thermoplastic polymer composition is determined by the total amount of compound (1) and glucose. The total amount of compound (1) and glucose in the first thermoplastic polymer composition is preferably not less than 0.001 part by weight (more preferably not less than 0.02 parts by weight, still more preferably not less than 0.1 part by weight, particularly preferably not less than 0.5 parts by weight), preferably not more than 3 parts by weight (more preferably not more than 2 parts by weight, still more preferably not more than 1 part by weight), relative to 100 parts by weight of the thermoplastic polymer.
When the first processing stabilizer containing at least one of compound (2)-compound (7) is used, the content of each of compound (2)-compound (7) in the first thermoplastic polymer composition is preferably not less than 0.001 part by weight (more preferably not less than 0.02 parts by weight), preferably not more than 3 parts by weight (more preferably not more than 2 parts by weight), relative to 100 parts by weight of the thermoplastic polymer.
The content of the second processing stabilizer in the second thermoplastic polymer composition is determined by the total amount of compound (8) and glucose. The total amount of compound (8) and glucose in the second thermoplastic polymer composition is preferably not less than 0.001 part by weight (more preferably not less than 0.02 parts by weight, still more preferably not less than 0.1 part by weight, particularly preferably not less than 0.5 parts by weight), preferably not more than 3 parts by weight (more preferably not more than 2 parts by weight, more preferably not more than 1 part by weight), relative to 100 parts by weight of the thermoplastic polymer.
When the second processing stabilizer containing at least one of compound (2)-compound (7) is used, the content of each of compound (2)-compound (7) in the second thermoplastic polymer composition is preferably not less than 0.001 part by weight (more preferably not less than 0.02 parts by weight), preferably not more than 3 parts by weight (more preferably not more than 2 parts by weight), relative to 100 to parts by weight of the thermoplastic polymer.
The content of the third processing stabilizer in the third thermoplastic polymer composition is determined by the total amount of compound (2) and glucose. The total amount of compound (2) and glucose in the third thermoplastic polymer composition is preferably not less than 0.001 part by weight (more preferably not less than 0.02 parts by weight, still more preferably not less than 0.1 part by weight, particularly preferably not less than 0.5 parts by weight), preferably not more than 3 parts by weight (more preferably not more than 2 parts by weight, still more preferably not more than 1 part by weight), relative to 100 parts by weight of the thermoplastic polymer.
When the third processing stabilizer containing at least one of compound (1), compound (3)-compound (8) is used, the content of each of compound (1), compound (3)-compound (8) in the third thermoplastic polymer composition is preferably not less than 0.001 part by weight (more preferably not less than 0.02 parts by weight), preferably not more than 3 parts by weight (more preferably not more than 2 parts by weight), relative to 100 parts by weight of the thermoplastic polymer.
The content of the fourth processing stabilizer in the fourth thermoplastic polymer composition is determined by the total amount of glucose and the compound selected from the group consisting of compound (3)-compound (7). The total amount of glucose and the compound selected from the group consisting of compound (3)-compound (7) in the fourth thermoplastic polymer composition is preferably 0.001-3 parts by weight, more preferably 0.02-2 parts by weight, still more preferably 0.02-1 part by weight, relative to 100 parts by weight of the thermoplastic polymer. The preferable range of weight ratio of the compound selected from the group consisting of compound (3)-compound (7) and glucose (i.e., compound selected from the group consisting of compound (3)-compound (7):glucose) in the fourth thermoplastic polymer composition is the same as the preferable range of weight ratio in the aforementioned fourth processing stabilizer.
When the fourth processing stabilizer containing at least one of compound (1), compound (2) and compound (8) is used, the content of each of compound (1), compound (2) and compound (8) in the fourth thermoplastic polymer composition is preferably 0.001-3 parts by weight, more preferably 0.02-2 parts by weight, relative to 100 parts by weight of the thermoplastic polymer.
Examples of the production method of the thermoplastic polymer composition of the present invention include a method including mixing the processing stabilizer of the present invention produced as mentioned above and a thermoplastic polymer and the like. This production method also includes, for example, a method including separately adding, when kneading a thermoplastic polymer, each component that can be contained in the processing stabilizer of the present invention, i.e., compounds (1)-(8), glucose and other additives, to a thermoplastic polymer, and mixing them (i.e., the processing stabilizer of the present invention and thermoplastic polymer).
Examples of the mixing method of a processing stabilizer and a thermoplastic polymer include (a) a method including dry-blending a processing stabilizer and a thermoplastic polymer, melt-kneading them and extruding the mixture in a single screw or multiscrew extruder to give pellets of a thermoplastic polymer composition; (b) a method including dissolving a processing stabilizer in a solvent such as cyclohexane and the like to give a solution of the processing stabilizer, adding the solution to a polymer solution after completion of thermoplastic polymer polymerization, and desolvating the mixture; and the like.
The obtained thermoplastic polymer composition may be supplied in a molten state without cooling to a molding machine for molding. The molding method is not particularly limited and, for example, molding method such as injection molding method, extrusion molding method, extrusion blow molding method, injection blow molding method, biaxial orientation blow molding method and the like can be used.
By cooling after molding, a thermoplastic polymer molded product comprised of the thermoplastic polymer composition of the present invention is obtained. Examples of the use of the obtained thermoplastic polymer molding product include electronic component (e.g., coil bobbin, connector, switch, resistor component, socket, relay, condenser case, fuse, motor, oven, printed circuit board, IC manufacturing equipment, lamp and the like), automobile part (e.g., air outlet garnish, hood vent, distributor cap, exhaust gas control valve and the like), clock component (e.g., machine component such as gear, cam and the like, ground plane and the like), camera component (e.g., bottom cover, barrel, lever and the like), component of leisure goods (e.g., reel and the like), household electrical appliance housing, illumination wiring equipment, film, bottle, fiber, septic tank, toilet tank, bath tub, unit bath, water tank, boats and ships, chemicals tank, pipe, corrugated plate, flat plate, paint, decorative laminate, mounting agent for electronic component, resin concrete and the like.
The present invention is explained in more detail in the following by referring to Examples and the like. In the following, “part” and “%” is, unless particularly explained, on the weight basis. In addition, the “melt flow rate” is described as “MFR”.
The components used in the following Examples and the like are as follows.
compound (1-1): 2,4-di-t-pentyl-6-[1-(3,5-di-t-pentyl-2-hydroxyphenyl)ethyl]phenyl acrylate (“Sumilizer (registered trade mark) GS(F)” manufactured by Sumitomo Chemical Company, Limited)
compound (1-2): 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (“Sumilizer (registered trade mark) GM” manufactured by Sumitomo Chemical Company, Limited)
compound (2-1): octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (“Irganox (registered trade mark) 1076” manufactured by BASF)
compound (2-2): 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (“Sumilizer (registered trade mark) GA-80” manufactured by Sumitomo Chemical Company, Limited)
compound (2-3): pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (“Irganox (registered trade mark) 1010” manufactured by BASF)
compound (3-1): tris(2,4-di-t-butylphenyl)phosphite (“Irgafos (registered trade mark) 168” manufactured by BASF)
compound (4-1): tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylene diphoshonite (“Sandostab (registered trade mark) P-EPQ” manufactured by Clariant)
compound (5-1): bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite (“Adekastab (registered trade mark) PEP-36” manufactured by ADEKA)
compound (5-2): bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite (“Ultranox (registered trade mark) 626” manufactured by GE Plastics)
compound (5-3): bis(2,4-dicumylphenyl)pentaerythritol diphosphite (“Doverphos S9228T” manufactured by Dover Chemical Corporation)
compound (6-1): 6,6′,6″-[nitrilotris(ethyleneoxy)]tris(2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepine) (“Irgafos (registered trade mark) 12” manufactured by BASF)
compound (7-1): 2,2-methylenebis(4,6-di-t-butylphenyl) octyl phosphite (“Adekastab (registered trade mark) HP-10” manufactured by ADEKA)
compound (8-1): 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepine (“Sumilizer (registered trade mark) GP” manufactured by Sumitomo Chemical Company, Limited)
D-glucose (manufactured by Wako Pure Chemical Industries, Ltd.)
In the following Example 1-1-Example 1-181, the first processing stabilizer containing compound (1) and D-glucose as essential components is used, in Example 2-1-Example 2-173, the second processing stabilizer containing compound (8) and D-glucose as essential components is used, in Example 3-1-Example 3-130, the third processing stabilizer containing compound (2) and D-glucose as essential components is used, and in Example 4-1-Example 4-196, the fourth processing stabilizer containing D-glucose and at least one selected from the group consisting of compounds (3)-(7) as essential components is used.
The processing stability of the thermoplastic polymer compositions obtained in the following Examples and the like was evaluated by the method of the following (1) or (2).
Dwell MFR tests were performed using the pellets of the thermoplastic polymer compositions. The test was based on JIS K 7210, and 0 min Dwell MFR (g/10 min) and 30 min Dwell MFR (g/10 min) were measured by a melt indexer (L217-E14011 manufactured by Technol Seven Co., Ltd.) under the conditions of temperature in a cylinder 270° C. and load 2.16 kg. The 0 min Dwell MFR was measured after 5-min preheating time after filling pellets of the thermoplastic polymer composition in the cylinder. The MFR variation rate was calculated by the following formula and using the thus-measured 0 min Dwell MFR and 30 min Dwell MFR:
MFR variation rate(%)=absolute value of(30 min Dwell MFR−0 min Dwell MFR)×100/(0 min Dwell MFR)
A smaller MFR variation rate means better processing stability of the thermoplastic polymer composition.
Dwell MFR tests were performed using the pellets of the thermoplastic polymer compositions. The test was based on JIS K 7210, 0 min Dwell MFR (g/10 min) and 30 min Dwell MFR (g/10 min) were measured by a melt indexer (L217-E14011 manufactured by Technol Seven Co., Ltd.) under the conditions of temperature in a cylinder 270° C. and load 2.16 kg. The 0 min Dwell MFR was measured after 5-min preheating time after filling pellets of the thermoplastic polymer composition in the cylinder. The 30 min Dwell MFR was measured after 30 min dwell time, including the preheating time, of the pellets of the thermoplastic polymer composition in the cylinder. The inhibition rate of MFR increment was calculated by the following formula and using the 30 min Dwell MFR obtained in the Example and the 30 min Dwell MFR of Comparative Example:
inhibition rate of MFR increment(%)=(30 min Dwell MFR of Comparative Example−30 min Dwell MFR of Example)×100/(30 min Dwell MFR of Comparative Example)
When polypropylene is used as a thermoplastic polymer, decomposition of polypropylene is accelerated by the heat of processing, and 30 min Dwell MFR increases. Therefore, in a thermoplastic polymer composition containing polypropylene, the processing stability of a thermoplastic polymer composition becomes higher as 30 min Dwell MFR is smaller and the inhibition rate of MFR increment is larger.
Compound (1-1) and D-glucose in the amounts described in Table 1 were mixed to produce a processing stabilizer.
Compound (1-1), D-glucose and compound (2-1) in the amounts described in Table 1 were mixed to produce a processing stabilizer.
The processing stabilizer (0.31 part) obtained in Example 1-1 and a styrene-butadiene block copolymer (“Asaflex 830” manufactured by Asahi Kasei Corp.) (100 parts) were dry-blended, the obtained mixture was knead-extruded by a single screw extruder having a screw diameter of 30 mm (“VS30-28 type extruder” manufactured by TANABE PLASTICS MACHINERY CO., LTD.) under the conditions of temperature 230° C. and screw rotation 50 rpm to give strands, and the strands were cut by a pelletizer to give a thermoplastic polymer composition as pellets. The results of the processing stability of the obtained thermoplastic polymer composition are shown in Table 2.
In the same manner as in Example 1-3 except that the stabilizer composition (0.51 part) obtained in Example 1-2 was used instead of the stabilizer composition obtained in Example 1-1, a thermoplastic polymer composition was obtained as pellets. The results of the processing stability of the obtained thermoplastic polymer composition are shown in Table 2.
Compound (1-1) and D-glucose in the amounts described in Table 1 were mixed to produce processing stabilizers.
Compound (1-1) and compound (2-1) in the amounts described in Table 1 were mixed to produce a processing stabilizer.
In the same manner as in Example 1-3 except that the stabilizer compositions (0.2 part) obtained in Example 1-5-Example 1-9 were used instead of the stabilizer composition obtained in Example 1-1, thermoplastic polymer compositions were obtained as pellets. The results of the processing stability of the obtained thermoplastic polymer composition are shown in Table 2.
In the same manner as in Example 1-3 except that compound (1-1) (0.3 part) alone was used instead of the processing stabilizer obtained in Example 1-1, a thermoplastic polymer composition was obtained as pellets. The results of the processing stability of the obtained thermoplastic polymer composition are shown in Table 2.
In the same manner as in Example 1-3 except that the processing stabilizer (0.5 part) obtained in Reference Example 1-1 was used instead of the processing stabilizer obtained in Example 1-1, a thermoplastic polymer composition was obtained as pellets. The results of the processing stability of the obtained thermoplastic polymer composition are shown in Table 2.
From the results shown in Table 2, it is clear that a combined use of compound (1) and glucose improves the processing stability of thermoplastic polymer compositions as compared to a single use of compound (1). In addition, it is clear that the processing stability of thermoplastic polymer compositions is improved by using glucose in combination, even when compound (2) is used in addition to compound (1).
By mixing the components described in Table 3-1-Table 3-3, processing stabilizers are obtained.
In the same manner as in Example 1-3 except that the thermoplastic polymers and processing stabilizers described in Table 4-1-Table 4-3 are used, thermoplastic polymer compositions are obtained as pellets.
The meanings of the abbreviations of the thermoplastic polymers described in Table 4-1-Table 4-3 are as follows.
P1-1: high density polyethylene (HDPE)
P1-2: low density polyethylene (LDPE)
P1-3: linear low density polyethylene (LLDPE)
P1-4: ethylene-vinyl alcohol copolymer (EVOH)
P1-5: ethylene-ethyl acrylate copolymer (EEA)
P1-6: ethylene-vinyl acetate copolymer (EVA)
P1-7: crystalline propylene homopolymer
P1-8: propylene-ethylene random copolymer
P1-9: propylene-α-olefin random copolymer
P1-10: propylene-ethylene-α-olefin copolymer
P1-11: polystyrene (PS)
P1-12: acrylonitrile-styrene copolymer (SAN)
P1-13: acrylonitrile-butadiene-styrene copolymer (ABS)
P1-14: special acrylic rubber-acrylonitrile-styrene copolymer
P1-15: acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS)
P1-16: polybutadiene rubber (BR)
P1-17: styrene-butadiene copolymer (SB)
P1-18: chlorinated polyethylene (CPE)
P1-19: polychloroprene
P1-20: chlorinated rubber
P1-21: poly(vinyl chloride) (PVC)
P1-22: poly(vinylidene chloride) (PVDC)
P1-23: methacrylate resin
P1-24: fluororesin
P1-25: polyacetal (POM)
P1-26: grafted poly(phenylene ether) resin
P1-27: poly(phenylene sulfide) resin (PPS)
P1-28: polyurethane (PU)
P1-29: polyamide (PA)
P1-30: poly(ethylene terephthalate) (PET)
P1-31: poly(butylene terephthalate) (PBT)
P1-32: polylactic acid (PLA)
P1-33: polycarbonate (PC)
P1-34: polyacrylate
P1-35: polysulfone (PPSU)
P1-36: poly(ether ether ketone) (PEEK)
P1-37: poly(ether sulfone) (PES)
P1-38: aromatic polyester
P1-39: diallyl phthalate prepolymer
P1-40: silicone resin (SI)
P1-41: 1,2-polybutadiene
P1-42: polyisoprene
P1-43: butadiene-acrylonitrile copolymer (NBR)
P1-44: ethylene-methyl methacrylate copolymer (EMMA)
Compound (8-1) and D-glucose in the amounts described in Table 5 were mixed to produce a processing stabilizer.
The processing stabilizer (0.11 part) obtained in Example 2-1 and an ethylene-vinyl alcohol copolymer (“EVAL F171B” manufactured by KURARAY CO., LTD.) (100 parts) were dry-blended, the obtained mixture was knead-extruded by a single screw extruder having a screw diameter of 30 mm (“VS30-28 type extruder” manufactured by TANABE PLASTICS MACHINERY CO., LTD.) under the conditions of temperature 230° C. and screw rotation 50 rpm to give strands, and the strands were cut by a pelletizer to give a thermoplastic polymer composition as pellets. The results of the processing stability of the obtained thermoplastic polymer composition are shown in Table 6.
Compound (8-1) and D-glucose in the amounts described in Table 5 were mixed to produce processing stabilizers.
In the same manner as in Example 2-2 except that the stabilizer compositions (0.2 part) obtained in Example 2-3-Example 2-7 were used instead of the stabilizer composition obtained in Example 2-1, thermoplastic polymer compositions were obtained as pellets. The results of the processing stability of the obtained thermoplastic polymer composition are shown in Table 6.
In the same manner as in Example 2-2 except that compound (8-1) (0.1 part) alone was used instead of the processing stabilizer obtained in Example 2-1, a thermoplastic polymer composition was obtained as pellets. The results of the processing stability of the obtained thermoplastic polymer composition are shown in Table 6.
From the comparison of Example 2-2 and Example 2-8-Example 2-12 with Comparative Example 2-1, it is clear that a combined use of compound (8) and glucose improves the processing stability of thermoplastic polymer compositions as compared to a single use of compound (8).
By mixing the components described in Table 7-1-Table 7-3, processing stabilizers are obtained.
In the same manner as in Example 2-2 except that the thermoplastic polymers and processing stabilizers described in Table 8-1-Table 8-3 are used, thermoplastic polymer compositions are obtained as pellets.
The meanings of the abbreviations of the thermoplastic m polymers described in Table 8-1-Table 8-3 are as follows.
P2-1: high density polyethylene (HDPE)
P2-2: low density polyethylene (LDPE)
P2-3: linear low density polyethylene (LLDPE)
P2-4: ethylene-ethyl acrylate copolymer (EEA)
P2-5: ethylene-vinyl acetate copolymer (EVA)
P2-6: crystalline propylene homopolymer
P2-7: propylene-ethylene random copolymer
P2-8: propylene-α-olefin random copolymer
P2-9: propylene-ethylene-α-olefin copolymer
P2-10: polystyrene (PS)
P2-11: acrylonitrile-styrene copolymer (SAN)
P2-12: acrylonitrile-butadiene-styrene copolymer (ABS)
P2-13: special acrylic rubber-acrylonitrile-styrene copolymer
P2-14: acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS)
P2-15: polybutadiene rubber (BR)
P2-16: styrene-butadiene copolymer (SB)
P2-17: styrene-butadiene block copolymer (SBS)
P2-18: chlorinated polyethylene (CPE)
P2-19: polychloroprene
P2-20: chlorinated rubber
P2-21: poly(vinyl chloride) (PVC)
P2-22: poly(vinylidene chloride) (PVDC)
P2-23: methacrylate resin
P2-24: fluororesin
P2-25: polyacetal (POM)
P2-26: grafted poly(phenylene ether) resin
P2-27: poly(phenylene sulfide) resin (PPS)
P2-28: polyurethane (PU)
P2-29: polyamide (PA)
P2-30: poly(ethylene terephthalate) (PET)
P2-31: poly(butylene terephthalate) (PBT)
P2-32: polylactic acid (PLA)
P2-33: polycarbonate (PC)
P2-34: polyacrylate
P2-35: polysulfone (PPSU)
P2-36: poly(ether ether ketone) (PEEK)
P2-37: poly(ether sulfone) (PES)
P2-38: aromatic polyester
P2-39: diallyl phthalate prepolymer
P2-40: silicone resin (SI)
P2-41: 1,2-polybutadiene
P2-42: polyisoprene
P2-43: butadiene-acrylonitrile copolymer (NBR)
P2-44: ethylene-methyl methacrylate copolymer (EMMA)
Compound (2-1) and D-glucose in the amounts described in Table 9 were mixed to produce a processing stabilizer.
Compound (2-1), D-glucose and compound (1-1) in the amounts described in Table 9 were mixed to produce a processing stabilizer.
Compound (2-1) and compound (1-1) in the amounts described in Table 9 were mixed to produce a processing stabilizer.
The processing stabilizer (0.21 part) obtained in Example 3-1 and a styrene-butadiene block copolymer (“Asaflex 830” manufactured by Asahi Kasei Corp.) (100 parts) were dry-blended, the obtained mixture was knead-extruded by a single screw extruder having a screw diameter of 30 mm (“VS30-28 type extruder” manufactured by TANABE PLASTICS MACHINERY CO., LTD.) under the conditions of temperature 230° C. and screw rotation 50 rpm to give strands, and the strands were cut by a pelletizer to give a thermoplastic polymer composition as pellets. The results of the processing stability of the obtained thermoplastic polymer composition are shown in Table 10.
In the same manner as in Example 3-3 except that compound (2-1) (0.2 part) alone was used instead of the processing stabilizer obtained in Example 3-1, a thermoplastic polymer composition was obtained as pellets. The results of the processing stability of the obtained thermoplastic polymer composition are shown in Table 10.
In the same manner as in Example 3-3 except that the stabilizer composition (0.51 part) obtained in Example 3-2 was used instead of the stabilizer composition obtained in Example 3-1, a thermoplastic polymer composition was obtained as pellets. The results of the processing stability of the obtained thermoplastic polymer composition are shown in Table 10.
In the same manner as in Example 3-3 except that the processing stabilizer (0.5 part) obtained in Reference Example 3-1 was used instead of the processing stabilizer obtained in Example 3-1, a thermoplastic polymer composition was obtained as pellets. The results of the processing stability of the obtained thermoplastic polymer composition are shown in Table 10.
Compound (2-2) and D-glucose in the amounts described in Table 9 were mixed to produce a processing stabilizer.
In the same manner as in Example 3-3 except that the processing stabilizer (0.2 part) obtained in Example 3-5 was used instead of the processing stabilizer obtained in Example 3-1, and polypropylene (“NOBRENE” manufactured by Sumitomo Chemical Company, Limited) (100 parts) was used instead of a styrene-butadiene block copolymer, a thermoplastic polymer composition was obtained as pellets. The results of the processing stability of the obtained thermoplastic polymer composition are shown in Table 10.
In the same manner as in Example 3-6 except that compound (2-2) (0.1 part) alone was used instead of the processing stabilizer obtained in Example 3-5, a thermoplastic polymer composition was obtained as pellets. The results of the processing stability of the obtained thermoplastic polymer composition are shown in Table 10.
From the results shown in Table 10, it is clear that a combined use of compound (2) and glucose improves the processing stability of thermoplastic polymer compositions as compared to a single use of compound (2). In addition, it is clear that the processing stability of thermoplastic polymer compositions is improved by using glucose in combination, even when compound (1) is used in addition to compound (2).
By mixing the components described in Table 11-1-Table 11-3, processing stabilizers are obtained.
In the same manner as in Example 3-3 except that the thermoplastic polymers and processing stabilizers described in Table 12-1 and Table 12-2 are used, thermoplastic polymer compositions are obtained as pellets.
The meanings of the abbreviations of the thermoplastic polymers described in Table 12-1 and Table 12-2 are as follows.
P3-1: high density polyethylene (HDPE)
P3-2: low density polyethylene (LDPE)
P3-3: linear low density polyethylene (LLDPE)
P3-4: ethylene-vinyl alcohol copolymer (EVOH)
P3-5: ethylene-ethyl acrylate copolymer (EEA)
P3-6: ethylene-vinyl acetate copolymer (EVA)
P3-7: propylene-ethylene random copolymer
P3-8: propylene-α-olefin random copolymer
P3-9: propylene-ethylene-α-olefin copolymer
P3-10: polystyrene (PS)
P3-11: acrylonitrile-styrene copolymer (SAN)
P3-12: acrylonitrile-butadiene-styrene copolymer (ABS)
P3-13: special acrylic rubber-acrylonitrile-styrene copolymer
P3-14: acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS)
P3-15: polybutadiene rubber (BR)
P3-16: styrene-butadiene copolymer (SB)
P3-17: styrene-butadiene block copolymer (SBS)
P3-18: chlorinated polyethylene (CPE)
P3-19: polychloroprene
P3-20: chlorinated rubber
P3-21: poly(vinyl chloride) (PVC)
P3-22: poly(vinylidene chloride) (PVDC)
P3-23: methacrylate resin
P3-24: fluororesin
P3-25: polyacetal (POM)
P3-26: grafted poly(phenylene ether) resin
P3-27: poly(phenylene sulfide) resin (PPS)
P3-28: polyurethane (PU)
P3-29: polyamide (PA)
P3-30: poly(ethylene terephthalate) (PET)
P3-31: poly(butylene terephthalate) (PBT)
P3-32: poly(lactic acid) (PLA)
P3-33: polycarbonate (PC)
P3-34: polyacrylate
P3-35: polysulfone (PPSU)
P3-36: poly(ether ether ketone) (PEEK)
P3-37: poly(ether sulfone) (PES)
P3-38: aromatic polyester
P3-39: diallyl phthalate prepolymer
P3-40: silicone resin (SI)
P3-41: 1,2-polybutadiene
P3-42: polyisoprene
P3-43: butadiene-acrylonitrile copolymer (NBR)
P3-44: ethylene-methyl methacrylate copolymer (EMMA)
Compound (3-1) (0.1 part) and D-glucose (0.01 part) were mixed to produce a processing stabilizer.
The processing stabilizer (0.11 part) obtained in Example 4-1 and polypropylene (“NOBRENE” manufactured by Sumitomo Chemical Company, Limited) (100 parts) were dry-blended, the obtained mixture was knead-extruded by a single screw extruder having a screw diameter of 30 mm (“VS30-28 type extruder” manufactured by TANABE PLASTICS MACHINERY CO., LTD.) under the conditions of temperature 230° C. and screw rotation 50 rpm to give strands, and the strands were cut by a pelletizer to give a thermoplastic polymer composition as pellets.
In the same manner as in Example 4-2 except that compound (3-1) (0.3 part) alone was used instead of the processing stabilizer obtained in Example 4-1, a thermoplastic polymer composition was obtained as pellets.
The composition of the processing stabilizer obtained in Example 4-1 is shown in Table 13, and the compositions and the results of processing stability of the thermoplastic polymer compositions obtained in Example 4-2 and Comparative Example 4-1 are shown in Table 14.
By mixing the components described in Table 15-1-Table 15-4, processing stabilizers are obtained. These processing stabilizers are predicted to improve the processing stability of a thermoplastic polymer composition (that is, they inhibit MFR variation rate or increase inhibition rate of MFR increment).
In the same manner as in Example 4-2 except that the thermoplastic polymers and processing stabilizers described in Table 16-1 and Table 16-2 are used, thermoplastic polymer compositions are obtained as pellets. The obtained thermoplastic polymer compositions are predicted to be superior in processing stability.
The meanings of the abbreviations of the thermoplastic polymers described in Table 16-1 and Table 16-2 are as follows.
P4-1: high density polyethylene (HDPE)
P4-2: low density polyethylene (LDPE)
P4-3: linear low density polyethylene (LLDPE)
P4-4: ethylene-vinyl alcohol copolymer (EVOH)
P4-5: ethylene-ethyl acrylate copolymer (EEA)
P4-6: ethylene-vinyl acetate copolymer (EVA)
P4-7: propylene-ethylene random copolymer
P4-8: propylene-α-olefin random copolymer
P4-9: propylene-ethylene-α-olefin copolymer
P4-10: polystyrene (PS)
P4-11: acrylonitrile-styrene copolymer (SAN)
P4-12: acrylonitrile-butadiene-styrene copolymer (ABS)
P4-13: special acrylic rubber-acrylonitrile-styrene copolymer
P4-14: acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS)
P4-15: polybutadiene rubber (BR)
P4-16: styrene-butadiene copolymer (SB)
P4-17: styrene-butadiene block copolymer (SBS)
P4-18: chlorinated polyethylene (CPE)
P4-19: polychloroprene
P4-20: chlorinated rubber
P4-21: poly(vinyl chloride) (PVC)
P4-22: poly(vinylidene chloride) (PVDC)
P4-23: methacrylate resin
P4-24: fluororesin
P4-25: polyacetal (POM)
P4-26: grafted poly(phenylene ether) resin
P4-27: poly(phenylene sulfide) resin (PPS)
P4-28: polyurethane (PU)
P4-29: polyamide (PA)
P4-30: poly(ethylene terephthalate) (PET)
P4-31: poly(butylene terephthalate) (PBT)
P4-32: poly(lactic acid) (PLA)
P4-33: polycarbonate (PC)
P4-34: polyacrylate
P4-35: polysulfone (PPSU)
P4-36: poly(ether ether ketone) (PEEK)
P4-37: poly(ether sulfone) (PES)
P4-38: aromatic polyester
P4-39: diallyl phthalate prepolymer
P4-40: silicone resin (SI)
P4-41: 1,2-polybutadiene
P4-42: polyisoprene
P4-43: butadiene-acrylonitrile copolymer (NBR)
P4-44: ethylene-methyl methacrylate copolymer (EMMA)
The thermoplastic polymer composition of the present invention containing compound (1), compound (2), at least one selected from the group consisting of compound (3)-compound (7), or compound (8) and glucose shows superior processing stability. The thermoplastic polymer composition of the present invention can be used for the production of, for example, electronic component, automobile part, clock component, camera component, component of leisure goods and the like.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2010-092969 | Apr 2010 | JP | national |
| 2010-146806 | Jun 2010 | JP | national |
| 2010-146807 | Jun 2010 | JP | national |
| 2010-146808 | Jun 2010 | JP | national |
| 2010-251754 | Nov 2010 | JP | national |
| 2010-252057 | Nov 2010 | JP | national |
| 2010-252058 | Nov 2010 | JP | national |
| 2010-252059 | Nov 2010 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2011/059263 | 4/14/2011 | WO | 00 | 10/15/2012 |
