JPH0812844A - Dispersant composition for thermoplastic resin - Google Patents

Abstract

PURPOSE:To obtain the subject composition low in viscosity even in the presence of a functionality-imparting agent, excellent in meterability, comprising a carbodiimide compound and at least one kind selected from polybutadiene-based dispersants and hydrogenated polybutadiene-based dispersants. CONSTITUTION:This composition comprises (A) 100 pts.wt. of at least one kind of dispersant selected from polybutadiene-based dispersants and hydrogenated polybutadiene-based dispersants and (B) pref. 1-130 pts.wt. of a carbodiimide compound of pref. the formula (R<1>-R<2> are each a 1-6C alkyl; R<5>-R<10> are each H or a 1-16C alkyl) (e.g. 2,6,2',6'-tetraisopropyldiphenylcarbodiimide). The component A is pref. liquid at normal temperature. This composition is homogeneously mixed with a thermoplastic resin (e.g. a polyester resin) followed by melt spinning to obtain uniform fibers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dispersant composition used to uniformly add and disperse a functionalizing agent such as a pigment or an antioxidant to a thermoplastic resin such as a polyester resin during molding. The present invention relates to a fiber manufacturing method for obtaining fibers in which a functionalizing agent is uniformly dispersed using a dispersant composition.

[0002]

2. Description of the Related Art Aromatic polyester resins mainly composed of polyethylene terephthalate are widely used due to their excellent properties. At present, various functionalizing agents are added by various addition methods in order to further improve the performance. However, when such a function-imparting agent is added, coloring and performance deterioration of the polyester resin itself may occur due to deterioration of the function-imparting agent caused by contact with molten polyester for a long time for uniform dispersion and stirring. It became a problem. In particular, it is difficult to uniformly disperse dyes and pigments, and it is necessary to knead for a long time to achieve this.

Therefore, a technique for uniformly dispersing the function-imparting agent in the molten polyester resin in a short time is required. As a typical example thereof, the function-imparting agent is mixed in advance with various dispersants to prepare a molten polyester resin. A technique was born in which this mixture was added just before molding and discharging, and the functionalizing agent was dispersed in a short time to supply a stable polyester resin molded product. However, this technique has a serious drawback in that a significant thickening occurs in the process of pre-mixing the functionalizing agent with the dispersant, and it is difficult to uniformly measure and disperse it in the molten polyester resin due to the high viscosity mixture. there were. Therefore, it is necessary to increase the ratio of the dispersant to the function-imparting agent in the mixture in order to prevent the viscosity from increasing, in other words, the function-imparting agent cannot be added at a high concentration. Further, there is a problem that the dispersant added more than necessary adversely affects the polyester resin.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a dispersant composition for adding / dispersing a function-imparting agent during molding of thermoplastic resin such as polyester resin. Another object of the present invention is to provide a dispersant composition capable of uniformly dispersing a function-imparting agent in a molten thermoplastic resin during molding of the thermoplastic resin. Another object of the present invention is to provide a dispersant composition having a small increase in viscosity and excellent meterability when it contains a functionalizing agent.

Still another object of the present invention is to provide a method for producing a fiber using the above dispersant composition to obtain a fiber in which a functionalizing agent is uniformly dispersed.

[0006]

According to the present invention, a first
And a carbodiimide compound, and at least one dispersant selected from a polybutadiene-based dispersant and a hydrogenated polybutadiene-based dispersant, and a dispersant composition for a thermoplastic resin. In addition, a dispersant composition containing at least one dispersant selected from polybutadiene-based dispersants and hydrogenated polybutadiene-based dispersants, a carbodiimide compound, and optionally a functionalizing agent other than the carbodiimide compound was melted. A method for producing a thermoplastic resin fiber is provided, which comprises uniformly mixing with a thermoplastic resin and then performing melt spinning to achieve the above-mentioned object of the present invention.

The present invention will be described in detail below, by which other objects, constitutions and advantages and effects of the present invention will become apparent.

The dispersants used in the dispersant composition of the present invention are polybutadiene dispersants and hydrogenated polybutadiene dispersants. It is preferable that the dispersant is liquid at room temperature.

The polybutadiene-based dispersant used as the dispersant in the dispersant composition of the present invention includes 1,2-addition of butadiene, cis-1,4 addition or trans-1,4 of butadiene.
Polybutadiene produced by addition, copolymerized with butadiene and a small amount of other conjugated or non-conjugated dienes such as isoprene and chloroprene, and copolymerized with butadiene and a small amount of vinyl monomers such as ethylene, propylene and methyl acrylate. Can be mentioned.

The polybutadiene-based dispersant is preferably liquid at room temperature, and its number average molecular weight maintains the miscibility of the dispersant composition of the present invention with the molten thermoplastic resin and the physical properties of the resin after mixing. From the viewpoint, 500 or more, more preferably 1,000 or more, particularly preferably 1,000 to
It is 3,000. It is preferably liquid at room temperature.

The hydrogenated polybutadiene-based dispersant, which is another dispersant used in the dispersant composition of the present invention, is obtained by hydrogenating a part or all of the hydrogen-carbon double bonds contained in the polybutadiene-based dispersant described above. It was done. The hydrogenation rate is usually 50 to 100 mol%.

The hydrogenated polybutadiene dispersant is preferably liquid at room temperature, and its number average molecular weight is the same as that of the polybutadiene dispersant including the preferred embodiment.

The presence of hydroxyl groups at the polymer terminals of the polybutadiene-based dispersant and the hydrogenated polybutadiene-based dispersant is preferable from the viewpoint of improving the compatibility between the polyester dispersant composition of the present invention and the polyester resin. A hydroxyl value of 10 to 100 mgKOH / g is suitable. When a hydroxyl group is present at the polymer terminal, a dispersant obtained by reacting the hydroxyl group with an aliphatic monocarboxylic acid such as oleic acid, lauric acid, stearic acid or various lactones can also be used.

Further, a carboxyl group may be present at the polymer terminals of both of these dispersants. When a carboxyl group is present at the polymer terminal, a product obtained by reacting this carboxyl group with a monohydric alcohol such as octyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol or decyl alcohol can also be used as a dispersant.

The above polybutadiene-based dispersants and hydrogenated polybutadiene-based dispersants can be used alone or in admixture of two or more.

The dispersant composition of the present invention contains a carbodiimide compound. By containing the carbodiimide compound, the viscosity becomes lower than that of the dispersant itself, and even if the dispersant composition of the present invention contains the functionalizing agent, the degree of thickening is low.

Preferred examples of the carbodiimide compound used in the present invention are represented by the following general formula (I)

[0018]

Embedded image

(Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents an alkyl group having 1 to 7 carbon atoms,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and each represents an alkyl group having 1 to 16 carbon atoms or a hydrogen atom. )

A carbodiimide compound represented by: Specific examples of the carbodiimide compound represented by the above formula (I) include 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide, 2,4,6,2 ′, 4 ′,
6'-hexaisopropyldiphenylcarbodiimide,
2,6,2 ', 6'-tetraisopropyl-4,4'-didodecyldiphenylcarbodiimide, 2,6,2', 6'-toteraisopropyl-3,3'-didodecyldiphenylcarbodiimide and the like can be mentioned. it can.

In the dispersant composition of the present invention, the dispersant 100
The carbodiimide compound is usually 1 to 130 parts by weight.
Part by weight, preferably 1 to 55 parts by weight. By blending the carbodiimide compound in the above range, the viscosity of the dispersant composition can be kept low, and the effect of suppressing the thickening of the dispersant composition due to the addition of the functionalizing agent can be appropriately maintained.

When the dispersant composition of the present invention is heated and used, more carbodiimide compound than the above range can be blended. For example, when heated to 50 to 100 ° C. and used, even if 100 to 250 parts by weight of the carbodiimide compound is blended with 100 parts by weight of the dispersant, the above-mentioned effects due to the blending of the carbodiimide compound are sufficiently exhibited.

The functionality-imparting agent is preferably added in an amount of 100 parts by weight or less based on 100 parts by weight of the dispersant, and particularly 1 to
An addition amount of 55 parts by weight is preferred. If it is added excessively, the thickening of the dispersant composition becomes remarkable.

Examples of the function-imparting agent include dyes, pigments, fluorescent whitening agents, color-adjusting agents, terminal terminators (terminal hydroxyl group blocking agents, terminal carboxyl group blocking agents, terminal linking agents), antistatic agents, deodorant antibacterial agents. Examples include various stabilizers such as agents, antifouling agents, catalyst deactivators, hygroscopic agents, stretchability improvers, conductive agents, light stabilizers, heat stabilizers, antioxidants, additives, and modifiers. .

The above-mentioned carbodiimide compound contained in the dispersant composition of the present invention itself functions as a stabilizer for the polyester resin and may also be a functionalizing agent. Therefore, a stabilized polyester resin processed product can be obtained by uniformly mixing the above-mentioned dispersant composition consisting essentially of the dispersant and the carbodiimide compound with the molten polyester resin.

The mixing of the dispersant and the carbodiimide compound can be carried out by using a kneader such as a kneader, a ball mill, a sand mill or a triple roll, alone or in combination.

The function-imparting agent other than carbodiimide can be added to the composition of the dispersant and the carbodiimide compound, which are preliminarily and uniformly mixed, and can be uniformly mixed and dispersed by using the above-mentioned kneader.

The dispersant composition of the present invention containing the function-imparting agent thus prepared has a low viscosity and therefore has sufficient meterability. Therefore, it can be stably added to the molten thermoplastic resin with good metering ability, and the function-imparting agent can be uniformly dispersed in the molten thermoplastic resin in a short time. Therefore, the thermal decomposition of the functionalizing agent and the reaction between the thermoplastic resin and the dispersant are remarkably controlled, and thus it is possible to extremely stably produce a processed thermoplastic resin product such as a fiber or a film having little quality unevenness. .

A polyester resin containing 90 mol% or more, particularly 95 mol% or more of ethylene terephthalate units is preferably used as the thermoplastic resin for uniformly dispersing the functionalizing agent using the dispersant composition of the present invention. You can The polyester resin may contain isophthalic acid, naphthalenedicarboxylic acid, adipic acid, oxybenzoic acid, trimellitic acid as an acid component, and also a component such as diethylene glycol, propylene glycol component, pentaerythritol as a diol component or a polyol component. Can be included.

Other suitable thermoplastic resins include polycarbonate resins, polyamides, polyurethanes and the like.

The thermoplastic resin is a stabilizer,
It may contain a functionalizing agent such as a coloring agent.

A method for uniformly mixing the dispersant composition of the present invention containing a function-imparting agent with a molten thermoplastic resin and then melt-spinning to obtain fibers will be described below by taking a polyester resin as an example. To do.

To mix the molten polyester resin and the dispersant composition, it is not necessary to employ a special method. For example, the dispersant composition is injected and added into the molten polyester before spinning while being measured by a gear pump or the like. After that, a method of mixing using a static mixer or the like and then discharging from a spinneret can be mentioned. Here, the amount of the dispersant composition added is 1 to 1 with respect to 100 parts by weight of the polyester.
The amount of the carbodiimide compound is preferably 1 part by weight, and the amount of the carbodiimide compound added is 0.1 part by weight based on 100 parts by weight of the polyester.
It is desirable that the amount is 05 to 3.0 parts by weight.

The polymer discharged from the spinneret may be drawn by a conventional method, for example, at a transaction speed of 1000 m / min, and then stretched at a ratio at which a desired elongation can be obtained. Particularly, suitable effects can be obtained even when the yarn is made so that the single yarn fineness is 5 denier or less.

[0035]

The present invention will be described in detail with reference to the following examples. In the examples, various physical properties were measured by the following methods. (1) Melt viscosity of dispersant composition Using a Rion rotational viscometer (VT-04), measurement was carried out at 25 ° C with a No. 2 rotor. (2) Filament strength Using a tensile tester, yarn length 25 cm, pulling speed 20 cm
/ Min, the temperature was 20 ° C, and the humidity was 65%.

(Examples 1 to 4) In 100.0 parts by weight of the liquid dispersant shown in Tables 1 and 2, 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide and a pigment phthalocyanine blue as a function-imparting agent were added. Was added at the ratio (parts by weight) shown in Tables 1 and 2, and the mixture was heated with stirring at 50 ° C. for 3 minutes, and then 2
The viscosity was measured by cooling to 5 ° C. The results are shown in Tables 1 and 2.

[0037]

[Table 1]

[0038]

[Table 2]

In Tables 1 and 2, the types of dispersants are as follows. Dispersant A Polybutadiene homopolymer Number average molecular weight 2600 to 3400, 1,2-vinyl 90% or more, 1,4-trans 10% or less Dispersant B Hydrogenated polybutadiene (hydrogenated above dispersant A) Number average molecular weight 3100, Iodine value (I ₂ mg / 100 g) 21 or less (99% or more hydrogenated) Dispersant C α, ω-polybutadiene glycol number average molecular weight 2600 to 3200, 1,2-vinyl 90% or more, 1,4-trans 10% Below, hydroxyl value 27.0 KOH mg / g or more Dispersant D α, ω-hydrogenated polybutadiene glycol (hydrogenating the above dispersant E) Number average molecular weight 3000, iodine value (I ₂ mg / 100 g) 21 or less (99% or more) Hydrogenation), hydroxyl value 25-35 KOH mg / g.

(Spinning Examples 1 to 9) Intrinsic viscosity 0.64 dl /
g (o-chlorophenol solvent, measured at a temperature of 35 ° C.),
285 polyethylene terephthalate with a terminal carboxyl group content of 19.5 eq / ton by an extruder
It was melted by heating at 0 ° C. and supplied to a melt spinning device. At this time, several kinds of the dispersant compositions shown in Table 1 and Table 2 were used for 4.1 parts by weight of the molten polyester and 4.1 parts, respectively.
A fixed amount of less than 7 parts by weight was supplied, and then the mixture was mixed in a pipe by using a static mixer manufactured by Kenix Co., Ltd., and then discharged from a spinneret having 24 discharge holes (average retention from supply to discharge). It was wound at a speed of 1100 m / min for 5 minutes. The obtained undrawn yarn is drawn according to a conventional method under the condition that the elongation of the filament is 20%,
A multifilament of 75 denier / 24 filament was obtained. The presence or absence of yarn breakage during spinning, and the dyeing unevenness test after cylindrically knitting this filament were carried out, and the dispersibility of the functionalizing agent (phthalocyanine blue pigment) was observed with a microscope. Further, the tensile strength of the obtained filament was measured. The above results are shown in Table 3.

[0041]

[Table 3]

From the above results, it is clear that by using the dispersant composition of the present invention, yarn breakage during spinning can be suppressed, and the pigment as the function-imparting agent can be uniformly dispersed. Similar results were obtained using any of antimony, germanium, and titanium compounds as the polymerization catalyst for the polyester resin.

The carbodiimides of the present invention do not need to be removed after spinning. As described above, the carbodiimide also has a function of stabilizing the polyester resin, and by remaining it, it is possible to provide an extremely stable polymer.

In order to confirm this, the same dispersant and carbodiimide compound as those used in Example 1 were used to prepare dispersant compositions having the composition ratios shown in Table 4 below. Filaments were prepared in the same manner as in the above spinning example and subjected to hot water treatment (conditions: 134 ° C.,
After 30 hours of autoclaving, the strength retention of the filament was measured. The results are shown in Table 4. As is clear from the results in Table 4, the polyester filament containing the dispersant composition of the present invention is excellent in strength retention.

[0045]

[Table 4]

[0046]

EFFECT OF THE INVENTION The dispersant composition for thermoplastic resins of the present invention has a low viscosity even when it contains a functional-imparting agent such as a pigment and a stabilizer, and therefore has excellent meterability. Therefore, it is possible to uniformly disperse the function-imparting agent in the molten resin, and as a result, it is possible to produce a molded product having a stable and uniform function, particularly a fiber by a melt spinning method.

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Claims (10)

[Claims] 1. A dispersant composition for a thermoplastic resin, comprising at least one dispersant selected from a polybutadiene dispersant and a hydrogenated polybutadiene dispersant, and a carbodiimide compound. 2. The dispersant composition for a thermoplastic resin according to claim 1, wherein the dispersant is liquid at room temperature. 3. A carbodiimide compound is blended in an amount of 1 to 130 parts by weight with respect to 100 parts by weight of a dispersant.
Alternatively, the dispersant composition for a thermoplastic resin according to any one of 2 and 3. 4. A carbodiimide compound represented by the following general formula (I): (Here, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents an alkyl group having 1 to 6 carbon atoms, and R ⁵ , R ⁶ , R 4
⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and each represents an alkyl group having 1 to 16 carbon atoms or a hydrogen atom. The dispersant composition for thermoplastic resin according to any one of claims 1 to 3, which is a compound represented by the formula (4). 5. The carbodiimide compound is 2,6,2 ′, 6 ′.
-The dispersant composition for a thermoplastic resin according to claim 4, which is tetraisopropyldiphenylcarbodiimide. 6. The method according to claim 1, further comprising a functionalizing agent.
5. The thermoplastic resin dispersant composition according to any one of 5 above. 7. The dispersant composition for a thermoplastic resin according to claim 6, wherein the functionalizing agent is a carbodiimide compound. 8. The dispersant composition for a thermoplastic resin according to claim 1, wherein the thermoplastic resin is a polyester resin. 9. A dispersant composition comprising at least one dispersant selected from polybutadiene-based dispersants and hydrogenated polybutadiene-based dispersants, a carbodiimide compound, and optionally a functional-imparting agent other than the carbodiimide compound. After uniformly mixing with the molten thermoplastic resin,
A method for producing a thermoplastic resin fiber, which comprises melt spinning. 10. The method for producing a thermoplastic resin fiber according to claim 9, wherein the thermoplastic resin fiber is a polyester fiber.