JP6144929B2 - Method for producing polybutylene terephthalate resin composition - Google Patents

Description

  The present invention relates to a resin composition using a polybutylene terephthalate resin as a base resin.

Polybutylene terephthalate resin (hereinafter also referred to as “PBT resin”) has a high thermal deformation temperature and excellent electrical properties, mechanical properties, weather resistance, chemical resistance, etc. Widely used in various applications such as automobile parts.
However, since PBT resin has an ester group in the molecule, it has a disadvantage that the physical properties are likely to deteriorate due to hydrolysis in a high temperature and high humidity environment. In such PBT resin, hydrolysis is suppressed. It is important to do. In addition, it is known that if the amount of terminal carboxyl groups of the PBT resin is large, the hydrolysis resistance is known to be affected, and various proposals have been made to reduce the amount of terminal carboxyl groups in order to improve the hydrolysis resistance. (For example, refer patent documents 1-3.).

  Methods for reducing the amount of terminal carboxyl groups include a method for adjusting polymerization conditions such as raw material charge ratio, polymerization temperature and pressure reduction method during polymerization, a method for reacting a terminal blocking agent, a method by solid phase polymerization, epoxy and carbodiimide. A method of adding a reactive compound such as is known.

JP 2001-114880 A JP 2006-063199 A JP 2010-143959 A

However, the conventional methods for improving the hydrolysis resistance have a problem that the viscosity is increased and the fluidity is lowered, and a toxic gas (isocyanate when carbodiimide is used) is generated. Moreover, although the reduction | decrease of the initial amount of terminal carboxyl groups and the physical property after a long-term durability test are examined, the hydrolysis rate has not been mentioned. The long-term durability test described above is performed assuming that it is continuously exposed to a high-temperature and high-humidity environment for a long period of time. It is also important that the reaction rate of is low, and this point has not been considered in the past.
The present invention has been made in view of the above-mentioned conventional problems, and its problem is to reduce the hydrolysis rate without causing various problems such as generation of toxic gas and decrease in fluidity. An object of the present invention is to provide a polybutylene terephthalate resin composition having excellent hydrolyzability.

The present invention for solving the above problems is as follows.
(1) It includes a polybutylene terephthalate resin and a (meth) acrylic acid alkyl ester- (meth) acrylic acid glycidyl polymer having an epoxy equivalent of 500 to 5000 g / eq, and a hydrolysis reaction rate constant k is 0.015 h ^−1. A polybutylene terephthalate resin composition characterized by being less than.

(2) The polybutylene terephthalate resin composition as described in (1) above, wherein the epoxy equivalent of the acrylic acid alkyl ester-glycidyl methacrylate polymer is 500 to 2000 g / eq.

(3) The ratio of the epoxy equivalent of the alkyl acrylate ester-glycidyl methacrylate polymer to the amount of terminal carboxyl groups of the polybutylene terephthalate resin is 0.5 to 4.0. ) Or (2) polybutylene terephthalate resin composition.

(4) The polybutylene terephthalate resin composition according to any one of (1) to (3), wherein the alkyl acrylate ester-glycidyl methacrylate polymer has a weight average molecular weight of 3000 to 7000.

(5) The polybutylene terephthalate resin composition according to any one of (1) to (4), wherein the melt viscosity measured at 260 ° C. and a shear rate of 1000 sec ⁻¹ is 200 Pa · s or less.

  According to the present invention, there is provided a polybutylene terephthalate resin composition having excellent hydrolysis resistance by reducing the hydrolysis rate without causing various problems such as generation of toxic gas and lowering of fluidity. be able to.

The polybutylene terephthalate resin composition of the present invention is a polybutylene terephthalate resin and a (meth) acrylic acid alkyl ester- (meth) acrylic acid glycidyl polymer (hereinafter referred to as “AGMA”) having an epoxy equivalent of 500 to 5000 g / eq. And the hydrolysis reaction rate constant k is less than 0.015 h ⁻¹ .
The PBT resin composition of the present invention blends specific AGMA so that the hydrolysis reaction rate constant k is less than 0.015 h ^−1, thereby slowing the progress of hydrolysis and improving hydrolysis resistance. It is intended.
In the present specification, the expression “(meth) acrylic acid” means acrylic acid or methacrylic acid.
Below, each component of the resin composition of this invention is demonstrated.

[Polybutylene terephthalate resin (PBT resin)]
The polybutylene terephthalate resin (PBT resin) is composed of a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof (C _1-6 alkyl ester, acid halide, etc.), and an alkylene glycol having at least 4 carbon atoms (1 , 4-butanediol) or an ester-forming derivative thereof (acetylated product, etc.) and a resin obtained by polycondensation. The PBT resin is not limited to homopolybutylene terephthalate but may be a copolymer containing 60 mol% or more (particularly 75 mol% or more and 95 mol% or less) of a butylene terephthalate unit.

  The amount of the terminal carboxyl group of the PBT resin is not particularly limited as long as the effect of the present invention is not inhibited. The amount of terminal carboxyl groups of the PBT resin is preferably 40 meq / kg or less, more preferably 30 meq / kg or less, and particularly preferably 25 meq / kg or less.

  The intrinsic viscosity (IV) of the PBT resin is not particularly limited as long as the effect of the present invention is not impaired. The intrinsic viscosity of the PBT resin is preferably 0.60 to 1.20 dL / g. From the viewpoint of preventing cracking and improving toughness for improving heating and cooling durability, it is more preferably 0.65 to 1.15 dL / g. When a PBT resin having an intrinsic viscosity in such a range is used, the resulting PBT resin composition is particularly excellent in moldability. In addition, the intrinsic viscosity can be adjusted by blending PBT resins having different intrinsic viscosities. For example, a PBT resin having an intrinsic viscosity of 0.9 dL / g can be prepared by blending a PBT resin having an intrinsic viscosity of 1.0 dL / g and a PBT resin having an intrinsic viscosity of 0.8 dL / g. The intrinsic viscosity (IV) of the PBT resin can be measured, for example, in o-chlorophenol at a temperature of 35 ° C.

In the PBT resin, as dicarboxylic acid components (comonomer components) other than terephthalic acid and its ester-forming derivatives, for example, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-dicarboxydiphenyl ether, etc. C _8-14 aromatic dicarboxylic acids; C _4-16 alkane dicarboxylic acids such as succinic acid, adipic acid, azelaic acid and sebacic acid; C _5-10 cycloalkane dicarboxylic acids such as cyclohexane dicarboxylic acid; these dicarboxylic acids Examples thereof include ester-forming derivatives of acid components (C _1-6 alkyl ester derivatives, acid halides, and the like). These dicarboxylic acid components can be used alone or in combination of two or more.

Among these dicarboxylic acid components, C _8-12 aromatic dicarboxylic acids such as isophthalic acid, and C _6-12 alkanedicarboxylic acids such as adipic acid, azelaic acid, and sebacic acid are more preferable.

In the PBT resin, as glycol components (comonomer components) other than 1,4-butanediol, for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol, neopentyl glycol, 1, C _2-10 alkylene glycol such as 3-octanediol; polyoxyalkylene glycol such as diethylene glycol, triethylene glycol and dipropylene glycol; cycloaliphatic diol such as cyclohexanedimethanol and hydrogenated bisphenol A; bisphenol A, 4, Bisphenols, such as aromatic diols such as 4'-dihydroxybiphenyl; ethylene oxide 2-mole adducts of bisphenol A, propylene oxide 3-mole adducts of bisphenol A, etc. Alkylene oxide adducts of C _2-4 of A; or ester-forming derivatives of these glycols (acetylated, etc.). These glycol components can be used alone or in combination of two or more.

Among these glycol components, C _2-6 alkylene glycol such as ethylene glycol and trimethylene glycol, polyoxyalkylene glycol such as diethylene glycol, and alicyclic diol such as cyclohexanedimethanol are more preferable.

Examples of comonomer components that can be used in addition to the dicarboxylic acid component and the glycol component include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and 4-carboxy-4′-hydroxybiphenyl. Aromatic hydroxycarboxylic acids; Aliphatic hydroxycarboxylic acids such as glycolic acid and hydroxycaproic acid; C _3-12 lactones such as propiolactone, butyrolactone, valerolactone, caprolactone (ε-caprolactone, etc.); esters of these comonomer components And forming derivatives (C _1-6 alkyl ester derivatives, acid halides, acetylated compounds, etc.).

[(Meth) acrylic acid alkyl ester- (meth) acrylic acid glycidyl polymer (AGMA)]
In the PBT resin composition of the present invention, AGMA having an epoxy equivalent of 500 to 5000 g / eq is blended. By blending the AGMA, the hydrolysis reaction rate constant can be reduced, and as a result, the PBT resin. It is possible to slow the progress of hydrolysis and maintain mechanical properties over a long period of time.

  In the PBT resin composition of the present invention, AGMA having an epoxy equivalent of 500 to 5000 g / eq is used, but if the epoxy equivalent is less than 500 g / eq, the hydrolysis reaction rate constant cannot be reduced, and 5000 g Also when it exceeds / eq, the hydrolysis reaction rate constant may not be sufficiently reduced. The epoxy equivalent is preferably 500 to 2000 g / eq, more preferably 1000 to 1500 g / eq.

  On the other hand, the weight average molecular weight of AGMA is preferably 3000 to 7000, more preferably 4000 to 6000, and particularly preferably 4500 to 5500. If the weight average molecular weight is 3000 or more, it is easy to suppress the occurrence of bleed-out, and if it is 7000 or less, compatibility is advantageous, and thus uneven appearance and variations in physical properties are easily suppressed.

In the present invention, AGMA is blended so that the hydrolysis reaction rate constant k is less than 0.015 h ⁻¹ , preferably less than 0.010 h ⁻¹ .
Here, the hydrolysis reaction rate constant k is an index indicating the rate of terminal carboxyl group formation by hydrolysis, that is, the rate of hydrolysis, and is determined as follows.
First, the chemical reaction formula in which a terminal carboxyl group (hereinafter also referred to as “CEG”) is generated by hydrolysis of the PBT resin is represented by the following formula (1).
_{~COO~ + H 2 O → ~COOH +} HO~ ··· (1)
When the reaction rate v in the above equation (1) is described by a linear equation with respect to the CEG concentration [CEG], the equation (2) is obtained.
v = d [CEG] / dt = k [CEG] (2)
[K is a hydrolysis reaction rate constant (h ⁻¹ ), and t is time (h). ]
The above equation (2) is transformed into the following equation (3), the initial CEG concentration (t = 0) is set as [CEG] ₀ (mmol / kg), and between [CEG] ₀ and [CEG], and When transforming by integrating between 0 and t, equation (4) is obtained.
d [CEG] / [CEG] = kdt (3)
ln [CEG] = kt + ln [CEG] ₀ (4)
In the equation (4), the relationship between t and ln [CEG] indicates a straight line with a slope k. Then, in the reaction of the formula (1), t and [CEG] are measured, a straight line is obtained from the measured data ([CEG] is converted into ln [CEG]) by the least square method, and the slope of the straight line is hydrolyzed. The reaction rate constant is k.
In the present invention, the amount of terminal carboxyl group of the PBT resin composition and the method of measuring the amount of terminal carboxyl group of the PBT resin are, for example, dissolving a resin composition and a pulverized sample of PBT resin in benzyl alcohol at 215 ° C. for 10 minutes. Thereafter, it can be measured by titrating with a 0.01N sodium hydroxide / benzyl alcohol solution.

On the other hand, AGMA is a copolymer of (meth) acrylic acid alkyl ester and (meth) acrylic acid glycidyl. Below, (meth) acrylic-acid alkylester is demonstrated.
The alkyl group of the (meth) acrylic acid alkyl ester may be linear or branched. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group. Examples of such (meth) acrylic acid alkyl esters include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and the like. Is preferred.

The blending amount of AGMA is such that the hydrolysis reaction rate constant k is less than 0.015 h ^−1, and therefore the (meth) acrylic acid alkyl ester- (meth) acrylic acid glycidyl heavy weight relative to the terminal carboxyl group amount of the polybutylene terephthalate resin. The ratio of the epoxy equivalent ratio of the coalescence is preferably set to be 0.5 to 4.0, more preferably 0.6 to 3.0, and more preferably 0.7 to 2. It is particularly preferable to set to 0 (for example, 1.5).

[Other ingredients]
The PBT resin composition of the present invention is, as necessary, other resins, antioxidants, stabilizers, antistatic agents, lubricants, plasticizers, crystal nucleating agents, colorants, as long as the effects of the present invention are not impaired. Conventional additives such as flame retardants and reinforcing fillers can be blended.

Although the PBT resin composition of the present invention can reduce the hydrolysis rate without lowering the fluidity, the melt viscosity measured at 260 ° C. and a shear rate of 1000 sec ⁻¹ should be 200 Pa · s or less. It can be set to 150 Pa · s or less.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

[Examples 1 to 4, Comparative Examples 1 to 10]
In each example and comparative example, PBT resin, (meth) acrylic acid alkyl ester- (meth) acrylic acid glycidyl polymer (AGMA), styrene-glycidyl methacrylate copolymer (SGMA), and ethylene-glycidyl methacrylate copolymer One type of polymer (EGMA) and an antioxidant are blended in the number of parts (parts by mass) shown in Table 1 below, and a twin-screw extruder having a 30 mmφ screw (manufactured by Nippon Steel Works) And kneaded at 260 ° C. to obtain a PBT resin composition in the form of pellets. However, in Comparative Example 1, only the PBT resin and the antioxidant were used.
In addition, the detail of said each component is as follows.
(1) PBT resin: manufactured by Wintech Polymer Co., Ltd., DURANEX (registered trademark) (inherent viscosity 0.68 dL / g, terminal carboxyl group amount 24 meq / kg)
(2) AGMA
AGMA1: NOF Corporation (weight average molecular weight 5000, epoxy equivalent 1100 g / eq)
AGMA2: NOF Corporation, (weight average molecular weight 5000, epoxy equivalent 2100 g / eq)
AGMA3: NOF Corporation, (weight average molecular weight 5000, epoxy equivalent 3800 g / eq)
AGMA4: NOF Corporation, Marproof G-0150M (weight average molecular weight 10,000, epoxy equivalent 310 g / eq)
AGMA5: NOF Corporation, Marproof G-2050M (weight average molecular weight 200000, epoxy equivalent 340 g / eq)
(3) SGMA
SGMA1: NOF Corporation, (weight average molecular weight 5000, epoxy equivalent 310 g / eq)
SGMA2: NOF Corporation, Marproof G-0130S (weight average molecular weight 9000, epoxy equivalent 530 g / eq)
SGMA3: NOF Corporation, (weight average molecular weight 5000, epoxy equivalent 1100 g / eq)
SGMA4: NOF Corporation, (weight average molecular weight 5000, epoxy equivalent 2100 g / eq)
SGMA5: NOF Corporation, (weight average molecular weight 5000, epoxy equivalent 3700 g / eq)
(4) EGMA: manufactured by Sumitomo Chemical Co., Ltd., Bond First E (glycidyl methacrylate / ethylene copolymer, glycidyl methacrylate 12 mass%, epoxy equivalent of about 1190 g / eq)
(6) Antioxidant: Tetrakis [methylene 3 (3,5 di-t-butyl 4-hydroxyphenyl) propionate] methane manufactured by BASF

The following measurements or evaluations were performed using the PBT resin compositions obtained in each of the examples and comparative examples.
(1) Hydrolysis reaction rate constant k
The obtained PBT resin composition pellets were subjected to an exposure treatment at 121 ° C. and 100% RH in a high-temperature humidifier, pulverized, dissolved in benzyl alcohol at 215 ° C. for 10 minutes, and then 0.01 N water The amount of terminal carboxyl groups was measured by titrating with a sodium oxide / benzyl alcohol solution. A straight line was obtained from the data of the treatment time t and the terminal carboxyl group amount (converted to ln [CEG]) by the least square method, and the slope of the straight line was defined as the hydrolysis reaction rate constant k. Table 1 shows the obtained values of k.
(2) Melt Viscosity Using a Capillograph manufactured by Toyo Seiki Co., Ltd., a 1 mmφ × 20 mmL / flat die was used as the capillary, and the melt viscosity at a barrel temperature of 260 ° C. and a shear rate of 1000 sec ⁻¹ was measured. The measurement results are shown in Table 1.
(3) 80% tensile strength life (h)
The obtained pellets were dried at 140 ° C. for 3 hours, and then injection molded under conditions of a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. to produce tensile test pieces in accordance with ISO 3167. The produced test piece was exposed and treated in a thermo-hygrostat under the conditions of 121 ° C. and 100% RH, and the tensile strength was measured every 24 hours in accordance with ISO527-1,2. The time required for the tensile strength to decrease to 80% of the initial strength was used as an index of tensile strength. The time is shown in Table 1. This evaluation test was performed only for Examples 1 and 2 and Comparative Example 4.

From Table 1, in Examples 1-4, the hydrolysis reaction rate constant k is less than 0.015 h ⁻¹ , and it is considered that hydrolysis is slow and various mechanical properties are maintained in a good state for a long time. It is done. As evidence, the results of Examples 1 and 2 were superior to those of Comparative Example 4 in the tensile strength life test. In general, it is known that the tensile strength life is longer as the melt viscosity is higher. However, since Examples 1 and 2 and Comparative Example 4 exhibit the same melt viscosity, the hydrolysis reaction rate constant k is smaller. Is presumed to be advantageous for long-term retention of mechanical properties.
On the other hand, Comparative Example 1 in which AGMA was not blended, Comparative Examples 2 to 4 in which AGMA having an epoxy equivalent outside the range specified in the present invention, Comparative Examples 5 to 9 in which SGMA was used instead of AGMA, In Comparative Example 10 using EGMA in place of AGMA and AGMA, the hydrolysis reaction rate constant k exceeds 0.015 h ⁻¹ , and it is found that the hydrolysis reaction rate constant k cannot be reduced with an epoxy compound other than AGMA. . In addition, these comparative examples are considered to undergo hydrolysis in a short time compared to the examples.

Claims (5)

Using a polybutylene terephthalate resin and an (meth) acrylic acid alkyl ester- (meth) acrylic acid glycidyl polymer having an epoxy equivalent of 500 to 5000 g / eq, the (meth) acrylic acid alkyl ester- (meth) acrylic acid glycidyl The manufacturing method of the polybutylene terephthalate resin composition characterized by including the process of mix | blending a polymer so that the hydrolysis reaction rate constant k obtained by measuring on the following conditions may be less than 0.015h- ¹ .
(conditions)
The pellets of the polybutylene terephthalate resin composition were subjected to exposure treatment at 121 ° C. and 100% RH in a high-temperature and high-humidifier, and then pulverized. The obtained pulverized sample was dissolved in benzyl alcohol at 215 ° C. for 10 minutes, By titrating with a 0.01N sodium hydroxide / benzyl alcohol solution, the initial concentration [CEG] of the terminal carboxyl group amount of the polybutylene terephthalate resin [ ₀ ] and the concentration [CEG] at time t are measured. Next, a straight line represented by the following formula is obtained from the treatment time t and the concentration of the terminal carboxyl group by the least square method, and the slope of the straight line is defined as a hydrolysis reaction rate constant k.
ln [CEG] = kt + ln [CEG] ₀
2. The method for producing a polybutylene terephthalate resin composition according to claim 1, wherein an epoxy equivalent of the alkyl acrylate ester-glycidyl methacrylate polymer is 500 to 2000 g / eq. The ratio of the epoxy equivalent ratio of the alkyl acrylate ester-glycidyl methacrylate polymer to the amount of terminal carboxyl groups of the polybutylene terephthalate resin is 0.5 to 4.0, according to claim 1 or 2. The manufacturing method of the polybutylene terephthalate resin composition of description. 4. The method for producing a polybutylene terephthalate resin composition according to claim 1, wherein the alkyl alkyl ester-glycidyl methacrylate polymer has a weight average molecular weight of 3000 to 7000. 5. 5. The method for producing a polybutylene terephthalate resin composition according to claim 1, wherein the melt viscosity measured at 260 ° C. and a shear rate of 1000 sec ⁻¹ is 200 Pa · s or less.