JP2002249653A - Molding member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding member which is obtained by alloying a plastic crystalline polyester resin and a thermoplastic amorphous polyester resin and is excellent in bending resistance, chemical resistance and dimensional stability of molding by suppressing physical property deterioration caused by an ester exchange reaction during melt blending. SOLUTION: This molding member is formed by hot kneading the following components; (A) a thermoplastic crystalline polyester resin, (B) a thermoplastic amorphous polyester resin, (C) a Ti compound and (D) a chelator at a blending ratio so that a weight ratio of the components (A)/(B) becomes 1/99-99/1 and a Ti content based on the sum of the components (A)-(D) becomes 1-10,000 ppm followed by molding.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded member excellent in physical properties such as moldability, dimensional accuracy, bending resistance and tensile elongation at break. More specifically, the present invention relates to a molded member suitable for use as a component of an OA device, a functional member, an exterior component and an interior material of an automobile, a component of a home appliance, and the like.

[0002]

2. Description of the Related Art Conventionally, various thermoplastic resins have been used for components and functional members of OA equipment, exterior parts and interior materials of automobiles, and components of home electric appliances.

The required performance of these thermoplastic resins is as follows:
It has high elastic modulus, excellent bending resistance and chemical resistance, high dimensional accuracy, and is transparent depending on the application.

As a general finding, thermoplastic resins can be roughly classified into thermoplastic crystalline resins and thermoplastic amorphous resins, and thermoplastic crystalline resins are excellent in bending resistance and chemical resistance, but are not suitable for molding shrinkage. The ratio is large, so dimensional stability is poor and there is no transparency.On the other hand, thermoplastic amorphous resin has excellent molding dimensional stability and transparency, but has problems such as poor bending resistance and poor chemical resistance. It has been said to have.

However, in many cases, molded members are required to be excellent in all of bending resistance, chemical resistance, molding dimensional stability and the like.

In order to satisfy these requirements, various studies have been made on improvement of physical properties by alloying a thermoplastic crystalline resin and a thermoplastic amorphous resin, and a certain result has been obtained.

[0007] In these studies, for example, in the field of thermoplastic ester resins, it is reported that a crystalline ester resin and an amorphous ester resin can be finely dispersed by promoting a transesterification reaction (copolymerization). Have been. However, in the conventional techniques, when transesterification (copolymerization) is promoted, the generation of a low molecular weight substance by depolymerization proceeds, and this leads to foaming of a molded member obtained and the progress of molecular chain cutting. However, there is a problem that the mechanical properties of the molded member are reduced due to a decrease in the molecular weight (e.g., the tensile elongation at break is reduced), and fine dispersion of both resins by promoting the transesterification reaction has not yet been put to practical use. .

[0008] For this reason, molded members in which physical properties are prevented from deteriorating by suppressing the transesterification reaction are actually used as practical products at present.

[0009]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned conventional problems and provides a molded member obtained by alloying a thermoplastic crystalline ester-based resin and a thermoplastic amorphous ester-based resin with an ester during melt mixing. It is an object of the present invention to provide a molded member that suppresses a decrease in physical properties due to an exchange reaction and is excellent in bending resistance, chemical resistance, molding dimensional stability, and the like.

[0010]

The molded member of the present invention comprises a component A; a thermoplastic crystalline ester resin, a component B, a thermoplastic amorphous ester resin, a component C, a Ti compound and a component D, a chelator. With the weight ratio of component A / component B being 1/9
The composition is characterized in that the mixture is heated and kneaded at a mixing ratio of 9 to 99/1, in which the weight ratio of the Ti element to the total of the components A to D is 1 to 10000 ppm, and then molded.

That is, the present inventors have conducted intensive studies to achieve the above object, and have found that a catalyst for copolymerizing a thermoplastic crystalline ester resin and a thermoplastic amorphous ester resin and for increasing the molecular weight thereof. When a compound containing a Ti-based compound and a chelator for suppressing the reactivity of the Ti-based compound is heated and kneaded, copolymerization by transesterification and high molecular weight are not affected by molding conditions. Can be obtained stably, and has better physical properties such as bending resistance than the resin composition obtained by a method in which the conventional transesterification reaction is suppressed, and the transparency may be improved depending on the conditions. Found that a molded member having
The present invention has been reached.

In the present invention, as the Ti-based compound as a catalyst, an alkyl titanate is preferable.
There is no particular limitation on the type of chelator as a reaction inhibitor for the system compound, but P-type compounds are preferable, and among them, phosphoric acid, phosphate, phosphate ester, phosphorous acid, and phosphite are particularly preferable. And phosphites.

The thermoplastic crystalline ester resin is preferably polyalkylene terephthalate (PAT), and the thermoplastic amorphous ester resin is preferably polyester such as polycarbonate (PC) or polyarylate (PAr).

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

First, the components and their proportions in the present invention will be described.

(Component A: Thermoplastic crystalline ester resin) The thermoplastic crystalline ester resin used in the present invention is not particularly limited, and is a thermoplastic resin having an ester skeleton in a main chain or a side chain, and having a crystal structure. What is necessary is just to have the property,
A general-purpose resin can be used. The thermoplastic crystalline ester resin used in the present invention has a crystallinity of 10%.
% Or more and 100% or less.

Specifically, among thermoplastic crystalline ester resins, PAT (polyalkylene terephthalate) is preferred, and PBT (polybutylene terephthalate), PET (polyethylene terephthalate) and PEN are particularly preferred.
(Polyethylene naphthalate) is more preferable, and PBT
Is particularly preferable because the crystallization rate is high and the change in crystallinity due to molding conditions is small, and the crystallinity is generally stable at about 30%.

Further, a copolymer component can be introduced into the thermoplastic crystalline ester resin used in the present invention as long as the effects of the present invention are not significantly impaired. Specific examples include those having an ester bond as a main chain and introducing an ester bond such as polymethylene glycol.

The molecular weight of the thermoplastic crystalline ester resin used in the present invention is not particularly limited. For example, a resin having a general molecular weight of about 10,000 to 100,000 can be used. When there is a demand for high mechanical properties such as elongation at break, those having a high molecular weight are preferred. In this case, the molecular weight is preferably 20,000 or more, more preferably 25,000 or more, and 30,000 or more.
It is particularly preferable that the number is 000 or more.

(Component B: Thermoplastic Amorphous Ester Resin) The thermoplastic amorphous ester resin used in the present invention is not particularly limited, and is a thermoplastic resin having an ester skeleton in a main chain or a side chain. Any material may be used as long as it is amorphous, and a general-purpose resin can be used. The thermoplastic amorphous ester resin used in the present invention refers to a resin having a crystallinity of less than 10%.

Specifically, PC (polycarbonate) or P
Polyester such as Ar (polyarylate) and PMMA
A resin having an ester bond in a side chain such as (polymethyl methacrylate) can be mentioned as a preferable example.
Among them, polyester is preferable, and PC can be particularly preferably used.

In the thermoplastic amorphous ester resin used in the present invention, a copolymer component can be introduced as long as the effects of the present invention are not significantly impaired. Specific examples include those having an ester bond as a main chain and introducing an ester bond such as polymethylene glycol.

The molecular weight of the thermoplastic amorphous ester resin used in the present invention is not particularly limited. For example, a resin having a general molecular weight of about 10,000 to 100,000 can be used. When high mechanical properties such as tensile elongation at break are required, those having a high molecular weight are preferable. In this case, the molecular weight is preferably 20,000 or more, more preferably 25,000 or more, and 30,000 or more.
It is particularly preferable that the number is 000 or more.

(Weight ratio of thermoplastic crystalline ester resin to thermoplastic amorphous ester resin) In the resin composition of the thermoplastic crystalline ester resin and the thermoplastic amorphous ester resin used in the present invention. Can be employed in a wide range of a weight ratio of thermoplastic crystalline ester resin / thermoplastic amorphous ester resin of 1/99 to 99/1. However, thermoplastic crystalline ester resins are generally excellent in chemical resistance and bending resistance, and thermoplastic crystalline ester resins are excellent in molding dimensional stability. It is preferable to set. In particular, the weight ratio of the thermoplastic crystalline ester resin / thermoplastic amorphous ester resin is 40/60 to 97.
/ 3 is preferred, 60/40 to 95/5 is more preferred, and 70/30 to 90/10 is particularly preferred.

The reason why the ratio of the thermoplastic crystalline ester resin is set to a large value as a particularly preferable ratio is that the thermoplastic amorphous ester resin can be sufficiently improved in molding dimensional stability with a small amount of blending. This is because the effect can be expected, and a slight excess of the thermoplastic amorphous ester-based resin may significantly deteriorate the chemical resistance such as a solvent at the time of coating.

(MFR ratio between thermoplastic crystalline ester resin and thermoplastic amorphous ester resin) MFR of both resins
If the ratio is too large, even if the production conditions are adjusted, good dispersibility may not be obtained, and uniform dispersion may not be achieved. Therefore, the MFR ratio is preferably as small as possible.

Specifically, the MFR of both resins is measured under the same conditions, and the MFR ratio is preferably within a range of about 1/20 to 20/1, and more preferably within a range of 1/10 to 10/1. .

Here, the method of measuring the MFR is based on JIS
According to K-7210, it is preferable to select a measurement temperature condition close to the resin processing temperature.

For example, when PBT and PC are selected, it is preferable to set the processing temperature of 260 ° C. as the measurement temperature and compare the MFR ratios of both resins. In addition, the load can be suitably measured by selecting, for example, 2.16 kg.

(Component C: Ti-based compound) In the present invention, the Ti-based compound is used as a catalyst for promoting the copolymerization of the thermoplastic crystalline ester-based resin and the thermoplastic amorphous ester-based resin and increasing the molecular weight.

The Ti-based compound is not particularly limited,
Alkyl titanates are preferred because of high activity, and among alkyl titanates, tetrabutyl titanate or tetrakis (2-ethylhexyl) ortho titanate is particularly preferred. These are TYZOR TOT (DuPo)
nt) or TYZOR TBT (DuPont) can be easily obtained.

The Ti-based compound is more effective when combined with an alkali metal, alkaline earth metal-containing compound or zinc-containing compound, and is therefore preferable. Among them, a compound containing an Mg element is preferably used in combination. .

The compound containing the Mg element is not particularly limited, but a magnesium salt of an organic acid is particularly preferred, and magnesium acetate is particularly preferred.

(Blending amount of Ti-based compound) If the blending amount of the Ti-based compound in the resin composition is too small, it may not work effectively. Therefore, it is necessary to increase the Ti-based compound to some extent. The weight ratio of the element is component A,
The amount is set to 1 ppm or more based on the total weight of B, C and the component D described later, more preferably 10 ppm or more, particularly preferably 20 ppm or more. on the other hand,
Since the ester-based resin may cause depolymerization due to the presence of a large amount of heavy metal, this ratio needs to be reduced to some extent, and the Ti element ratio is 10,000 ppm or less, preferably 1,000 ppm or less. More preferably, it is 500 ppm or less. Hereinafter, the weight ratio of the Ti element of the Ti-based compound to the total weight of the components A to D may be referred to as “Ti concentration”.

When a Ti-based compound is used in combination with an Mg-containing compound such as magnesium acetate, the amount of the Ti-based compound used is
Mg / Ti = 8 / by weight concentration ratio of Mg element to element
2-2 / 8 is preferred, and about 5/5 is most preferred.

(Component D; Chelator) In the present invention, if the activity of the polymerization catalyst is too high, the depolymerization of the resin is promoted to cause a problem such as a decrease in mechanical properties due to a decrease in molecular weight, and foaming due to generation of a low molecular weight substance. There is.

Therefore, in the present invention, in order to suppress this depolymerization, the metal in the polymerization catalyst, that is, the T
A chelator capable of coordinating with i to form a complex is used as a reaction inhibitor.

The type of the chelator is not particularly limited, and a known chelator can be used.

Examples thereof include P-based compounds such as phosphites, phosphates and phosphates, and hydrazines. These include, for example, Irgaphos 168 (manufactured by Nippon Ciba Geigy Co., Ltd.) and PEP36 ( Asahi Denka Kogyo Co., Ltd.), Sand Stub P-EPQ (Clariant Japan Co., Ltd.) phosphite, IRGANOX
MD1024 (manufactured by Ciba Geigy Japan), CDA-
6 (manufactured by Asahi Denka Kogyo KK) can be easily obtained from the market as hydrazines. Among them, P-based compounds are most preferred as reaction inhibitors for Ti-based compounds as catalysts.

Hereinafter, the P-based compound as a chelator will be described in detail.

The Ti-based compound is effective as a catalyst for copolymerization or high molecular weight, but also promotes depolymerization as a side reaction. If the activity is too high, the depolymerization may take precedence. In the present invention, P is used as a chelator.
The system compound coordinates to Ti of the Ti system compound. Thereby, the reaction regularity as a catalyst is increased, and the depolymerization of a side reaction can be suppressed, and the copolymerization and the increase in the molecular weight can be promoted.

The P-based compounds include phosphoric acid, phosphate,
One or more selected from the group consisting of phosphate esters, phosphorous acid, phosphites, and phosphites.

The phosphate and phosphite are not particularly limited as long as they are metal salts, but alkali metal salts or alkaline earth metal salts are preferred.

The phosphoric ester is represented by the following general formula (I)
Are shown.

[0045]

Embedded image

(In the formula (I), R ¹ , R ² , and R ³ are each independently hydrogen or an alkyl group or an aryl group having 1 to 20 carbon atoms; Z is a single bond or an oxygen atom; Is an oxygen atom.)

Specific examples of the phosphoric ester include triethyl phosphate, tributyl phosphate, triphenyl phosphate and the like.

The phosphites include those represented by the following general formulas (II) to (IV).

[0049]

Embedded image

In the formula (II), R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group, an aralkyl group or an alkylaryl group; At least one of a single bond and an oxygen atom is an oxygen atom.)

Specific examples thereof include triethyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, tristearyl phosphite, triphenyl phosphite,
Tricresyl phosphite, tris (nonylphenyl)
Phosphite, tris (2,4-di-t-butylphenyl) phosphite, decyl-diphenyl phosphite,
Examples include phenyl-di-2-ethylhexyl phosphite, phenyl-didecyl phosphite, tris (biphenyl) phosphite, and tricyclohexyl phosphite.

[0052]

Embedded image

In the formula (III), R⁷, R⁸, R⁹, R^TenHaso
Each independently of the formula (II)^Four, R^Five, R ⁶Belongs to the definition of
Wherein Z has the same definition as Z in formula (II)
You. Y is an alkylene group having 1 to 30 carbon atoms, arylene
Group, cycloalkylene group, aralkylene group, alkyl
Shows an arylene group. )

As a specific example, tetraphenyl-
4,4'-isopropylidene-diphenol diphosphite, tetratridecyl-4,4'-isopropylidene-diphenol diphosphite, tetratridecyl-
4,4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphite, tetrakis (2,4-
Di-t-butylphenyl-4,4'-biphenylene) phosphite;

[0055]

Embedded image

In the formula (IV), R ¹¹ is an alkyl group having 1 to 30 carbon atoms, an aryl group, a cycloalkyl group, an aralkyl group or an alkylaryl group, and R ¹² is a C 1 to C 2 group.
0 is an alkylene group, and Z has the same definition as Z in formula (II). )

As a specific example, bis (stearyl)
Pentaerythritol diphosphite, bis (2,6-
Di-t-butylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite and the like.

Among the various compounds described above, tributyl phosphite, triphenyl phosphite, bis (stearyl) pentaerythritol diphosphite and bis (2,6-di-t-butylphenyl) pentaerythritol diphosphite are particularly preferred. Is preferred.

(Blending amount of chelator) The blending amount of the chelator in the resin composition is not particularly limited. However, if the amount is small, the addition effect as a reaction inhibitor is hardly exhibited, and the effect is remarkably effective from the time when the concentration exceeds a certain concentration. Demonstrate. Therefore, in the present invention, the weight of the element chelating to Ti is preferably at least 100 ppm, more preferably at least 300 ppm, particularly preferably at least 500 ppm, based on the total weight of components A to D. If the compounding amount of the chelator is too large, the catalytic activity of the Ti-based compound is lost, and a good molded member cannot be obtained.
m or less, especially 3000 ppm or less. In the following, T of the chelator with respect to the total weight of the components A to D is used.
The weight ratio of the element chelating to i may be referred to as “chelating element concentration”.

(Additional compounding material; optional component) The resin composition constituting the molded member of the present invention may contain optional compounding components according to various purposes.

Specifically, an antioxidant such as Irganox 1010 (trade name) manufactured by Ciba-Geigy Japan, a heat stabilizer, various plasticizers, a light stabilizer, an ultraviolet absorber, a neutralizing agent, a lubricant, an anti-fog agent And various additives such as an anti-blocking agent, a slip agent, a crosslinking agent, a crosslinking aid, a coloring agent, a flame retardant, and a dispersant.

Further, as far as the effects of the present invention are not significantly impaired, compounding materials such as various thermoplastic resins, various elastomers, thermosetting resins, fillers and the like can be compounded as the second and third components.

The thermoplastic resin as an additional component includes polypropylene, polyethylene (high density, medium density, low density, linear low density), propylene ethylene block or random copolymer, rubber or latex component, for example, ethylene / propylene Copolymer rubber, styrene / butadiene rubber, styrene / butadiene / styrene block copolymer or hydrogenated derivative thereof, polybutadiene, polyisobutylene, polyamide, polyamideimide, polyacetal, polyarylate, polycarbonate, polyimide, liquid crystalline polyester, poly Sulfone, polyphenylene sulfide, polybisamide triazole, polyetherimide, polyetheretherketone, acrylic, polyvinylidene fluoride, polyvinyl fluoride,
Chlorotrifluoroethylene, ethylene tetrafluoroethylene copolymer, hexafluoropropylene, perfluoroalkyl vinyl ether copolymer, alkyl acrylate copolymer, polyester ester copolymer, polyether ester copolymer, polyether amide copolymer One consisting of a polymer, a polyurethane copolymer or the like or a mixture of two or more thereof can be used.

As the thermosetting resin, for example, a resin composed of one kind of an epoxy resin, a melamine resin, a phenol resin, an unsaturated polyester resin, or a mixture of two or more kinds thereof can be used.

The various fillers include, for example, calcium carbonate (heavy and light), talc, mica, silica,
Alumina, aluminum hydroxide, zeolite, wollastonite, diatomaceous earth, glass fiber, glass beads, bentonite, asbestos, hollow glass beads, graphite, molybdenum disulfide, titanium oxide, carbon fiber, aluminum fiber, styrene steel fiber, brass In addition to fillers such as fibers, aluminum powder, wood powder, rice hulls, graphite, metal powder, conductive metal oxides, organometallic compounds, and organometallic salts, as additives, antioxidants (phenolic, sulfuric,
Phosphate esters, etc.), lubricants, various organic and inorganic pigments, UV inhibitors, antistatic agents, dispersants, neutralizing agents, foaming agents, plasticizers, copper damage inhibitors, flame retardants, crosslinkers, flowability Improvers and the like can be mentioned.

Next, the melt-kneading, the molding method, the physical properties of the molded article, the use and the like in the present invention will be described.

(Melting, Kneading and Molding) In the present invention, the above-mentioned components A to D and the above-mentioned additional components added as required are heated and kneaded, then molded and solidified into a desired shape to obtain a molded member. However, it is particularly preferable that these components are once formed into a pellet shape by heating and kneading as a molded member, and the pellet is further melt-molded to form a molded member of another shape.

In such a melt-kneading step, in the present invention, the following conditions are set in order to obtain good effects by the action of a Ti-based compound as a polymerization catalyst and a chelator such as a P-based compound. Is important.

That is, the reactivity when the Ti-based compound acts as a catalyst has the following characteristics.

At low temperatures (from the melting point of the thermoplastic crystalline ester-based resin to about +40 deg), the copolymerization, high molecular weight, and depolymerization are competitive reactions. Although quantification is difficult, copolymerization and high molecular weight tend to be dominant in low temperature and short time (about 1 to 5 minutes), and for a long time (about 5 to 1).
(0 minutes or more), the depolymerization often predominates.

Under conditions of high temperature (the melting point of the thermoplastic crystalline ester resin is about +40 deg to +80 deg), depolymerization often becomes dominant (regardless of the length of time).

For this reason, it is necessary to perform heat kneading and melt molding at a relatively low temperature. However, if the time is too short, the copolymerization and the increase in the molecular weight do not proceed, and high physical properties are not exhibited.
On the other hand, if the time is too long, the depolymerization becomes dominant and deteriorates. Therefore, it is necessary to select the processing conditions while determining the optimum residence time.

On the other hand, when, for example, a P-based compound is blended as a chelator, the generated Ti—P complex is
The reaction rate of copolymerization and high molecular weight is slow because the activity is slow, but compared to the original Ti-based compound,
It shows the following reactivity.

At low temperatures (from the melting point of the thermoplastic crystalline ester resin to about +40 deg), the copolymerization, the increase in the molecular weight, and the depolymerization have low reactivity, so that it does not easily proceed.

At a high temperature (the melting point of the thermoplastic crystalline ester-based resin + about 40 deg. To +80 deg.), In a short time (about 1 to 5 minutes), the reaction of copolymerization and high molecular weight takes precedence, and (5 minutes or more), copolymerization, increase in molecular weight, and depolymerization are often antagonized or the depolymerization reaction has priority.

Accordingly, in the present invention, as an example of a suitable processing means, when each component is heated and kneaded to form a pellet, the molten state is changed to a high temperature for a short time (for example, the melting point of the thermoplastic crystalline ester resin at the resin temperature). +40 to +80 deg,
It is preferably adjusted to about +60 deg; residence time in a molten state of 0.5 to 5 minutes, preferably about 1 minute), and a reaction of copolymerization and high molecular weight is performed at the stage of heating and kneading. There is no particular limitation on the means of this heating and kneading, and any known technique can be used. A twin screw extruder can be particularly preferably used.

Next, the pellet is melt-molded at a low temperature (the melting point of the thermoplastic crystalline ester-based resin +0 to +40 deg, preferably about +30 deg) to obtain a molded member.
Even when a molded member is obtained in this manner, a known technique can be used, and for example, an injection molding machine, an extrusion molding machine, or the like can be used. At such a low temperature, the Ti-P complex hardly promotes the depolymerization, so that the depolymerization does not proceed even if the molding conditions (residence time and the like) slightly vary. Further, since the copolymerization and the increase in the molecular weight have already been almost completed, high physical properties can be exhibited even if the residence time is short.

This technique utilizes the characteristic of the reactivity of the Ti-P complex as a catalyst to promote the copolymerization and high molecular weight reaction during pelletization by heating and kneading, and to co-produce the pellet in melt molding. It is important to suppress the reactions of polymerization, high molecular weight, and depolymerization.

The Ti—P complex is 0.5 to 60 ° C. to 150 ° C.
If the mixture is heated for about 10 to 10 hours, the catalytic activity temporarily increases. Therefore, before heating and kneading, the kneading raw material containing only the Ti compound or the Ti compound is preliminarily prepared at 60 to 150 ° C for about 0.5 to 10 hours. It is also effective to increase the reaction rate of copolymerization and high molecular weight by heating to a low temperature. It is not clear why the catalytic activity is increased by prior heating, but in a normal state, the catalytic activity of a Ti-based compound is reduced by taking in water in the air as water of crystallization. It is considered that the catalytic activity is increased by removing water.

(Chemical Bond between Thermoplastic Crystalline Ester Resin and Thermoplastic Amorphous Ester Resin) In the present invention, the molecular chains of the thermoplastic crystalline ester resin and the thermoplastic amorphous ester resin are combined. By forming a chemical bond between the molecular chains, the affinity between the two resins is improved, the fine dispersion of the form is promoted, and the high bending resistance of the thermoplastic crystalline ester resin and the thermoplastic amorphous ester resin A molded member having both dimensional stability and (depending on conditions, further transparency) can be obtained.

The proportion of the chemical bond is not particularly limited, but is preferably basically large. Specifically, the molecular chain of the thermoplastic crystalline ester resin and the molecule of the thermoplastic amorphous ester resin are The total mass of the thermoplastic crystalline ester-based resin and the thermoplastic amorphous ester-based resin per mole of the chemical bond between the chains (hereinafter, this mass is referred to as “mass to chemical bond”) is 1, It is preferably not more than 100,000 g, more preferably not more than 300,000 g, particularly preferably not more than 100,000 g.

The method of measuring the amount of the chemical bond is not particularly limited, but can be measured, for example, by NMR.

PB as a thermoplastic crystalline ester resin
T, the measurement example when PC is used as the thermoplastic amorphous ester resin is shown below. Measurement model JEOLSXSX400 Solvent 1,1,1,2,2,2-hexafluoroisopropanol / d-chloroform = 3/7 (volume ratio) Number of integration 128 times Standard TMS

As a result of the measurement, the charts shown in FIGS. 1 and 2 were obtained. FIG. 2 is an enlarged view of a portion II in FIG.

The benzene ring hydrogen of terephthalic acid (TPA) has a different chemical shift between the case where the carboxylic acid is bonded to butanediol and the case of bisphenol A (BPA). Therefore, the bond between TPA and PBT-PC in the PBT molecular chain is different. It is possible to obtain the quantitative ratio with the TPA.

(Dispersion Form of Thermoplastic Crystalline Ester Resin and Thermoplastic Amorphous Ester Resin) In general, even if two kinds of thermoplastic resins are melt-mixed, they are not completely mixed and may have a sea-island structure. Are known. If there is a large difference in the volume fraction of both thermoplastic resins, the larger the volume fraction is at sea, the smaller the volume fraction is, the easier it is to take an island structure, and if the difference is small, the melt viscosity difference It affects the sea-island structure, and it is said that the smaller the melt viscosity is, the easier it is to become the sea and the larger the melt viscosity is, the more it is likely to be an island.

In general melt mixing, the dispersion particle size is 100 n.
However, in the present invention, the dispersion particle size can be reduced to several nm or less by optimizing the conditions, whereby the molded member can be practically made transparent. Generally, a molded member containing a thermoplastic crystalline ester-based resin such as PBT is known to have no transparency, but a transparent molded member can be obtained by using the method according to the present invention.

There is no particular limitation on the method of checking the dispersion state.
After staining with uO ₄ , a known method such as preparation of an ultrathin section and observation with a TEM can be used.

(Uses of the Molded Member of the Present Invention) The use of the molded member of the present invention is not particularly limited. Components and functional members of OA equipment, exterior parts and interior parts of automobiles, constituent parts of home appliances, general-purpose films It can be widely used as such.

Among them, it can be suitably used in the field of OA equipment which has strict physical properties such as dimensional accuracy, bending resistance and tensile elongation at break, especially for functional members. For example, as an endless belt shape, an electrophotographic copying machine, a laser beam When used as an intermediate transfer belt, a transfer belt, a photoreceptor belt, or the like in an image forming apparatus such as a printer or a facsimile machine, it is preferable because there are few problems such as cracks and elongation.

Hereinafter, an endless belt as an example of a preferred use example of the molded member of the present invention will be described.

(Endless Belt) In order to obtain the endless belt of the present invention, the above-mentioned components A to D and other additional components blended as required are mixed by, for example, a twin-screw kneading extruder and pelletized. A method of forming an endless belt later is particularly preferably used.

The molding method is not particularly limited, and can be obtained by employing a known method such as a continuous melt extrusion molding method, an injection molding method, a blow molding method, or an inflation molding method, and is particularly desirable. This is a continuous melt extrusion molding method. In particular, an internal cooling mandrel method or a vacuum sizing method of a downward extrusion method capable of controlling the inner diameter of the extruded tube with high precision is preferable, and an internal cooling mandrel method is most preferable.

In addition, since the endless belt having better physical properties can be obtained by optimizing the temperature and the residence time during the molding, it is preferable to adjust the conditions in accordance with each composition.

(Physical Properties of Endless Belt) According to the present invention, an endless belt having the following physical properties can be obtained.

When the endless belt of the present invention is used in an image forming apparatus, for example, as an intermediate transfer belt, if the bending resistance is poor, cracks occur and an image cannot be obtained. Endless belts are preferred.

The degree of bending resistance is determined according to JIS P-8115.
Can be quantitatively evaluated by following the method for measuring the folding endurance of
It can be determined that an endless belt having a larger number of fold-resistant times is less likely to be cracked and has excellent bending resistance.

As a specific numerical value, if it is 500 times or more, it can be used while exhibiting a function as an endless belt, but practically, it is preferably 5,000 times or more, and if it is 10,000 times or more, it is further used. Preferably 300
When the number of times is at least 00, cracks are particularly difficult to occur, so that it is particularly preferable.

Tensile elasticity If the tensile elasticity of the endless belt is low, for example, when it is used in an image forming apparatus as an intermediate transfer belt, a slight elongation occurs due to tension, which may cause a problem such as color misregistration. Higher tensile modulus is more preferable, and specifically, 1000 MPa or more is preferable, and 1500 MPa
It is more preferably at least 2000 MPa, more preferably at least 2,000 MPa, and particularly preferably at least 2,500 MPa, since defects such as color misregistration can be greatly suppressed.

In general, a soft plastic has a high number of folds, but tends to have a low tensile elasticity. On the contrary, a hard plastic can obtain a high tensile elasticity, but is brittle, and often has only a low number of folds. . In the present invention, it can be said that the present invention is useful in the sense that a high folding endurance can be obtained while maintaining the characteristic of a high tensile elastic modulus inherent to PBT or PC.

Surface Resistivity The endless belt according to the present invention can be provided with conductivity by blending a conductive filler or a substance exhibiting conductivity with the resin composition, if necessary. In this case, the resistance region of the endless belt varies depending on the purpose, but is preferably selected from the range of surface resistivity of 1 to 1 × 10 ¹⁶ Ω.

The more preferable range of the surface resistivity varies depending on the application. For example, when used as a photoreceptor belt, the surface resistivity is adjusted so that electric charges on the outer surface can escape to the inner surface as needed.
Surface resistivity as low as 1 × 10 ⁶ Ω, preferably 1 × 10 ⁶ to 1 × 10 ¹¹ Ω, which facilitates charging and transfer when used as an intermediate transfer belt, and A high region of 1 × 10 ¹⁰ to 1 × 10 ¹⁶ Ω, which is easily charged and hardly damaged even at a high voltage, is preferable.

The distribution of the surface resistivity in one endless belt is preferably narrow. In each of the preferable surface resistivity regions, the maximum value in one belt is the minimum value of 100.
It is preferably within a factor of 10, more preferably within a factor of 10.

The surface resistivity of the endless belt can be easily measured by, for example, Hiresta and Loresta manufactured by Dia Instruments Co., Ltd. and R8340A manufactured by Advantest Co., Ltd.

The thickness of the endless belt is preferably 50 to 1000 μm, more preferably 80 to 500 μm, and more preferably 100 to 200 μm.
It is particularly preferable if it is μm.

(Use of Endless Belt) The use of such an endless belt is not particularly limited. However, an intermediate transfer belt, a conveyance transfer belt, and an image forming apparatus such as an electrophotographic copying machine, a laser beam printer, and a facsimile machine are used.
When used as a photoreceptor belt or the like, there are few problems such as cracks and elongation, and it can be used stably for a long period of time.

[0107]

The present invention will be described more specifically with reference to the following examples and comparative examples.

In the following Examples and Comparative Examples, films were produced with the following raw materials and molding conditions, and the evaluations were made. The results are shown in Table 1.

(Raw Materials) The following raw materials were used, and the mixing ratio was as shown in Table 1. Component A: PBT (weight-average molecular weight 40,000; weight-average molecular weight in terms of PS 122,000) Component B: PC (weight-average molecular weight 28,000; weight-average molecular weight in terms of PS 64,000) Component C: Ti-based compound (titanium) (IV) Butoxide) Component D: P-based compound (Sandstub P-EPQ (PEP
Q): Tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylylenediphosphonite (structural formula is as follows; Clariant Japan K.K.) or hydrazines (IRGANOX MD1024; Nippon Ciba Geigy) Co., Ltd.)

[0110]

Embedded image

The MFR (260 ° C. 2.16 kg) of the component A and the component B measured by the above-mentioned method was 7 g / 10 min for the component A and 3 g / 10 min for the component B.
And the MFR ratio of both resins is 2.33 / 1.

(Heat Kneading) The resin composition was pelletized for each raw material using a twin-screw kneading extruder (PMT32 manufactured by IKG). The kneading conditions were set at a set temperature of the kneader of 240.
° C, screw rotation speed 100 rpm, discharge speed 15
g / h. The residence time in the molten state in the kneader under these conditions is about 1 minute on average.

(T-die film molding) An evaluation film was molded from the above resin composition pellets using a T-die film molding machine having a diameter of 20 mm. Before molding, the resin composition pellets were dried at 130 ° C. for 8 hours and used for molding. In addition, in order to evaluate the residence time dependency of the physical properties of the molded film, the residence time was adjusted, and molding was performed under the following two conditions.

Condition A: residence time 6 minutes, film thickness 1
Molding by adjusting the thickness range to be ± 15 μm with the target of 50 μm. Condition B: Molding by adjusting the thickness range to be ± 15 μm with the target of the residence time of 15 minutes and the film thickness of 150 μm.

Under the condition B, molding was performed by slowing the rotation of the screw so that the residence time was longer than that under the condition A, and the take-off speed was adjusted so that the film thickness was the same as that under the condition A.

(Evaluation) Appearance and Form The film appearance was examined by visual observation. The form is R
Inspection was carried out by staining with uO ₄ and visually observing with a TEM. The dispersed particle size was measured by measuring 100 island portions in the TEM image and expressed as a median value.

-Folding resistance JIS P-8115 compliant Each sample was measured three times, and the average value (two significant figures)
Was used as a representative value. The number of times of folding is an index of the bending fatigue resistance of the film, and a larger number means that the film is harder to crack and stronger.

Example 1 A Ti-based compound was blended with the components shown in Table 1, and
0.6 parts by weight of P-based compound PEPQ was blended as a chelator to obtain a resin composition pellet. However, all the raw materials were kept at 80 ° C. for 6 hours before kneading, and the kneading was performed after adjusting the reactivity of the Ti-based compound.

When this pellet was formed into a T-die film under the condition A, it was possible to obtain a very transparent and extremely high folding endurance number of 32,000 times, although the film was slightly turbid. Further, even when a T-die film was formed under the condition B, a transparent and very good good film having a folding endurance of 34,000 times could be obtained.

From the results, it can be seen that the obtained molded member has high physical properties, and that physical property differences due to molding conditions hardly appear, so that it is thermally stable and easy to handle. The development of the high physical properties is due to the effect of the Ti-based compound serving as a catalyst for copolymerization and high molecular weight. The relaxation of the molding condition caused the P-based compound to coordinate with the Ti-based compound and increase the reaction regularity of the catalyst. It is considered to be an effect.

The mass of the obtained resin with respect to chemical bond was measured by the above-mentioned method, and as a result, it was 120,000 g / mol.

Example 2 With the components shown in Table 1, PEPQ as a chelator was further added to 1 part by weight in excess of Example 1 to obtain resin composition pellets. However, all raw materials before kneading should be 8
The mixture was kept at 0 ° C. for 6 hours to adjust the reactivity of the Ti compound, and then used for kneading.

When this pellet was formed into a T-die film under the condition A, it was possible to obtain a transparent and excellent film having an extremely high folding endurance of 44,000 times. In addition, even when the T-die film was formed under the condition B, a transparent and very good film having a folding endurance of 46,000 times could be obtained.

From the results, it can be seen that, as in Example 1, the obtained molded member has high physical properties, and since there is little difference in physical properties depending on the molding conditions, it is thermally stable and easy to handle. The development of the high physical properties is due to the effect of the Ti-based compound serving as a catalyst for copolymerization and high molecular weight. The relaxation of the molding condition caused the P-based compound to coordinate with the Ti-based compound and increase the reaction regularity of the catalyst. It is considered to be an effect.

The mass of the obtained resin with respect to the chemical bond was measured by the method described above, and was found to be 100,000 g / mol.

Example 3 In the composition shown in Table 1, 1 part by weight of hydrazine IRGANOX MD1024 (manufactured by Nippon Ciba Geigy Co., Ltd.) was blended in place of PEPQ as a chelator in the same manner as in Example 2, and a resin composition pellet was prepared. Obtained. However, all the raw materials before kneading were kept at 80 ° C. for 6 hours, and the kneading was performed after adjusting the reactivity of the Ti-based compound.

When this pellet was formed into a T-die film under the condition A, a transparent and excellent film having an extremely high folding endurance of 20,000 could be obtained. In addition, even when a T-die film was formed under the condition B, a transparent and very good film having a folding endurance of 24,000 times could be obtained.

From the results, it can be seen that the obtained molded member has high physical properties and hardly shows a difference in physical properties depending on the molding conditions as in Example 1, so that it is thermally stable and easy to handle. The development of high physical properties is due to the effect of the Ti-based compound, which is a catalyst for copolymerization and high molecular weight, and the relaxation of molding condition dependence is the effect of hydrazines coordinating to the Ti-based compound and increasing the reaction regularity of the catalyst. It is considered to be.

The mass of the obtained resin with respect to chemical bond was measured by the above-mentioned method, and as a result, it was 110,000 g / mol.

Comparative Example 1 A resin composition pellet was obtained by heating and kneading the components shown in Table 1 without mixing the Ti compound and the chelator. In Comparative Example 1, since no Ti-based compound was present, depolymerization of a side reaction did not proceed, and it is considered that the compound was thermally stable.

When the obtained resin composition pellets were formed into a T-die film under condition A, an opaque film was obtained. When the number of folding times of this film was measured, it was 320
Zero values were obtained. Further, the film formed by the T-die under the condition B had some foaming flaws on the surface, but had almost the same physical properties as the condition A product. The reason why some foaming occurred in condition B is
It is considered that general thermal deterioration partially occurred under the condition where the residence time was long because the heat stabilizer was not added.

Comparative Example 2 Based on the composition of Comparative Example 1, PEPQ was used as a chelator.
Was mixed with 1 part by weight of the components shown in Table 1 to obtain a resin composition pellet.

When the obtained resin composition pellets were formed into a T-die film under the condition A, an opaque film was obtained. When the folding number of this film was measured, it was 480.
A value of 0 was obtained. Further, the film formed by the T-die under the condition B had almost the same physical properties as the product of the condition A.

From these results, it can be seen that the physical properties are almost the same as those of Comparative Example 1 even if PEPQ is added in a large excess.

Comparative Example 3 Based on the composition of Comparative Example 1, only the Ti compound was blended, and the mixture was heated and kneaded with the components shown in Table 1 without a chelator to obtain resin composition pellets.

When the obtained resin composition pellets were formed into a T-die film under the condition A, they were transparent and had a folding endurance of 42.
A very high good film of 000 times could be obtained. This is presumably because the Ti-based compound acted as a catalyst due to the thermal history of the resin under the T-die molding conditions A, and the copolymerization and high molecular weight progressed.

Next, the same pellet was formed by T-die molding under the condition B. However, since the resin coming out of the die outlet foamed and the viscosity was extremely reduced, it was drawn down, and it was necessary to secure the film shape. Could not. This is because the Ti-based compound also acts as a catalyst for the depolymerization reaction, and their copolymerization, high molecular weight, and depolymerization reaction compete with each other, but as the residence time becomes longer, this depolymerization becomes dominant. It is considered that the molecular weight was rapidly decreased, and the physical properties were decreased.

Comparative Example 4 is excellent in that a film having high physical properties can be obtained if the conditions are selected. However, the molding conditions are limited, and if the conditions are not satisfied, the physical properties are extremely deteriorated. It has problems that are difficult to handle.

[0139]

[Table 1]

[0140]

As is clear from the above Examples and Comparative Examples, according to the present invention, it is excellent in bending resistance, chemical resistance, and molding dimensional stability, has low physical property dependence on molding conditions, and is thermally resistant. A molded member that is stable and has excellent handling properties and molding workability is provided.

[Brief description of the drawings]

FIG. 1 is an NMR chart of a mixed reaction product of PBT and PC.

FIG. 2 is an enlarged view of a portion II in FIG.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 67/03 C08L 67/03 69/00 69/00 (72) Inventor Makoto Morikoshi Toho, Yokkaichi City, Mie Prefecture No. 1 in Mitsubishi Chemical Corporation (72) Inventor Norihiro Otsu 1 in Tohocho, Yokkaichi-shi, Mie F-term in Mitsubishi Chemical Corporation (reference) 4F071 AA44 AA48 AA50 AA81 AB25 AC05 AC15 AE22 AF26 AF30 AH07 AH16 BB06 BC01 BC07 4J002 BG06X CF06W CF07W CF08W CF16X CG04X DH037 DH047 EC076 EW047 EW067 EW087 FD207 GN00 GQ00

Claims (4)

[Claims] 1. A component A; a thermoplastic crystalline ester resin; a component B; a thermoplastic amorphous ester resin; a component C; a Ti compound and a component D; a chelator; 1/99 to 99/1, weight ratio of Ti element to total of components A to D is 1 to 1
A molded member obtained by heating and kneading at a mixing ratio of 0000 ppm and then molding. 2. The molded member according to claim 1, wherein the chelator is a P-based compound. 3. The method according to claim 2, wherein the Ti compound is an alkyl titanate, and the P compound is a phosphoric acid, a phosphate, a phosphate, a phosphorous acid, a phosphite, and a phosphite. A molded member, which is one or more selected from the group consisting of: 4. The method according to claim 1, wherein said thermoplastic crystalline ester resin is polyalkylene terephthalate, and said thermoplastic amorphous ester resin is polycarbonate or polyarylate. Characterized molded member.