JP5509686B2 - Molded body of thermoplastic resin composition containing deformed crosslinked dispersed phase - Google Patents

Description

  The present invention relates to a molded thermoplastic resin composition containing a deformed crosslinked dispersed phase, and the crosslinked thermoplastic resin that has been previously crosslinked to a certain degree of crosslinking is made into a thermoplastic resin finely down to the micron order in the melt kneading process. The present invention relates to a molded article obtained by stretching and molding a dispersed and structured crosslinked dispersed phase-containing thermoplastic resin composition.

  The usefulness of a molded product containing a deformed dispersed phase is known for improving the surface impact by a surface-dispersed rubber in a film molded product and improving the barrier property by a surface-dispersed barrier component in a stretched film or blow-molded product. However, in addition to the uniformity and stability of the dispersed structure being a major issue, the resin composition containing the dispersed phase is controlled to have rheological properties advantageous for melt processing, and the deformation of the dispersed phase relative to the deformation of the matrix in the dispersed phase It is very difficult to give following ability. For this reason, it is an advanced technology to adjust a thermoplastic resin molded body having excellent moldability, a stable and uniform dispersed phase structure, and containing a dispersed phase having a high degree of deformation following deformation during molding. is necessary. A thermoplastic elastomer containing a crosslinked resin or a crosslinked rubber component as a crosslinked dispersed phase by a dynamic vulcanization method has been extensively researched and developed by Monsanto, and is marketed under the trademark “Santoprene”.

  In Patent Document 1 and Non-Patent Document 1, a thermoplastic elastomer obtained by a dynamic vulcanization method is prepared by blending a rubber component such as EPDM and a rubber cross-linking agent into polypropylene (PP) and melt-kneading with high shear. It discloses a dynamic cross-linking in which the EPDM rubber is dispersed in the PP resin while causing the vulcanization (cross-linking) of the EPDM rubber. In this case, melt kneading is carried out with a composition having more EPDM rubber components than PP components, and at the same time, crosslinking of EPDM rubber is caused in the kneading process and at the same time phase inversion of PP and EPDM rubber components is performed in order to use PP as a matrix. Manufacturing technology is required. The dispersed dispersion particles of the thermoplastic elastomer obtained here are particulate dispersions with a high degree of cross-linking, and because of the high degree of cross-linking, strain hardening is not manifested in the non-linear region in the melt elongational viscosity, improving moldability. Further improvement is necessary to achieve this.

Patent Document 2 discloses a thermoplastic elastomer film in which a crosslinked elastomer component is oriented in a disk shape in a film surface direction. In this case, it contains cross-linked dispersed particles by the dynamic cross-linking method, but since the cross-linking can be controlled only in the region where the cross-linking degree of the dispersed particles is high, there is no expression of strain hardening in the nonlinear region in the melt elongation viscosity. It is necessary to improve the property, and the deformation followability of the crosslinked particles by stretching is low.
Patent Document 3 discloses that a film is formed using a resin composition obtained by melt-kneading a radiation-crosslinked polycaprolactone and an aliphatic polyester. However, the specifically disclosed crosslinked polycaprolactone has a high radiation dose and molecular degradation and promotes biodegradability, and there is no description regarding the dispersibility and dispersion structure of the crosslinked polycaprolactone. There is no description about the improvement of the specific rheological properties of the resin composition by the dispersion of the crosslinked polycaprolactone.
In Patent Document 4, a pre-dispersion composed of a matrix component that can be easily removed after molding and a dispersion component of a thermoplastic resin is melt-compressed or stretch-molded to form a molded product obtained by deforming thermoplastic resin-dispersed particles. Have been described. However, the objective is to produce deformed resin-dispersed particles by dissolving and removing the matrix components of the molded product, and using the stretched molded product of the preliminary dispersion as it is, the stretched molded product exhibits the characteristics of the deformed resin-dispersed particles. It is not a thing.

JP 59-58043 A JP 2006-315339 A JP 2000-256471 A JP 2007-262334 A

Rubber chemistry and Technology, 1996, Volume 69, p.476

  The present invention is intended to solve the above-mentioned problems, and provides a thermoplastic resin-based molded article containing a crosslinked dispersed phase deformed into a state advantageous for imparting functionality in a wide range of combinations of thermoplastic resins. It is.

As a result of extensive research, the present inventors have obtained a thermoplastic resin composition in which a cross-linked thermoplastic resin that has been previously cross-linked to a specific degree of cross-linking is refined to a micron order by melt-kneading into a thermoplastic resin and has a dispersed structure. The present inventors have found that a method for stretching a thermoplastic resin composition molded body containing a crosslinked dispersed phase highly deformed in the stretching direction can be obtained.

That is, the present invention
(1) A cross-linked thermoplastic resin composition (A ′) having the following characteristics (a) obtained by cross-linking the non-crosslinked thermoplastic resin (A) and a non-crosslinked thermoplastic resin (B) are melt-kneaded. The thermoplastic resin composition obtained above forms a dispersed phase in which (A ′) is dispersed in a particle size of at most 20 μm in (B) or (A ′) and (B) Forming a cross-linked structure having a co-continuous structure interlaced with each other (hereinafter, the dispersed phase and the crosslinked phase are collectively referred to as a crosslinked dispersed phase) , and in a non-linear region in the melt uniaxial elongation viscosity, It is a thermoplastic resin composition having strain-hardening properties, and is a molded body obtained by melt-stretching the thermoplastic resin composition, and the crosslinked dispersed phase in the molded body is used for stretching during molding. Including a deformed crosslinked dispersed phase characterized by being deformed in the stretching direction. A molded thermoplastic resin composition.
(A) A solvent gel is formed with the solvent without dissolving in the solvent of the non-crosslinked thermoplastic resin (A).
(B) The following strain hardening coefficient in a log-log plot curve of time-uniaxial extension viscosity obtained by measuring the melt uniaxial extension viscosity of the thermoplastic resin at a temperature of at least 10 ° C. higher than the melting point of the non-crosslinked thermoplastic resin (B) Is 2 or more.
Strain hardening coefficient = a2 / a1
a1: slope of linear region in log-log plot curve of time-uniaxial extensional viscosity
a2: Slope of nonlinear region in log-log plot curve of time-uniaxial extensional viscosity

(2) The cross-linked thermoplastic resin composition (A ′) has a frequency in the frequency range of 0.1 to 10 rad / s in a logarithmic plot curve of frequency-storage elastic modulus obtained by melt viscoelasticity measurement in the linear region. The thermoplastic resin composition molded article containing the deformed crosslinked dispersed phase according to the above (1), which is in a crosslinked state in which the slope of the storage elastic modulus with respect to is 0.2 to 1.0.
(3) The cross-linked thermoplastic resin composition (A ′) has a storage elastic modulus in a frequency-storage elastic log-log plot curve in a frequency range of 0.1 to 10 rad / s in melt viscoelasticity measurement in the linear region. (1) or (2), wherein the absolute value of the difference between α and β is 0.15 or less, where α is the slope and β is the slope of the loss modulus in the logarithmic plot curve of the frequency-loss modulus. A molded product of a thermoplastic resin composition containing a deformed crosslinked dispersed phase.
(4) The thermoplastic resin composition containing the deformed crosslinked dispersed phase according to any one of (1) to (3), wherein the crosslinked thermoplastic resin composition (A ′) is irradiated with radiation. Molded body.
(5) The crosslinked thermoplastic resin composition (A ′) is crosslinked by irradiating a pellet obtained by melt-kneading a non-crosslinked thermoplastic resin and a crosslinking aid (1) to (1) to (4) A thermoplastic resin composition molded article containing the deformed crosslinked dispersed phase according to any one of (4).
(6) The crosslinked thermoplastic resin composition (A ′) is obtained by blending a crosslinking aid and / or an organic peroxide with the non-crosslinked thermoplastic resin (A) and crosslinking by melt kneading. A thermoplastic resin composition molded article containing the deformed crosslinked dispersed phase according to any one of (1) to (5).
(7) The crosslinked thermoplastic resin composition (A ′) according to any one of (1) to (6), wherein at least 50% by weight is any one of a polyamide resin, a polyester resin, and a polyolefin resin. A molded thermoplastic resin composition containing a deformed crosslinked dispersed phase.
(8) crosslinked thermoplastic resin composition (A ') is obtained by melt kneading a resin composition containing a port re-caprolactone 50 to 99.9 parts by weight and the crosslinking aid 0.1-3 parts by weight pellets A thermoplastic resin composition molded article containing the deformed crosslinked dispersed phase according to any one of (1) to (7), wherein the composition is irradiated with an absorbed dose of 0.5 to 25 kGy.
(9) crosslinked thermoplastic resin composition (A ') is, pellets of the resin composition obtained by melt kneading including port re ester elastomer 50 to 99.9 parts by weight and the crosslinking aid 0.1-3 parts by weight The thermoplastic resin composition molded article containing the deformed crosslinked dispersed phase according to any one of (1) to ( 7 ), which is irradiated with an absorbed dose of 0.5 to 60 kGy.
(10) crosslinked thermoplastic resin composition (A ') is the absorption pellets of the resin composition obtained by melt kneading including polyamides 50 to 99.9 parts by weight and the crosslinking aid 0.1-3 parts by weight The thermoplastic resin composition molded article containing the deformed crosslinked dispersed phase according to any one of (1) to ( 7 ), which is irradiated with a dose of 0.5 to 20 kGy.

The crosslinked dispersed phase-containing thermoplastic resin composition used in the present invention has a high degree of strain-hardening property, so that it is not only excellent in moldability such as extrusion molding, blow molding, foam molding, film molding, Since the cross-linked dispersed phase is adjusted to a specific cross-linked state, the degree of deformation following the stretching direction in deformation during melting is very high, and includes a cross-linked dispersed phase that is easily deformed by stretching during molding. It becomes a thermoplastic resin molding. For this reason, the molded article of the present invention can contain a highly deformed dispersed phase without passing through a complicated molding machine or molding process in a combination of various resins and resin compositions. Therefore, it is possible to develop functionalities such as barrier properties, optical properties, impact resistance, and heat resistance.

FIG. 1 is a diagram (photograph) showing an SEM image of the thermoplastic resin compositions of Example 1 and Comparative Example 1 before stretching. FIG. 2 is a diagram (photograph) showing a phase contrast microscopic image of a stretched cross-section sample (b) obtained in Example 5 and a cross-section perpendicular to the stretch direction (b). FIG. 3 is a view (photograph) showing an SPM image of the thermoplastic resin composition of Comparative Example 7 before stretching. FIG. 4 is a diagram (photograph) showing a differential interference microscope image before stretching of the thermoplastic resin composition of Example 2, and a diagram (photograph) showing a differential interference microscope image and a TEM image after stretching. FIG. 5: is a figure (photograph) which shows the TEM observation image of the film-form molded article which melt-stretched and adjusted to the uniaxial direction about the thermoplastic resin composition of Example 1 and Example 6. FIG. FIG. 6 shows the frequency-storage elastic modulus and loss elasticity at 190 ° C. of the crosslinked thermoplastic resin B-1 prepared as the crosslinked thermoplastic resin composition (A ′) in the present invention and PCL before being crosslinked. It is a figure which shows the log-log plot curve about a rate and melt viscosity.

The present invention will be specifically described below. The thermoplastic resin composition of the present invention can be obtained by forming a finely dispersed structure of the crosslinked thermoplastic resin composition (A ′) and the non-crosslinked thermoplastic resin (B) or (A) by melt-kneading. The crosslinked thermoplastic resin composition (A ′) is a modified thermoplastic resin (composition) crosslinked by introducing a bridge structure into the molecular chain of the non-crosslinked thermoplastic resin (A). It has a specific degree of cross-linking that makes it insoluble in the solvent of (A).
Specific resins corresponding to the non-crosslinked thermoplastic resins (A) and (B) include polyethylene (PE), polypropylene (PP), polymethylpentene (TPX), ethylene-propylene copolymer (EPM), Ethylene-propylene-diene copolymer (EPDM), ethylene-methyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-acrylic acid copolymer (EAA), ethylene-vinyl acetate Olefin resins such as copolymer (EVA). Biodegradable and cross-linked polyester resins such as polycaprolactone (PCL), polybutylene succinate (PBS), polybutylene succinate / adipate (PBSA). Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polycarbonate (PC), polyacrylate (PAR), polybutylene terephthalate / polytetramethylene glycol block copolymer And polyester resins such as polybutylene terephthalate / polylactone block copolymers, polybutylene naphthalate / polylactone block copolymers, and polybutylene terephthalate / polymer prolactone copolymers. Nylon 6 (NY6), nylon 66 (NY66), nylon 46 (NY46), nylon 11 (NY11), nylon 12 (NY12), nylon 610 (NY610), nylon 612 (NY612), metaxylylene adipamide (MXD6) ), Hexamethylenediamine-terephthalic acid polymer (6T), hexamethylenediamine-terephthalic acid and adipic acid polymer (66T), hexamethylenediamine-terephthalic acid and ε-caprolactam copolymer (6T / 6), trimethylhexa Methylenediamine-terephthalic acid (TMD-T), metaxylylenediamine and adipic acid and isophthalic acid polymer (MXD-6 / I), trihexamethylenediamine, terephthalic acid and ε-caprolactam copolymer (TMD-T / 6) Diamino Examples include dicyclohexylenemethane (CA) and polyamide resins such as isophthalic acid and lauryl lactam polymers, but are not limited to these, and are not limited to the above. This includes polymers and polymer alloy compounds.

  In order to obtain the thermoplastic resin composition in the present invention, it is important to appropriately control the degree of cross-linking of the cross-linked thermoplastic resin composition (A ′), and this specific cross-linking degree can be adjusted. However, it enables the realization of the present invention and easy application to various resins. Hereinafter, preferred forms of the crosslinked thermoplastic resin composition (A ′) in the present invention will be described.

The crosslinked thermoplastic resin composition (A ′) in the present invention must be crosslinked at least until it is insolubilized in the solvent of the non-crosslinked thermoplastic resin (A). Although it is preferable to adjust beforehand by the bridge | crosslinking in the melt kneading of use, etc., it is not limited to these. Among cross-linking methods that introduce a cross-linked structure into the molecular chain, cross-linking by radiation irradiation in particular can control the cross-linking degree of the cross-linked thermoplastic resin composition (A ′) in a state where the cross-linking density is uniform and the cross-linking density is not excessively increased. This is particularly preferable because it can be easily performed.

The solvent for the non-crosslinked thermoplastic resin is a solvent capable of dissolving the thermoplastic resin before crosslinking, and a solvent suitable for each thermoplastic resin may be selected. For example, nylon includes formic acid, sulfuric acid, etc., but formic acid is preferred. For polyester, a mixed solvent of phenol and tetrachloroethane, dichlorobenzene and the like can be mentioned, and a mixed solvent of phenol and tetrachloroethane is preferable.

  Crosslinking by radiation irradiation can cause intermolecular crosslinking by irradiating with electron beam or gamma ray (γ ray). The wavelength differs depending on the type of radiation, and gamma rays having a wavelength shorter than that of the electron beam can be cross-linked to the inside of the thick thermoplastic resin. The total amount of absorbed energy (absorbed dose) is expressed in gray (Gy). Radiation irradiation is particularly preferable for crosslinking of the crosslinked thermoplastic resin composition (A ′) of the present invention because the absorbed dose can be freely controlled and the degree of crosslinking of the thermoplastic resin can be controlled. Since the cross-linking by radiation irradiation to pellets and the like may not provide a uniform degree of cross-linking unless the transmitted dose is made uniform between the upper and lower portions to be irradiated, especially when pellets are cross-linked with radiation, the wavelength is short. Since a uniform degree of crosslinking can be obtained by crosslinking with gamma rays, the present invention is the optimum crosslinking method. The absorbed dose of radiation irradiation in the present invention is preferably 0.5 to 50 kGy. If it is less than 0.5 kGy, it becomes difficult to control the absorbed dose, and if it exceeds 50 kGy, the crosslinking proceeds too much, and depending on the type of polymer, the progress of molecular cutting proceeds so much that the crosslinked part and the non-crosslinked part are extremely uneven. You can only get things. Crosslinked thermoplastic resins with non-uniform cross-linked parts and non-crosslinked parts have a high apparent gelling ratio, but dispersibility in non-crosslinked thermoplastic resins may deteriorate, or may be dispersed in non-crosslinked thermoplastic resins. However, there may be a case where a crosslinked dispersed phase thermoplastic resin having sufficient strain hardening property cannot be obtained.

In adjusting the degree of crosslinking of the crosslinked thermoplastic resin composition (A ′) by irradiation, the crosslinking thermoplastic resin (A ′) is crosslinked by kneading a crosslinking aid in advance into the thermoplastic resin (A) to be crosslinked. Processing efficiency can be promoted. Specific crosslinking aids include triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethylallyl isocyanurate (TMPTA), trimethylolpropane trimethacrylate (TMPTA), trishydroxyethyl isocyanuric acrylate ( THEICA) and N, N′-m-phenylenebismaleimide (MPBM) can be exemplified, but not limited thereto. Triallyl cyanurate (TAC) and triallyl isocyanurate (TAIC) are preferable in terms of ease of handling. These crosslinking aids can be used alone or in combination of two or more. The amount of the crosslinking aid is 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, based on 100 parts by weight of the thermoplastic resin to be crosslinked. If it is 0.01 parts by weight or less, the effect of promoting the crosslinking efficiency is reduced. On the other hand, when the amount is 10 parts by weight or more, the dispersion of the crosslinking aid itself is not uniform, and a crosslinked thermoplastic resin having a uniform crosslinking density cannot be obtained. Furthermore, the addition of a large amount of crosslinking aid is not preferable because not only the efficiency as the crosslinking aid is deteriorated but also the physical properties of the crosslinked thermoplastic resin composition (A) and the molded article prepared by the present invention are lowered.

  A cross-linking thermoplastic resin composition (A ′) can be produced by blending a cross-linking aid into a thermoplastic resin to be cross-linked, mixing well, and then irradiating the pellets obtained by melt kneading with radiation. . The apparatus for melting and kneading the crosslinking aid is not particularly limited, but it is preferable to use a twin screw extruder. The cylinder temperature of the twin-screw extruder is 10 to 50 ° C. from the glass transition temperature when the crosslinked thermoplastic resin composition (A ′) is a crystalline resin, and when the crosslinked thermoplastic resin is an amorphous resin, Alternatively, it is preferable to set at a higher temperature. The residence time in the melt kneading process is generally about 30 seconds to 15 minutes. The degree of crosslinking of the crosslinked thermoplastic resin composition (A ′) can be controlled by the blending amount of the crosslinking aid used and the absorbed dose of the irradiated radiation.

  When the crosslinking of the crosslinked thermoplastic resin composition (A ′) in the present invention is crosslinked with an organic peroxide, an organic peroxide and a crosslinking aid are blended with the thermoplastic resin (A) to be crosslinked, It can be manufactured by melt kneading. The degree of cross-linking is determined by the type and amount of organic peroxide and cross-linking aid, the temperature of melt kneading and the residence time during melt kneading. As the crosslinking agent, an organic peroxide is generally used. Specific examples of the organic peroxide include benzoyl peroxide, 1,1-bis-t-butylperoxy-3,3,5-trimethylcyclohexane, dicumyl peroxide, di- (t-butylperoxy) m. -Diisopropylbenzene, 2,5-dimethyl-2-5-di-t-butylperoxyhexane, 2,5-dimethyl-2-5-t-butylperoxyhexane-3, etc. It is not limited to. The addition amount of the organic peroxide is 0.02 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin to be crosslinked. Preferably it is 0.05-3 weight part. As the crosslinking aid, the same crosslinking aid used at the time of crosslinking by radiation irradiation can be used. The blending amount of the crosslinking aid is also the same.

  In the crosslinking treatment stage of the crosslinked thermoplastic resin composition (A ′) in the present invention, a melting or kneading apparatus for adding a crosslinking aid or kneading with an organic peroxide is a single-screw extruder, two There are a screw extruder, a pressure kneader, a Banbury and the like, and a twin screw extruder is particularly preferable.

  The degree of crosslinking of the crosslinked thermoplastic resin composition (A ′) in the present invention needs to be increased, for example, by crosslinking any thermoplastic resin by the method described above until it is insolubilized in a solvent. In the case where it is dissolved in a solvent, the crosslinked dispersed phase-containing thermoplastic resin composition having a strain-hardening property used in the present invention cannot be prepared unless the degree of crosslinking is sufficient even if a crosslinked structure is introduced.

The crosslinked thermoplastic resin composition (A ′) in the present invention has a certain degree of crosslinking that is insoluble in a solvent and is compatible with an uncrosslinked thermoplastic resin and is not crosslinked. It is preferable that the cross-linking is suppressed to such a degree as to melt and disperse uniformly without forming a gel of 100 μm or more by melt kneading at a shear rate of 300 sec ⁻¹ or more. More preferably, when a film molded product of 200 μm or less is melt-molded using pellets obtained by melt-kneading with a thermoplastic resin that has not been crosslinked using a twin-screw extruder at a shear rate of 300 sec ⁻¹ or more, the film Has good surface properties and no irregularities due to gels of 100 μm or more. Here, when the surface is in a state where irregularities due to gel are formed, it means that the crosslinked thermoplastic resin composition to be dispersed has been excessively crosslinked, and a crosslinked dispersed phase having a dispersion scale of 20 μm or less is present. It becomes difficult to adjust the thermoplastic resin composition to be contained.

  Adjustment of the preferable crosslinking state of the crosslinked thermoplastic resin (A ′) in the present invention can be controlled by the amount of the crosslinking aid and the absorbed dose of the irradiated radiation when crosslinking is performed using radiation. When the crosslinking aid and organic peroxide are melt kneaded, the degree of crosslinking depends on the type and amount of the organic peroxide and crosslinking aid, the temperature of the melt kneading, and the residence time of the melt kneading. It is determined. Comparison of the degree to which an arbitrary thermoplastic resin and resin composition to be cross-linked have optimum cross-linking conditions and cross-linking conditions, and the desired degree of cross-linking is dispersed in the non-cross-linked resin under a constant shear level above the melting point Soft and uniform gel state. Generally, the degree of swelling of the solvent used as an index of the degree of crosslinking and the degree of gelation are not suitable because the gel uniformity cannot be evaluated. To evaluate the soft and uniform gel state, the insolubility evaluation including shape retention in good solvents, dispersibility to compatible resins, and loss elastic modulus and storage elastic modulus in melt viscoelasticity measurement shown in this patent are used. Using the obtained parameter as an index, obtaining the desired crosslinked state is the most efficient and accurate.

  The cross-linked thermoplastic resin composition (A ′) in the present invention undergoes a cross-linking treatment when the degree of cross-linking is increased in the process of adjusting the cross-linking degree, and the storage elastic modulus at the time of melting in the melt viscoelasticity measurement. Will increase more than before. This can be confirmed by the fact that the storage elastic modulus increases with respect to an arbitrary frequency after the crosslinking treatment in the relationship between the frequency and the storage elastic modulus at the time of melting. This increase in storage modulus can be seen in the decrease of the slope of storage modulus with respect to frequency in the frequency-storage modulus log-log plot curve when the system crosslinks uniformly.

  The crosslinked thermoplastic resin composition (A ′) preferably has a reduced slope due to the introduction of a crosslinked structure into the molecular chain. More preferably, a frequency-storage modulus log-log plot of a single non-crosslinked thermoplastic resin that is uniform and generally non-alloyed with a large slope in the range of at least 0.1 to 10 rad / s. While the slope of the storage elastic modulus with respect to the frequency is close to 2 in the curve, it is preferably increased to a range of 0.2 to 1.0, more preferably 0.2 to 0.6. is there. The optimum value of this slope differs depending on the thermoplastic resin to be crosslinked, but if this value is greater than 1.0, it indicates that crosslinking is insufficient, and it is melt-kneaded with the non-crosslinked thermoplastic resin (B). But there is no rheology improvement effect. Further, if the introduction of the bridge structure is not sufficient, the relaxation behavior in the melt-dispersed state is rapid and the dispersion structure is not stable, so that it is difficult to form a stable fine dispersion structure with the non-crosslinked thermoplastic resin (B). Conversely, when the storage modulus in the logarithmic plot curve of the frequency-storage modulus is cross-linked until the slope of the storage modulus becomes smaller than 0.2, it means that it is already a hard gel and viscoelastic properties close to a solid. However, unless the particles are adjusted to the dispersed particle scale in advance, it is difficult to form a finely dispersed structure to 20 μm or less by melt kneading with the non-crosslinked thermoplastic resin (B).

  The cross-linked thermoplastic resin composition (A ′) in the present invention preferably has a storage elastic modulus of 1E + 5 Pa or less in the range of 0.1 to 10 rad / s in the viscoelasticity measurement above the melting point. When it is 1E + 5 Pa or higher, it is a region where the shape can be maintained as a solid even at a melting temperature or higher, and even in kneading with a twin-screw extruder, a gel lump with poor dispersion exceeding 20 μm is formed in the thermoplastic resin composition. Therefore, 1E + 5 Pa or less is preferable.

  Since the crosslinked thermoplastic resin composition (A ′) in the present invention has the above-mentioned characteristics, the crosslinked thermoplastic resin composition (A ′) is non-crosslinked by melt-kneading with the non-crosslinked thermoplastic resin (B). In the thermoplastic resin (B), an average particle diameter can be dispersed to 20 μm or less, or a co-continuous structure in which the (A ′) and the (B) are intricate can be formed.

  In order to obtain a disperse phase that is easily deformed following the stretching at the time of melting, the cross-linked thermoplastic resin (A ′) in the present invention has a moderately elastic behavior in a low shear rate region corresponding to the melt stretching. Is preferably structured as In general, in a thermoplastic resin at the time of melting, the shear rate dependency of the storage elastic modulus is larger than the shear rate dependency of the loss elastic modulus, and at least in the frequency range of 0.1 to 10 rad / s obtained by melt viscoelasticity measurement. If the slope of the storage elastic modulus in the logarithmic plot curve of frequency-storage elastic modulus is α, α can be treated as a frequency-dependent parameter of the storage elastic modulus. If the slope of the loss modulus in the log-log plot curve of the frequency-storage modulus is β, β can be treated as a frequency dependence parameter of the loss modulus. Furthermore, α-β can be treated as a frequency-dependent parameter of tan δ. In the case of a general thermoplastic resin, α> β and the absolute value of α-β is close to 1.0.

  Regarding α-β of the crosslinked thermoplastic resin composition (A ′) in the present invention, the larger this value, the smaller the storage elastic modulus relative to the loss elastic modulus at low shear, and the more difficult it is to stretch. It shows that. As a dispersion that can be easily stretched at the time of melting, the absolute value of α-β of the crosslinked thermoplastic resin composition (A ′) in the present invention is 0.15 or less regardless of the size of α and β. preferable. More preferably, the absolute value of α-β is 0.10 or less. When α and β are α> β and the absolute value of α-β exceeds 0.15 or more with respect to the crosslinked dispersed phase of the crosslinked dispersed phase-containing thermoplastic resin composition used in the present invention, the loss in the low shear region The storage elastic modulus is too low for the elastic modulus and does not follow the stretching of the system. When α and β are α <β and the absolute value of α-β exceeds 0.15 for the cross-linked dispersed phase of the cross-linked dispersed phase-containing thermoplastic resin composition used in the present invention, viscoelasticity that is almost solid. It is characteristic and is too hard to disperse the dispersed phase.

  In the process of adjusting the degree of crosslinking of the crosslinked thermoplastic resin composition (A ′) in the present invention, depending on the function desired to be imparted to the finally-dispersed dispersed phase, the crosslinking is not inhibited or promoted excessively. As long as the degree of crosslinking can be easily adjusted, other resins, functional fillers, additives and the like can be blended. As fillers and compounding agents, for example, reinforcing materials such as glass fibers, carbon fibers, various inorganic fillers, heat stabilizers, UV stabilizers, weather resistance improvers, antioxidants, flame retardants, conductive fillers, thermal conductivity The compounding agents and additives such as fillers, antistatic agents, pigments and dyes are not limited to these. If these functional compounding agents are blended and crosslinked before crosslinking with the non-crosslinked thermoplastic resin (A), in the thermoplastic resin molded article of the present invention, an oval, fibrous, flat or The compounding agent can be selectively restrained in the dispersed phase of the cross-linked thermoplastic resin (A ′) deformed into another irregularly stretched shape, and higher-order dispersion structure control and functional design are possible.

It is preferable that at least 50% by weight in the crosslinked thermoplastic resin composition (A ′) is any one of a polyamide resin, a polyester resin, and a polyolefin resin.
When at least 50% by weight of the crosslinked thermoplastic resin composition (A ′) is a polyester resin, 50 to 99.9 parts by weight of polycaprolactone is crosslinked with 100 parts by weight of the crosslinked thermoplastic resin composition (A ′). Pellets obtained by melt-kneading a resin composition containing 0.1 to 3 parts by weight of an auxiliary agent are preferably irradiated with an absorbed dose of 0.5 to 25 kGy.
Further, when at least 50% by weight in the crosslinked thermoplastic resin composition (A ′) is a polyester resin, 50 to 99.9 parts by weight of the polyester elastomer with respect to 100 parts by weight of the crosslinked thermoplastic resin composition (A ′). And pellets obtained by melt-kneading a resin composition containing 0.1 to 3 parts by weight of a crosslinking aid are preferably irradiated with an absorbed dose of 0.5 to 60 kGy.
When at least 50% by weight in the crosslinked thermoplastic resin composition (A ′) is a polyamide-based resin, 50 to 99.9 parts by weight of polyamide and crosslinking aid are added to 100 parts by weight of the crosslinked thermoplastic resin composition (A ′). The pellet obtained by melt-kneading the resin composition containing 0.1 to 3 parts by weight of the agent is preferably irradiated with an absorbed dose of 0.5 to 20 kGy.
When the above range is not satisfied, it may be difficult to obtain a crosslinked thermoplastic resin composition (A ′) having desired characteristics.

  The thermoplastic resin composition in the present invention can be obtained by melt-kneading the crosslinked thermoplastic resin composition (A ′) and the non-crosslinked thermoplastic resin (B). The blending ratio of the crosslinked thermoplastic resin composition (A ′) and the non-crosslinked thermoplastic resin (B) is preferably (A ′) :( B) = 1: 99 to 95: 5. When (A ′) is less than 1 and (B) exceeds 99, the rheology improving effect of the non-crosslinked thermoplastic resin (B) becomes poor, (A ′) exceeds 95 and (B) is less than 5. And the characteristic of (B) becomes difficult to express and it is disadvantageous also in cost.

The thermoplastic resin composition of the present invention obtained by melt-kneading the crosslinked thermoplastic resin composition (A ′) and the non-crosslinked thermoplastic resin (B) is at least from the melting point of the non-crosslinked thermoplastic resin (B). In the logarithmic plot curve of time-uniaxial extensional viscosity obtained by melt uniaxial extensional viscosity measurement at a temperature higher than 10 ° C., the following strain hardening coefficient must be 2 or more.
Strain hardening coefficient = a2 / a1
a1: slope of linear region in log-log plot curve of time-uniaxial extensional viscosity
a2: The slope of the nonlinear region in the logarithmic plot curve of time-uniaxial extensional viscosity When the strain hardening coefficient is less than 2, the rheology improving effect of the non-crosslinked thermoplastic resin (B) is poor. The strain hardening coefficient is preferably about 4 to 50 in terms of ease of production of the composition and molding stability.

  The combination of the non-crosslinked thermoplastic resin (A) and the non-crosslinked thermoplastic resin (B), which are thermoplastic resins before being subjected to the crosslinking treatment, is preferably compatible, and is a resin of the same system Is preferred. For example, combinations of polyester resins, polyamide resins, polyolefin resins, and the like are preferable.

  Further, in the present invention, a functional filler or additive may be added depending on the function desired to be expressed in the molded body even during the melt kneading of the crosslinked thermoplastic resin composition (A ′) and the non-crosslinked thermoplastic resin (B). A material etc. can be mix | blended. For example, reinforcing materials such as glass fibers, carbon fibers, various inorganic fillers, heat stabilizers, UV stabilizers, weather resistance improvers, antioxidants, flame retardants, conductive fillers, heat conductive fillers, antistatic agents, These are compounding agents and additives such as pigments and dyes, but are not limited thereto. In the melt-kneading of the crosslinked thermoplastic resin composition (A ′) and the non-crosslinked thermoplastic resin (B) that have already undergone crosslinking treatment, the blended fillers and additives have a very high melt elastic modulus. Since it does not easily enter the crosslinked thermoplastic resin composition (A ′) even under melt shearing, it is selectively dispersed in the matrix phase of the non-crosslinked thermoplastic resin (B). This enables higher-order distributed structure control and functional design.

Furthermore, the thermoplastic resin composition in the present invention is a mixture obtained by mixing a cross-linked thermoplastic resin composition (A ′) and a non-cross-linked thermoplastic resin (B), and, if necessary, a compounding agent, an injection molding machine, an extrusion It is possible to directly put into a machine, an extrusion stretching machine, etc., melt and knead, and to directly form a molded body. Even in such a case, the shear rate during melt-kneading is important for structuring the crosslinked thermoplastic resin composition (A ′) with the non-crosslinked thermoplastic resin (B). The shear rate during melt kneading needs to be 300 sec ^-1 or more. The shear rate is preferably 500 sec ⁻¹ or more, more preferably 1000 sec ⁻¹ or more.

  In an injection molding machine, an extruder, etc., melt kneading is possible even from a hopper into which a mixture is introduced to a mold or a die, and the cross-linked thermoplastic resin composition (A ′) and non-cross-linking heat are changed depending on the shear rate between them. A method in which a plastic resin (B) and other compounding agents are microstructured and further molded in a mold at the tip of a molding apparatus is stretched in a molten or non-molten state, or molded with a die. It can also extend | stretch in a molten state or a non-molten state.

  The molded product obtained by molding the thermoplastic resin composition in the present invention as described above is in a state in which the crosslinked state of the crosslinked thermoplastic resin composition (A ′) has a specific viscoelasticity as described above. Therefore, the crosslinked dispersed phase is easily deformed in the stretching direction following the stretching at the time of molding, and can be deformed into an elliptical shape, a fibrous shape, a flat shape, or other irregularly stretched shapes.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded. The measurement methods, evaluation methods, and experimental methods employed in the examples and comparative examples are shown below.
(1) Method for measuring storage elastic modulus and loss elastic modulus of crosslinked thermoplastic resin when melted:
Using TA Instruments ARES and a 25 mm parallel plate as a measurement jig, dynamic viscoelasticity measurement is performed under the following conditions, and frequency-storage elastic modulus, frequency-loss elastic modulus and frequency-shear viscosity log-log plots Obtained.
・ Strain = 10%
・ Temperature = at least 10 ° C. of the crystalline melting point of DSC ・ Initial Frequency = 100 rad / s
・ Final Frequency = 0.1 rad / s
・ Gap = 0.7-1.5mm
・ Geometry Type = Parallel Plate (Diameter = 25mm)
The crosslinked thermoplastic resin composition in which the crosslinking proceeded too much in the crosslinked thermoplastic resin preparation example was determined to be “impossible to measure” because the storage elastic modulus could not be measured with ARES manufactured by TA Instruments.
Further, the slope α of the storage elastic modulus in the frequency-storage elastic modulus logarithmic plot curve in the frequency range of 0.1 to 10 rad / s of the crosslinked thermoplastic resin composition and the loss elastic modulus in the frequency-loss elastic modulus logarithmic plot curve. The slope β was obtained, and α-β that was a frequency dependent parameter of tan δ was obtained.

(2) Solvent dissolution test method for crosslinked products:
Diameter Φ approx. 3mm x Length approx. 3mm Cut pellet shaped cross-linked product, polyester resin is immersed in a mixed solvent of phenol and tetrachloroethane for normal temperature x 40 hr or more, polyamide type is immersed in formic acid at normal temperature x 40 hr or more, solvent The presence or absence of the residue after removal was confirmed visually. A transparent solvent gel remained in the swollen shape of the pellet before immersion, and when the same number of solvent swollen gels as the number of immersed pellets could be confirmed, it was expressed as “insoluble”. It is dissolved in the solvent and removed together with the solvent when removing the solvent, or the shape of the solvent swollen gel is greatly collapsed from the soaked pellet shape, and it is expressed as “dissolved” when it is divided and does not retain the shape X.

(3) Dispersion test method for non-crosslinked thermoplastic resin of crosslinked product:
With respect to the crosslinked thermoplastic resin composition X (A ′) obtained by subjecting any thermoplastic resin X (A) to a crosslinking treatment, dispersibility in the non-crosslinked thermoplastic resin X (A) was evaluated as follows. .
Cross-linked thermoplastic resin X (A ′) and non-crosslinked thermoplastic resin X (A) subjected to cross-linking treatment are used for a twin screw extruder (Ikegai Iron Works Co., Ltd., PCM30) at least 10 ° C. or more than the melting point of both resins. At a high cylinder temperature setting and a screw rotation speed of 120 rpm, the sum of X (A ′) and X (A) is 100 parts by weight, and the ratio of X (A) / X (A ′) = 70 parts by weight / 30 parts by weight. The mixture was melted and kneaded, extruded into a strand form in a water bath, cooled, and then cut to obtain pellets of a resin composition. The obtained resin composition pellets were dried by vacuum drying until the moisture content was 0.05% by mass or less, and then a sheet-like molded product having a thickness of 200 μm was formed by extrusion molding.
It was confirmed by visual observation that the obtained sheet surface state was free of irregularities due to the gel product, or whether there was a gel product having a maximum length (diameter) of 100 μm or more. In the case of a sheet having a thickness of 200 μm, it was confirmed that unevenness was always observed when a gel product having a thickness of 100 μm or more was present. Therefore, a sheet having a smooth sheet surface was determined to be “dispersed”. A 200 μm sheet with conspicuous irregularities, or a sheet with no smooth strands without forming a sheet, was designated as “dispersion failure”. When the relationship between visual observation and the gel product is difficult to understand, the cross-linked thermoplastic resin composition X (A ′) is converted into the non-cross-linked thermoplastic resin X (A) by a transmission electron microscope (TEM) or a scanning electron microscope (SEM). ) To confirm the structure dispersed inside. In addition, regarding a resin such as polylactic acid, which has a strong tendency to decompose by radiation, the structure was observed with a scanning probe microscope (SPM) in order to show a decomposition tendency during observation with an electron microscope.

(4) Measuring method of strain hardening coefficient in log-log plot curve of time-uniaxial extensional viscosity:
Using TA Instruments ARES, EVF (Extensional Visibility Fixture) manufactured by TA Instruments was used as a measurement jig. The measurement conditions were a temperature up to at least 10 to 50 ° C. higher than the DSC melting point of the measurement resin at a strain rate of at least 1.0 (s ⁻¹ ), and the obtained time-uniaxial extensional viscosity double logarithmic plot curve was as follows. The strain hardening coefficient represented by the formula was obtained.
Strain hardening coefficient = a2 / a1
a1: slope of linear region in log-log plot curve of time-uniaxial extensional viscosity
a2: The slope of the nonlinear region in the logarithmic plot curve of time-uniaxial extensional viscosity Here, a1 was determined as follows without using a simple method.
That is, using TA Instruments ARES and a 25 mm parallel plate as a measuring jig, strain = 10%, temperature = same temperature as uniaxial extensional viscosity measurement, and GAP = 0.7 to 1.5 mm under frequency 0. The frequency dependence data of the shear viscosity in the range of 1 to 100 rad / s was obtained, and the triple value of the shear viscosity obtained from this: 3ηs was plotted on the log-log plot of time-shear viscosity, and the slope of the plot line Was the slope a1 of the linear region in the logarithmic plot curve of time-extension viscosity.

(5) Dispersion structure observation method:
Depending on the characteristics of the sample, (a) TEM (transmission electron microscope), (b) SEM (scanning electron microscope) can be used to observe the structure of the crosslinked thermoplastic resin composition (A ′) and non-crosslinked thermoplastic resin (B). ), (C) SPM (scanning probe microscope), (d) phase microscope, (e) differential interference microscope, and the like.
In the examples and comparative examples, specifically, observation with an electron microscope is performed by wrapping pellets obtained by melt-kneading a crosslinked thermoplastic resin composition (A ′) and a non-crosslinked thermoplastic resin (B) in a photocurable resin. Polishing after embedding and staining with 5-10% phosphotungstic acid aqueous solution was observed with SEM, or frozen sections obtained with cryomicrotome were stained with RuO ₄ with TEM. The method is not limited. The SPM, phase microscope, and differential interference microscope were also observed using frozen sections obtained with a cryotome.

The observed morphology of the sample was determined and described as follows.
A dispersion structure with a uniform dispersion order and a uniform dispersion shape is defined as “uniform” in the uniformity of the dispersion structure, and a dispersion structure with a dispersion order non-uniform and a dispersion shape is not uniform in the uniformity of the dispersion structure. Non-uniform ”.
Regarding the dispersion form, if at least one of a plurality of types of melt-kneaded resins is made into a matrix and other resins are dispersed in the form of particles in the matrix, it is referred to as “independent dispersion” and the plurality of types of resins that are melt-kneaded. In the case where the two have a co-continuous structure intermingled with each other, it is regarded as “co-continuous”. In the case of “independent dispersion”, the particle size of the observed dispersed particles is described as the dispersion order, and in the case of a co-continuous structure, the width of the phase in the continuous phase having an apparently small ratio in the observed image is represented by the dispersion order. It was. In addition, the case where no clear micron-order structure was observed was defined as “no structure”. The particle diameter of the dispersed particles was measured from the observation image using the maximum diameter of each particle in the observation image as the particle diameter. The dispersion order of the width of the phase and the dispersed particle size in the continuous phase were confirmed by 10 observation images.
Concerning the usefulness of the structure, the dispersion order is 10 μm or less and uniformly dispersed and “independent dispersion” or “co-continuous” is designated as ○ as a useful structure for functional design, and the dispersion order, structure uniformity, dispersion Those which do not satisfy these in the form were marked as “x” as a structure not sufficiently useful for functional design.

(6) Method for measuring stretch followability of dispersed phase:
A thermoplastic resin containing a dispersed phase is melted by a twin-screw extruder (Ikegai PCM30 die diameter 5 mm × 1 hole), and a strand extruded from a circular die having a diameter of 5 mm by discharge of 3 kg / hr is melted to have a strand diameter of 1 A sample was obtained by solidifying after stretching to 6 mm and cutting it to a length of 100 mm. The obtained melt-stretched strand-shaped sample having a diameter of 1.6 mm and a length of 100 mm is calculated to be 9.76 times as long as the swell phenomenon when extruded from a circular die is not taken into consideration. Regardless, it was judged that the film was stretched at least 9.76 times.
The stretching followability of the dispersed phase was evaluated by confirming the shape of the dispersed phase by observing the structure of the cross section in the stretching direction. Structure observation depends on the characteristics of the sample: (b) TEM (transmission electron microscope), (b) SEM (scanning electron microscope), (c) SPM (scanning probe microscope), (d) phase microscope, (e) differentiation An interference microscope was used. Specifically, the electron microscopic observation is performed by embedding the sample in a photocurable resin and then polishing and staining with a 5 to 10% phosphotungstic acid aqueous solution with an SEM, or a frozen section obtained with a cryomicrotome. _Although what was dye | stained by ₄ was observed by TEM, this does not limit the method of structure observation. The SPM, phase microscope, and differential interference microscope were also observed using frozen sections obtained with a cryotome.
The shape of the dispersed phase in the cross-section in the observed stretching direction largely follows the stretching direction and is deformed into a fiber, and the observed dispersed phase L (length in the stretching direction) / D (relative to the stretching direction) If the dispersion diameter in the vertical direction) is 4 or more, it is considered that the dispersion phase has stretchability.

<Raw materials used in Examples and Comparative Examples>
PA6: “Toyobo Nylon T-800” manufactured by Toyobo Co., Ltd., which is 6 nylon with relative viscosity RV = 2.5
MXD6: MXD6 nylon with relative viscosity RV = 2.1, “Toyobo Nylon T-600”
PA66: 66 nylon with relative viscosity RV = 2.78, “Torea Milan CN3001N”
PCL: “PCL-H7” manufactured by Daicel Chemical Industries, which is a polycaprolactone having a molecular weight of 70000
PLA: “Lacia H100” manufactured by Mitsui Chemicals, which is polylactic acid having a melting point of 164 ° C.
Polyester elastomer (A): “GS430” manufactured by Toyobo Co., Ltd., which is a polybutylene terephthalate / polycaprolactone = 57/43 (% by weight) copolymer having a melting point of about 210 ° C. and a solution viscosity of 1.45 dl / g.
Polyester elastomer (b): “GP84D” manufactured by Toyobo Co., Ltd., which is a polybutylene terephthalate / PTMG = 53/47 (wt%) copolymer having a melting point of about 203 ° C. and a solution viscosity of 1.95 dl / g.
PBT: Polyethylene terephthalate having a relative viscosity of IV = 0.8 “1200S” manufactured by Toray Industries, Inc.
PET: “RE530” manufactured by Toyobo Co., Ltd., which is a polyethylene terephthalate having a relative viscosity of IV = 0.63.
Crosslinking aid A: “TMAIC” which is trimethallyl isocyanurate manufactured by Nippon Kasei Co., Ltd.
Crosslinking aid B: “TAIC” which is triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd.
Mold release agent: Montanate ester wax "WE40" manufactured by Clariant
Stabilizer: “Irganox B1171” manufactured by Ciba Specialty Chemicals

<Production and Evaluation of Crosslinked Thermoplastic Resin Composition>
The thermoplastic resin to be crosslinked and the crosslinking aid are mixed in the ratios described in Tables 1 to 4, and the temperatures described in Tables 1 to 4 using a twin-screw extruder (Ikegai PCM30 die diameter 5 mm × 1 hole), A pellet-shaped thermoplastic resin composition was obtained by melt-kneading by screw rotation kneading and cutting the strand after cooling. The obtained pellets are dried and placed in an aluminum moisture-proof bag, and irradiated with γ-rays until the dose shown in Tables 1 and 2 is reached with a γ-ray irradiation device (MDS Nordion, model JS10000HD) using Co-60 as a radiation source. Thus, a crosslinking treatment was performed to obtain a crosslinked thermoplastic resin composition in which the crosslinking state was specifically controlled. The obtained crosslinked thermoplastic resin composition was evaluated for solvent solubility and dispersibility in a non-crosslinked thermoplastic resin. Further, a logarithmic plot of frequency-storage elastic modulus, loss elastic modulus, and shear viscosity was obtained for the crosslinked thermoplastic resin composition, and the slope of the storage elastic modulus with respect to the frequency was obtained. The obtained evaluation results are shown in Tables 1 to 4.

Among the cross-linked thermoplastic resin compositions A-1 to D-3 cross-linked under the cross-linking conditions shown in Tables 1 to 4, those that are insoluble in a good solvent and described as ◯ are described in the table. It was confirmed that the crosslinking proceeded until it became insoluble in the good solvent. Among the crosslinked thermoplastic resin compositions A-1 to D-3, the dispersibility with respect to the non-crosslinked thermoplastic resin was kneaded and evaluated at the temperatures shown in the table, and “dispersed” It was confirmed that the dispersibility with respect to the plastic resin was good. Furthermore, the crosslinked thermoplastic resin compositions A-1, B-1, C-1, and D-1 that are insoluble in a good solvent and adjusted to be dispersible with respect to the non-crosslinked thermoplastic resin are: Viscoelastic properties at the time of melting are in the range of at least 0.1 to 10 rad / s in the logarithmic plot of frequency-storage modulus, and the slope of storage modulus with respect to frequency is 0.2 to 1.0, and the frequency dependence of tan δ The absolute value of α-β which is a parameter is 0.15 or less, which is confirmed to be suitable as the crosslinked resin composition (A ′) in the present invention. Further, the storage elastic modulus in the viscoelasticity measurement above the melting point is It was confirmed that it was 1E + 5 Pa or less in the range of at least 0.1 to 10 rad / s. Regarding the cross-linked thermoplastic resins A-1 to D-3 described in Tables 1 to 4, those for which cross-linking has progressed excessively were described as being incapable of measurement because the test piece for melt viscoelasticity measurement could not be adjusted.

Examples 1-6, Comparative Examples 1-8
The combinations and ratios of the crosslinked thermoplastic resin composition and the non-crosslinked thermoplastic resin described in Tables 5 and 6 are described in Tables 5 and 6 using a twin-screw extruder (Ikegai PCM30 die diameter 5 mm × 1 hole). The thermoplastic resin composition pellets of Examples 1 to 6 and Comparative Examples 1 to 6 were obtained by melt-kneading under the melt-kneading conditions and cooling and cutting the strands. About the obtained composition, (1) Strain hardening coefficient in a time-extension viscosity logarithmic curve, (2) Dispersion structure observation was performed, and the result was described in Table 5,6.
In the structural observation of the thermoplastic resin compositions of Example 1 and Comparative Examples 1 and 2, the frozen sections obtained with a cryomicrotome were stained with a phosphotungstic acid aqueous solution, followed by SEM observation, and the results were described. The structure of the thermoplastic resin compositions shown in Example 2, Example 3, Example 6, and Comparative Example 4 was observed by TEM observation of a frozen section obtained by a cryomicrotome and stained with RuO _4. Was described. Structural observation of the thermoplastic resin compositions shown in Example 4, Example 5, Comparative Example 6, and Comparative Example 7 was performed by phase contrast microscopy and SPM observation of frozen sections obtained with a cryomicrotome. Since Comparative Examples 2, 5, and 8 are crosslinked thermoplastic resin compositions that are more crosslinked than the degree of crosslinking in the present invention, a finely structured crosslinked dispersed phase cannot be obtained, and the crosslinked thermoplastic resin is 300 μm or more. It was a state which can confirm visually coarse gel-like stuff.
Next, the thermoplastic resin compositions of the above Examples and Comparative Examples were further melted and stretched by a twin screw extruder (Ikegai PCM30 die diameter 5 mm × 1 hole) to evaluate the stretch followability of the dispersed phase. The results are shown in Tables 5 and 6.

A dispersed phase greatly deformed by stretching a thermoplastic resin having a uniform and finely structured crosslinked dispersed phase and exhibiting strain-hardening properties as shown in Examples 1 to 6 in a molten state. I could get it easily.
Comparative Examples 3, 4, 6, and 7 include a relatively fine dispersed phase in the structure, but the dispersed phase is not crosslinked and has not been imparted with appropriate melting rheological properties. When the thermoplastic resin composition is used, the dispersed phase does not deform following the melt stretching, so that it cannot be an effective adjustment method for obtaining the desired molded article.
In Comparative Examples 2, 5, and 8, since the crosslinked thermoplastic resin does not have a fine structure because the degree of crosslinking of the crosslinked thermoplastic resin is too high, if the crosslinked thermoplastic resin in such an inappropriate crosslinked state is used, the desired molding is performed. It cannot be an effective adjustment method to obtain the body.
Even in PA6 and MXD6, which show high compatibility in Comparative Example 1 and apparently uniform in micron order SEM observation, a molded product is obtained by adjusting PA6 to an appropriate cross-linked state by the adjustment method shown by the present invention. Accordingly, PA6 can be dispersed independently in the matrix of MXD6, and a molded body deformed in the stretching direction can be obtained.

Next, a supplementary explanation will be given with respect to the drawings.
FIG. 1 shows SEM observation results before stretching of the compositions shown in Example 1 and Comparative Example 1. The composition of Example 1 shows that the crosslinked PA6 (white part) has an independent dispersion structure without being homogenized with respect to MXD6 (black part). Since the composition of Comparative Example 1 kneaded uncrosslinked PA6 with MXD6, it was highly compatible and no independent dispersion form of PA6 was observed.
FIG. 2 shows the cross-sectional direction of the stretched strand sample obtained in Example 5 and the structural observation results of the cross-section perpendicular to the stretch direction. The disperse phase (white portion) has a continuous structure, but the state of deformation in the stretching direction is clearly shown.
FIG. 3 shows the SPM observation result before stretching of the composition shown in Comparative Example 7. Dispersion diameter and dispersion state are greatly different in the two images observed in the same sample pellet, indicating that the structure is inhomogeneous although it is dispersed independently with a dispersion diameter of a certain shape or less. Has been.

FIG. 4 shows a differential interference microscope image before stretching, a differential interference microscope image after stretching, and a TEM image of the composition shown in Example 2. In the differential interference microscope image, a cross-linked dispersed phase is shown in a dark contrast in the figure, and in the TEM image, a cross-linked dispersed phase is shown in a thin contrast in the figure. The stretched molded body obtained by the adjusting method of the present invention clearly shows the state of the dispersed phase greatly deformed in the stretching direction.
FIG. 5 shows a TEM observation image of a film-like molded article prepared by adjusting the resin composition by the method shown in Example 1 and Example 6, and adjusting the resin composition by melt stretching in a uniaxial direction at a different stretching ratio from that of Example. It is shown. The film prepared by the adjustment method shown in Example 1 was drawn at a draw ratio of about 20 times, and the film prepared by the adjustment method shown in Example 6 was drawn at a draw ratio of about 4. Film. Both samples clearly show that the crosslinked dispersed phase is well deformed following stretching.

The molded article of the present invention contains a crosslinked dispersed phase that is easily deformed to a high degree by simply stretching a thermoplastic resin composition containing a crosslinked dispersed phase satisfying specific conditions at the time of molding. In addition, various cross-linked dispersed phases and non-cross-linked resins can be combined, so by selecting the functionality of the dispersed phase, very useful functionalities such as barrier properties, optical properties, impact resistance, heat resistance, etc. Can be expressed efficiently, and contribute greatly to the industry.

Claims (10)

Obtained by melt-kneading a crosslinked thermoplastic resin composition (A ′) having the following characteristics (a) obtained by crosslinking the non-crosslinked thermoplastic resin (A) and the non-crosslinked thermoplastic resin (B): The thermoplastic resin composition forms a dispersed phase in which (A ′) is dispersed in a particle size of at most 20 μm in (B), or (A ′) and (B) are involved in each other. The co-continuous structured cross-linked phase is formed (hereinafter, the dispersed phase and the cross-linked phase are collectively referred to as a cross-linked dispersed phase) , and in the nonlinear region in the melt uniaxial elongation viscosity, A molded body obtained by melt-stretching the thermoplastic resin composition, wherein the crosslinked dispersed phase in the molded body follows the stretching at the time of molding. Contains a deformed crosslinked dispersed phase characterized by being deformed in the stretching direction Thermoplastic resin composition molded article.
(A) A solvent gel is formed with the solvent without dissolving in the solvent of the non-crosslinked thermoplastic resin (A).
(B) The following strain hardening coefficient in a log-log plot curve of time-uniaxial extension viscosity obtained by measuring the melt uniaxial extension viscosity of the thermoplastic resin at a temperature of at least 10 ° C. higher than the melting point of the non-crosslinked thermoplastic resin (B) Is 2 or more.
Strain hardening coefficient = a2 / a1
a1: slope of linear region in log-log plot curve of time-uniaxial extensional viscosity
a2: Slope of nonlinear region in log-log plot curve of time-uniaxial extensional viscosity The cross-linked thermoplastic resin composition (A ′) has a storage elasticity with respect to frequency within a frequency range of 0.1 to 10 rad / s in a logarithmic plot curve of frequency-storage elastic modulus obtained by melt viscoelasticity measurement in the linear region. The thermoplastic resin composition molded article containing a deformed crosslinked dispersed phase according to claim 1, wherein the molded article is in a crosslinked state where the gradient of the rate is 0.2 to 1.0. When the crosslinked thermoplastic resin composition (A ′) has a frequency-storage elastic modulus logarithmic plot curve, the slope of the storage elastic modulus is α in the frequency range of 0.1 to 10 rad / s in melt viscoelasticity measurement in the linear region. The modified cross-linked dispersion according to claim 1 or 2, wherein the absolute value of the difference between α and β is 0.15 or less, where β is the slope of the loss modulus in the logarithmic plot curve of the frequency-loss modulus logarithm. A thermoplastic resin composition molded body containing a phase. The thermoplastic resin composition molded article containing a deformed crosslinked dispersed phase according to any one of claims 1 to 3, wherein the crosslinked thermoplastic resin composition (A ') is irradiated with radiation. The crosslinked thermoplastic resin composition (A ') is formed by irradiating a pellet obtained by melt-kneading the non-crosslinked thermoplastic resin (A) and a crosslinking aid. A molded thermoplastic resin composition containing the deformed crosslinked dispersed phase. The crosslinked thermoplastic resin composition (A ′) is obtained by blending a non-crosslinked thermoplastic resin (A) with a crosslinking aid and / or an organic peroxide and crosslinking by melt kneading. A thermoplastic resin composition molded article containing the deformed crosslinked dispersed phase according to any one of -5. The deformed crosslinked dispersed phase according to any one of claims 1 to 6, wherein at least 50% by weight in the crosslinked thermoplastic resin composition (A ') is any one of a polyamide resin, a polyester resin and a polyolefin resin. A molded thermoplastic resin composition. Absorbent crosslinked thermoplastic resin composition (A ') is, pellets of the resin composition obtained by melt kneading which includes a port re-caprolactone 50 to 99.9 parts by weight and the crosslinking aid 0.1-3 parts by weight The thermoplastic resin composition molded article containing a deformed crosslinked dispersed phase according to any one of claims 1 to 7, which is irradiated with a dose of 0.5 to 25 kGy. Crosslinked thermoplastic resin composition (A ') is absorbed dose pellets of the resin composition obtained by melt kneading including port re ester elastomer 50 to 99.9 parts by weight and the crosslinking aid 0.1-3 parts by weight The thermoplastic resin composition molded article containing a deformed crosslinked dispersed phase according to any one of claims 1 to 7 , which is irradiated with radiation of 0.5 to 60 kGy. Crosslinked thermoplastic resin composition (A ') is, Polyamide 99.9 parts by weight and absorb the resin composition containing a crosslinking assistant 0.1-3 parts by weight obtained by melt kneading the pellets dose 0 The thermoplastic resin composition molded article containing the deformed crosslinked dispersed phase according to any one of claims 1 to 7 , which is irradiated with radiation of 5 to 20 kGy.