JPS62242516A - Manufacture of oriented resin body - Google Patents

Abstract

PURPOSE:To enhance mechanical properties of a resin composition by orienting or rolling a shape imparter of resin composition containing low melting point components in a temperature of more than the temperature of transition area or less than rubber-type area and then cooling down quickly and orienting or rolling in a temperature of less than that of transition area. CONSTITUTION:A resin composition containing at least one of low melting point components is primarily oriented as a shape imparter of film, fiber material, etc. This process is carried out in a temperature more than that of transfer area of resin composition containing low-melting component and less than that of rubber-type area. The temperature of transfer area means the temperature of a range in which a resin composition turns from a state of glass into a state of rubber. Next, the primary orienting substance is cooled down in a quickly lowered temperature down to less than transfer area, before relaxation of stress is completed, retaining the substance to be oriented. By said process, resin composition can be cool-oriented without phase separation of whiting. Next, the secondary orientation is carried out to get oriented resin body, film or fiber type, etc. This is a cold orientation in a temperature less than that of transfer area.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical details] The present invention relates to a method for producing a stretched resin body using a resin composition containing a low melting point component and capable of obtaining a stretched resin body having excellent mechanical properties.

[Background technology]

First, mechanical properties such as strength and modulus of elasticity are improved by stretching a shaped polymer (unstretched product). However, for example, in the case of polyvinyl chloride containing di(2-ethylhexyl) phthalate as a low melting point component,
Even if cold stretching or rolling is attempted, whitening or phase separation becomes significant, and the mechanical strength of the stretched product tends to decrease instead.

In order to prevent this, it is necessary to carry out stretching at a high temperature above the temperature at which the resin begins to soften. However, when stretched at high temperatures, intermolecular slippage tends to occur, so the stretching effect is reduced. It becomes difficult to appear.

Therefore, even if the resin composition contains a low melting point component,
The development of a manufacturing method that can efficiently improve mechanical properties and obtain stretched resin bodies with excellent mechanical properties is awaited.

[Purpose of the invention]

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a stretched resin body that can obtain a stretched resin body with excellent mechanical properties.

[Disclosure of the invention]

In order to achieve the above objectives, the inventors have conducted repeated research. As a result, surprisingly, it has been found that if an excipient of a resin composition containing a low melting point component is stretched or rolled at a temperature above the transition region of the resin composition and below the temperature of the rubbery region and then rapidly cooled, the excipient is The shape can be cold-stretched or cold-rolled without causing phase separation or whitening, and if the stretched or rolled product is cold-stretched or cold-rolled after the quenching, a stretched resin with excellent mechanical properties can be obtained. He discovered that it was possible to obtain a new body and completed this invention.

Therefore, the present invention provides a method for stretching or rolling a shaped body of a resin composition containing a low melting point component at a temperature higher than or equal to the temperature of the transition region of the resin composition and lower than the temperature of the rubbery region, and then rapidly cooling the shape of the resin composition, and The gist is a method for producing a stretched resin body that is stretched or rolled at a temperature below the temperature of the region.

The present invention will be explained in detail below.

The resin composition used in this invention contains at least one low melting point component. Here, the low melting point component is
It is a component that, when blended, lowers the melting point of the polymer contained in the resin composition, regardless of whether it is a monomer or a polymer. Furthermore, the low melting point component may be reactive or non-reactive.

The non-reactive low melting point component is used as a so-called plasticizer, and is used, for example, to lower the rigidity, softening temperature, glass transition temperature, melting point, etc. of the resin composition. Examples of non-reactive low-melting components include di(2-ethylhexyl) phthalate, dibutyl phthalate, diethyl phthalate, dibutyl sebacate, and di(2-ethylhexyl) adipate.
-ethylhexyl), dibutyl maleate, tributyl acetyl citrate, tricresyl phosphate, etc., but are not limited to these.

In addition to the above-mentioned effect as a plasticizer, the reactive low melting point component is used to improve the physical properties of the resin composition through reaction of the components. Alternatively, it is used primarily for the purpose of improving the physical properties of the resin composition through reaction, rather than for its effect as a plasticizer. For example, if a component that causes a curing reaction is used as the reactive low melting point component and is cured after second stretching (or rolling), the mechanical properties of the stretched resin body will be further improved. Examples of the reactive low melting point component include, but are not limited to, styrene, divinylbenzene, triallylisocyanurate, trimethylolpropane trimethacrylate, and pentaerythritol triacrylate. Further, an initiator, catalyst, aggravating agent, etc. may be added as necessary.

Although not particularly limited, the blending ratio of low melting point components varies greatly depending on the purpose of use, but in any case,
0.1 to 9 per 100 parts by weight of the main component polymer
Examples of the resin (polymer) used in this invention, which is preferably within the range of 0 parts by weight, include polyvinyl chloride, polystyrene, polyphenylene oxide (hereinafter referred to as rPPOJ), methacrylate-styrene copolymer, polymethyl methacrylate, etc. However, it is not limited to those listed here. PPO may be used in combination with one or more types of polymers, as required, for the purpose of improving the performance or changing the properties of the obtained stretched resin body, for example. Furthermore, so-called additives and fillers, typified by antioxidants, ultraviolet absorbers, etc., seem to be added to resin compositions for the purpose of improving the performance of stretched resin products. Good too.

A resin composition consisting of the above-mentioned components is made into a shaped body such as a film or a fibrous body. This shaped body is first subjected to primary stretching. This first stretching is performed at a temperature that is higher than the temperature of the transition region of the resin composition containing the low melting point component and lower than the temperature of the rubbery region. When the temperature-modulus (E') curve F of the resin composition is as shown in FIG. 1, range A is a transition region, range B is a rubbery region, and range C is
The temperature is above the temperature of the transition region and below the temperature of the rubbery region, where the range is the glassy region and the range E is the fluid region. Tg is the glass transition point. The higher the stretching speed is, the more preferable it is, and the higher the stretching ratio is, the more preferable it is. However, since the primary purpose of the primary stretching is to perform cold stretching without causing phase separation or whitening of the resin composition during the subsequent rapid cooling, it is not necessarily necessary to use high speed and high magnification. Specific stretching conditions vary depending on the type of polymer, low melting point component, etc., but in any case, conditions must be selected that will not cause whitening.

Here, the term "temperature in the transition region" refers to the temperature range in which the resin composition changes from a glass state to a rubber state. The temperature in the rubbery region refers to a temperature lower than the temperature at which the resin composition melts and begins to flow, but higher than the transition region. These regions are obtained, for example, in the following manner, but are not limited to this method. When the elastic modulus of the resin composition is measured using a viscoelasticity spectrometer, a curve F as shown in FIG. 1 is obtained. Based on this,
The temperature of the transition zone, the temperature of the rubbery zone, is determined. The criterion is that the elastic modulus E' is 10'' in the transition region.
Region A is a high value of about (dyne/cd) and changes greatly with temperature to a small value of 10' (dyne/cJA) or less. For the rubbery region, the elastic modulus E' is between 10' and 10' (dyne/cd
] This is region B, which changes gradually with temperature.

Next, the first drawn product is rapidly cooled. This rapid cooling is one of the features of this invention. The quenching is performed by rapidly lowering the temperature to a temperature lower than the temperature of the transition region while holding the stretched product and before stress relaxation is completed. In this way, the resin composition may undergo phase separation or whitening. (Cold stretching is possible.)

Thereafter, the first stretched product is subjected to second stretching to obtain a stretched resin body in the form of a film or fiber. Performing this second stretching is also one of the features of the present invention. The second stretching is cold stretching performed at a temperature below the temperature of the transition region. In FIG. 1, the range is at a temperature below the temperature of the transition region. The stretching conditions such as the stretching temperature and magnification for the second stretching are appropriately selected according to the type of resin, resin composition, or low melting point component, etc., within a range that does not cause phase separation or whitening.

Excipients of resin compositions containing low melting point components are difficult to cold stretch as they are due to phase separation or whitening, and furthermore, it is difficult to improve mechanical strength by stretching at high temperatures above the temperature of the rubbery region. By producing a stretched product in the manner described above, the mechanical strength of the shaped body can be effectively improved and a stretched resin body with excellent mechanical properties can be obtained.

In addition, instead of performing the first stretching, the excipient may be rolled within the same temperature range using a rolling method, and the obtained rolled product may be rapidly cooled.Instead of performing the second stretching, ,
Further rolling may be performed within the same temperature range using a rolling method. In the above description, films and fibers are used as excipients of the resin composition, and a stretched resin body in the form of a film or a fiber is obtained. However, in the production method according to the present invention, the present invention is not limited to this. For stretching, stretching methods such as -axial stretching, two-wheel stretching, dry stretching, and wet stretching can be used.

Heat, radiation, and
The thermal properties, mechanical properties, and chemical resistance of the drawn product can be further improved by adding ultraviolet rays or the like to cause a crystallization or curing reaction of the drawn product.

When a stretched resin body in the form of a film or sheet is produced by the production method of the present invention, it can be used, for example, in the production of laminates, etc. Next, Examples and Comparative Examples will be explained (Example 1) A resin composition consisting of 90 parts by weight of polyvinyl chloride and 10 parts by weight of di(2-ethylhexyl phthalate) was molded into a sheet-like body with a thickness of 800 μm by an extrusion method. For this sheet-like material, the stretching temperature, speed, and magnification were 60℃ and 60℃, respectively.
3. After performing the first stretching under the condition of On1n-'.1.7, the stretched product was rapidly cooled to the temperature shown in Table 1 as the temperature for the second stretching while the stretched product was being held. This stretched product was further cold-stretched (secondary stretching) at a stretching temperature, speed, and magnification of 20°C, 1.5 m1n-', and 2.5 to obtain a resin stretched product.

(Example 2.3) Using the resin composition shown in Table 1, it was formed into a film by a casting method, and then the first stretching and second stretching were carried out as shown in Table 1. A stretched resin body was made in the same manner as in Example 1, except that the conditions shown were changed (Example 4.5) A stretched resin body was made in the same manner as in Example 2.3. After that, crosslinking treatment was performed by irradiating with 60 Mrad electron beam.
A cured stretched resin body (hereinafter, such a stretched resin body is referred to as a stretched cured body) was obtained.

(Comparative Example 1) A film was made in the same manner as in Example 2. This film was not subjected to any stretching or the like.

(Comparative Example 2) Using a film produced in the same manner as in Example 2, primary stretching was performed under the same conditions as in Example 2, but instead of rapid cooling, the film was slowly cooled while being held.

Next, an attempt was made to cold stretch the obtained stretched product, but the cold stretching was impossible due to the brittleness.

The stretched resin bodies obtained in Examples 1 to 3, the stretched and cured bodies obtained in Example 4.5, and the film obtained in Comparative Example 1 were tested for tensile strength and tensile strength according to the provisions of ASTM D638. Mechanical strength in terms of elastic modulus and elongation was measured. The results are shown in Table 1.

From Table 1, it can be seen that the stretched resin body obtained in Example 2 is different from the film obtained in Comparative Example 1, even though the resin composition having the same composition as that of the film obtained in Comparative Example 1 is used. It can be seen that the mechanical strength is superior to that of . Furthermore, it can be seen that the stretch-cured body obtained in Example 4 has even better mechanical strength. Furthermore, it can be seen that the stretched resin bodies and stretched cured bodies obtained in Example 1.3.5 also have excellent mechanical strength.

〔Effect of the invention〕

The method for producing a stretched resin body according to the present invention includes stretching or rolling a shaped body of a resin composition containing a low melting point component at a temperature higher than the temperature of the transition region of the resin composition and lower than the temperature of the rubbery region. Since the resin is rapidly cooled and further stretched or rolled at a temperature lower than the temperature of the transition region, a stretched resin body having excellent mechanical strength can be obtained.

[Brief explanation of drawings]

FIG. 1 is a graph showing the temperature-modulus curve of a polymer. A...Temperature range in the transition region B...Temperature range in the rubbery region C...Temperature range above the transition region temperature and below the rubbery region temperature D...Below the transition region temperature (glassy region) temperature range

Claims (2)

[Claims] (1) A shaped body of a resin composition containing a low melting point component is stretched or rolled at a temperature higher than the temperature of the transition region of the resin composition and lower than the temperature of the rubbery region, and then rapidly cooled, and further A method for producing a stretched resin body by stretching or rolling at a temperature below (2) The method for producing a stretched resin body according to claim 1, wherein the stretched or rolled resin body is stretched or rolled at a temperature lower than the temperature of the transition region, and then subjected to a curing reaction.