JP7070623B2 - Polyester resin composition - Google Patents

Description

The present invention relates to a polyester resin composition having excellent transparency, heat resistance, and stretchability.

Polyester is highly versatile because it has excellent properties such as heat resistance, mechanical strength, transparency, chemical resistance, and gas barrier properties, and it is also easily available at a price. Currently, it is used for beverages and foods. It is a resin widely used for containers, packaging materials, molded products, films, etc. Among them, polycyclohexylenedimethylene methylene terephthalate (PCT), which mainly contains terephthalic acid as an acid component and 1,4-cyclohexanedimethanol as a diol component, has a high melting point of 290 ° C. and a high crystallization rate. Therefore, it is widely used for injection molding applications that require heat resistance, and various studies have been made for biaxially stretched film applications. Biaxially stretched film using polycyclohexylenedimethylene methylene terephthalate is expected to be used in applications such as flexible substrates, ITO protective films, prism sheets for smartphones and tablets, and liquid crystal protective films by taking advantage of its heat resistance. Has been done. In these applications, since the temperature at the time of use becomes high, it is necessary to withstand a harsh heat resistance test of 80 to 200 ° C. × several minutes to several days.

For example, Patent Document 1 describes a biaxially stretch-oriented polyester film made of polycyclohexylenedimethylene methylene terephthalate, which is stretched or oriented at a specific stretching ratio and stretching temperature, and subsequently stretched at 260 ° C. or higher. Disclosed is a film having excellent heat resistance, which is heat-set while maintaining the dimensions of the stretched film at the actual film temperature of the above.

On the other hand, Patent Document 2 describes the polyester comprising (a) a terephthalic acid residue, (b) a 1,4-cyclohexanedimethanol residue, and (c) another dicarboxylic acid or diol residue. Disclosed is a biaxially stretched polyester film having excellent heat resistance.

Japanese Patent Publication No. 2005-530908 Japanese Patent Publication No. 2008-524396

However, the films disclosed in Patent Documents 1 and 2 have problems such as film shrinkage depending on the application used in a high temperature and long-term environment such as a flexible circuit board.
An object to be solved by the present invention is to solve the above-mentioned problems and to provide a polyester resin composition having excellent transparency, heat resistance, and stretchability. Another object of the present invention is to provide a polyester-based biaxially stretched film having excellent transparency and shrinkage resistance during heating.

The gist of the present invention is as follows.

[1] Polycyclohexylene methylene terephthalate resin containing 90 mol% or more of terephthalic acid unit as a dicarboxylic acid component (a-1) and 90 mol% or more of 1,4-cyclohexanedimethanol unit as a diol component (a-2). (A) 1 part by mass or more of the polyallylate resin (B) having a higher glass transition temperature measured according to JIS K7198A than the polycyclohexylenemethylene terephthalate resin (A) with respect to 100 parts by mass. A polyester resin composition containing a portion or less.
[2] The polyester resin composition according to [1], which has a single glass transition temperature.
[3] When the resin composition is heated to a temperature 30 ° C. higher than the crystal melting temperature using a differential scanning calorimeter (DSC) at a heating rate of 10 ° C./min and lowered at 10 ° C./min, the crystal melts. The polyester resin composition according to [2] or [3], wherein the difference between the temperature and the temperature lowering crystallization temperature is 40 ° C. or higher and 80 ° C. or lower.
[4] A polyester-based biaxially stretched film comprising the polyester resin composition according to any one of [1] to [3].
[5] Polycyclohexylene methylene terephthalate resin containing 90 mol% or more of terephthalic acid unit as the dicarboxylic acid component (a-1) and 90 mol% or more of 1,4-cyclohexanedimethanol unit as the diol component (a-2). (A) A method for producing a polyester resin composition, wherein the polyarylate resin (B) is melt-kneaded at a ratio of 1 part by mass or more and 50 parts by mass or less at 260 ° C. or higher and 350 ° C. or lower with respect to 100 parts by mass.

The polyester resin composition proposed by the present invention has improved heat resistance and stretchability without impairing the transparency of the polycyclohexylenedimethylene methylene terephthalate resin, and is a polyester-based biaxially stretched film obtained from this resin composition. Has excellent transparency and shrinkage resistance when heated, so that it can be suitably used for applications that require heat resistance and optical characteristics.

The outline of the results of the temperature dispersion measurement of dynamic viscoelasticity in crystalline resin materials is shown (quoted from Kenkichi Murakami (1986) "Easy Leology-From the Basics to the Cutting Edge-" Industrial Books).

Hereinafter, the present invention will be described in detail. However, the content of the present invention is not limited to the embodiments described below.

<Polyester resin composition>
The polyester resin composition according to an example of the embodiment of the present invention (hereinafter, may be referred to as “the present resin composition”) contains 90 mol% or more of terephthalic acid unit as the dicarboxylic acid component (a-1) and a diol component. Compared to the polycyclohexylene methylene terephthalate resin (A) with respect to 100 parts by mass of the polycyclohexylene dimethylene terephthalate resin (A) containing 90 mol% or more of 1,4-cyclohexanedimethanol unit as (a-2). It is a polyester resin composition containing 1 part by mass or more and 50 parts by mass or less of the polyallylate resin (B) having a high glass transition temperature.

As a method for improving the heat resistance of the polycyclohexylene dimethylene terephthalate resin, a method of adding a crystal nucleating agent for the purpose of improving crystallinity is known. In this method, the degree of crystallization is improved by adding the crystal nucleating agent, and the heat resistance is also improved accordingly, but the crystallization rate is generally improved, so that there is a problem that the stretchability is deteriorated.
Further, a method of promoting crystallization and improving heat resistance by performing heat treatment in an in-line process or an outline process is known, but there is a limit to the degree of crystallization that can be finally reached, and a process called heat treatment is performed. There is also the problem that productivity is reduced due to the addition.
In the present invention, it has been found that a polyallylate resin, which is an amorphous resin having a higher glass transition temperature than a polycyclohexylene dimethylene terephthalate resin, exhibits compatibility with a polycyclohexylene dimethylene terephthalate resin, and polycyclohexylene dimethylene is found. It has been found that a resin composition containing a terephthalate resin and a polyarylate resin exhibits excellent transparency, heat resistance, and stretchability.
Since the polyester resin composition of the present invention is extremely excellent in heat resistance, the polyester-based biaxially stretched film obtained from this resin composition is excellent in transparency and shrinkage resistance at the time of heating, and is used for applications requiring heat resistance and optical properties. Can also be suitably used.

It is important that the resin composition of the present invention contains 1 part by mass or more and 50% by mass or less of the polyarylate resin (B) with respect to 100 parts by mass of the polycyclohexylene methylene terephthalate resin (A).

In the resin composition of the present invention, it is important that the content ratio of the polyarylate resin (B) is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polycyclohexylene methylene terephthalate resin (A). It is preferably 3 parts by mass or more or 45 parts by mass or less, more preferably 5 parts by mass or more or 40 parts by mass or less, and further preferably 10 parts by mass or more or 35 parts by mass or less. When the proportion of the polyarylate resin (B) is 1 part by mass or more, the heat resistance of the resin composition of the present invention is sufficient, and the crystallization temperature can be lowered, so that the stretchability of the resin composition can be reduced. Is improved. On the other hand, when the proportion of the polyarylate resin (B) is 50 parts by mass or less, the crystallinity of the resin composition is maintained, and the shrinkage resistance of the obtained biaxially stretched film at the time of heating is sufficient.

The crystal melting temperature Tm of the polyester resin composition can be measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC) according to JIS K7121 (2012), and is at 200 ° C. or higher, 350. It is preferably 210 ° C. or higher, 340 ° C. or lower, more preferably 220 ° C. or higher and 330 ° C. or lower, further preferably 230 ° C. or higher and 320 ° C. or lower, and 240 ° C. or higher. It is particularly preferable that the temperature is 310 ° C. or lower, and it is particularly preferable that the temperature is 250 ° C. or higher and 300 ° C. or lower. As long as the crystal melting temperature Tm of the polyester resin composition is within the range, the polyester resin composition has an excellent balance between heat resistance and melt moldability.

(1) Glass transition temperature This resin composition preferably has a single glass transition temperature. Having a single glass transition temperature means that the temperature dispersion of dynamic viscoelasticity is measured under the conditions of strain 0.1%, frequency 10 Hz, and heating rate 3 ° C./min (dynamic viscoelasticity measurement by JIS K7198A method). This resin composition means that there is only one peak of the main dispersion of the loss tangent (tan δ). If the glass transition temperature of the resin composition is single, the resins contained in the resin composition are compatible with each other, resulting in a transparent polyester resin composition.

Here, the main variance will be further described. As shown in FIG. 1, in general, when the temperature of the crystalline resin is gradually increased from a low temperature, the thermal motion of the entire side chain (γ dispersion), the local motion of the main chain (β dispersion), and the amorphous region Peaks corresponding to relaxation mechanisms such as microBrownian motion (αa dispersion) of the main chain, motion of molecular chains in the crystal (αc dispersion), melting, and flow are observed. Among these, the micro Brownian motion (αa dispersion) of the main chain in the amorphous region is called main dispersion because the activation energy is higher than that of other relaxation mechanisms and the corresponding peak is also large. The low temperature mitigation mechanism is called subdispersion). Since the glass transition temperature is the temperature at which the microBrownian motion of the main chain occurs in the amorphous region, it can be said that the peak of the main dispersion in the temperature dispersion measurement of dynamic viscoelasticity indicates the glass transition temperature. ..

Next, the dynamic viscoelastic behavior of the polymer blend system will be described. Polymer blend systems are divided into compatible and incompatible combinations.
The compatible system means a system in which two or more kinds of resins to be mixed are completely mixed at the molecular level. At this time, the amorphous region mixed at the molecular level can be regarded as a single phase, and microBrownian motion also occurs at a single temperature. Therefore, in the case of a compatible system, the glass transition temperature is single and the peak of the main dispersion is also single. Further, the temperature takes a value in a range between the respective resins to be blended, depending on the blend ratio.
On the other hand, in the case of the incompatible system, the two or more kinds of resins to be mixed are not mixed and exist as a two-phase system (or more). Therefore, there are two or more main dispersion peaks indicating the glass transition temperature at the same positions as each of the blended resins. In the case of incompatibility, if the refractive indexes of the respective resins are not very close to each other, light is scattered at the interface between the matrix and the domain, and the transparency of the resin composition is impaired. In addition, when an external force such as tension or bending is applied, peeling occurs at the interface, which causes deterioration of mechanical properties and whitening. Further, in the production of a stretched film, interfacial peeling occurs during stretching, which causes breakage and whitening.
In the present invention, since the resins constituting the present resin composition are compatible with each other, the present resin composition and the molded product obtained by using the composition have excellent transparency.

When the glass transition temperature of the present resin composition is single, the temperature is preferably 110 ° C. or higher and 300 ° C. or lower, more preferably 115 ° C. or higher or 290 ° C. or lower, and 120 ° C. or higher or 280 ° C. or higher. It is more preferably ° C. or lower, particularly preferably 125 ° C. or higher or 270 ° C. or lower, and particularly preferably 130 ° C. or higher or 260 ° C. or lower. As long as the glass transition temperature of the present resin composition is within the range, the present resin composition has an excellent balance between heat resistance and stretch moldability.
The glass transition temperature is the main loss tangent (tan δ) measured at a strain of 0.1%, a frequency of 10 Hz, and a heating rate of 3 ° C./min using a temperature dispersion measurement of dynamic viscoelasticity according to JIS K7198A. Evaluated at the peak of the variance.

(2) Heat of Crystal Melting The heat of crystal melting ΔHm of this resin composition is preferably 25 J / g or more and 50 J / g or less, more preferably 26 J / g or more or 45 J / g or less, and 27 J / g or more. Alternatively, it is more preferably 40 J / g or less. When ΔHm is 25 J / g or more, the present resin composition has sufficient crystallinity and is excellent in shrinkage resistance when the obtained biaxially stretched film is heated. On the other hand, when ΔHm is 50 J / g or less, the crystallinity of the present resin composition is also suitable for stretch moldability.
The amount of heat of crystal melting ΔHm of this resin composition is measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC) according to JIS K7121 (2012).

(3) Difference between crystal melting temperature and temperature lowering crystallization temperature As a guideline for making the crystallization rate of this resin composition preferable, a differential scanning calorimeter (DSC) is used to heat this resin composition at a heating rate of 10 ° C./min. The crystal melting temperature and the temperature-decreased crystallization temperature when the temperature of the crystallization peak when the temperature is raised to 30 ° C. higher than the crystal melting temperature and the temperature is lowered at 10 ° C./min is defined as the temperature-decreasing crystallization temperature. The difference is used. The difference between the crystal melting temperature and the temperature lowering crystallization temperature is preferably 40 ° C. or higher and 80 ° C. or lower, preferably 45 ° C. or higher or 75 ° C. or lower, and further preferably 50 ° C. or higher or 70 ° C. or lower. .. If the difference between the crystal melting temperature and the temperature-decreasing crystallization temperature is 40 ° C. or more, the crystallization of the present resin composition is not too fast, and the crystals are sufficiently crystallized during the quenching process with the casting roll in the manufacturing process of the biaxially stretched film. Since an amorphous sheet having low properties is obtained and crystallization is not rapidly promoted even in the subsequent stretching process, troubles such as breakage are less likely to occur and the stretchability is excellent. On the other hand, if the difference between the crystal melting temperature and the temperature-decreasing crystallization temperature is 80 ° C. or less, the crystallization rate is not too slow. Therefore, crystallization is completed in the heat treatment process after stretching, and a biaxially stretched film having excellent heat resistance is obtained. You can get it.

In the present invention, the resin composition contains a resin other than the polycyclohexylene methylene terephthalate resin (A) and the polyallylate resin (B) as long as the effects of the present invention are not impaired. It can be tolerated.
Other resins include polystyrene-based resins, polyvinyl chloride-based resins, polyvinylidene chloride-based resins, chlorinated polyethylene-based resins, polyester-based resins, polycarbonate-based resins, polyamide-based resins, polyacetal-based resins, acrylic resins, and ethylene acetate. Vinyl copolymer, polymethylpentene resin, polyvinyl alcohol resin, cyclic olefin resin, polylactic acid resin, polybutylene succinate resin, polyacrylonitrile resin, polyethylene oxide resin, cellulose resin, polyimide resin , Polyurethane resin, polyphenylene sulfide resin, polyphenylene ether resin, polyvinyl acetal resin, polybutadiene resin, polybutene resin, polyamideimide resin, polyamide bismaleimide resin, polyetherimide resin, polyether ether ketone Examples thereof include resins, polyether ketone resins, polyether sulfone resins, polyketone resins, polysulfone resins, aramid resins, and fluororesins.

Further, in the present invention, in addition to the above-mentioned components, the present resin composition may appropriately contain additives that are generally blended, as long as the effects of the present invention are not significantly impaired. The additives include recycled resins generated from trimming losses such as ears, silica, talc, kaolin, and calcium carbonate, which are added for the purpose of improving and adjusting the molding processability, productivity, and various physical properties of the porous film. Inorganic particles such as titanium oxide, pigments such as carbon black, flame retardants, weather resistance stabilizers, heat stabilizers, antistatic agents, melt viscosity improvers, cross-linking agents, lubricants, nucleating agents, plasticizers, antiaging agents, etc. Additives such as antioxidants, light stabilizers, UV absorbers, neutralizers, antifogging agents, antiblocking agents, lubricants, and colorants can be mentioned.

Hereinafter, the polycyclohexylene methylene terephthalate resin (A) and the polyarylate resin (B) constituting the present resin composition will be described.

<Polycyclohexylenedimethylene methylene terephthalate resin (A)>
The polycyclohexylene methylene terephthalate resin is a resin containing terephthalic acid and 1,4-cyclohexanedimethanol as main components. In particular, the polycyclohexylenemethylene terephthalate resin (A) used in the present invention contains 90 mol% or more of terephthalic acid units as the dicarboxylic acid component (a-1) and 1,4-cyclohexanedimethanol as the diol component (a-2). A resin containing 90 mol% or more of methanol units.

It is important that the dicarboxylic acid component (a-1) constituting the polycyclohexylenedimethylene methylene terephthalate resin (A) contains 90 mol% or more of terephthalic acid. Of the dicarboxylic acid components (a-1), terephthalic acid is preferably 92 mol% or more, more preferably 94 mol% or more, further preferably 96 mol% or more, and 98 mol% or more. It is particularly preferable that all (100 mol%) of the dicarboxylic acid component (a-1) is terephthalic acid. By using 90 mol% or more of terephthalic acid as the dicarboxylic acid component (a-1), the glass transition temperature, melting point, and crystallinity of the polycyclohexylenedimethylene methylene terephthalate resin (A) are improved, and thus the present resin. The heat resistance of the composition is improved.

The polycyclohexylene methylene terephthalate resin (A) may be copolymerized with an acid component other than terephthalic acid in an amount of less than 10 mol% for the purpose of improving moldability and heat resistance. Specifically, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,5-furandicarboxylic acid, 2,4-frangicarboxylic acid. , 3,4-Frangicarboxylic acid, benzophenone dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenylether dicarboxylic acid and other aromatic dicarboxylic acids; cyclohexanedicarboxylic acid, Examples thereof include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, and sebacic acid. Among these, isophthalic acid, 2, 5-Frangicarboxylic acid, 2,4-frangicarboxylic acid and 3,4-frangicarboxylic acid are preferable.

It is important that the diol component (a-2) constituting the polycyclohexylene dimethylene terephthalate resin (A) contains 90 mol% or more of 1,4-cyclohexanedimethanol. Of the diol components (a-2), 1,4-cyclohexanedimethanol is preferably 92 mol% or more, more preferably 94 mol% or more, still more preferably 96 mol% or more. It is particularly preferable that the content is 98 mol% or more, and it is particularly preferable that all (100 mol%) of the diol component (a-2) is 1,4-cyclohexanedimethanol. By adjusting the diol component (a-2) to 90 mol% or more of 1,4-cyclohexanedimethanol, the compatibility with the polyallylate resin (B) is improved, and further, the polycyclohexylene methylene terephthalate resin (A) is improved. ), The melting point and crystallinity are improved, and the heat resistance of the present resin composition is improved.

The polycyclohexylene methylene terephthalate resin (A) may be copolymerized with a diol component other than 1,4-cyclohexanedimethanol in an amount of less than 10 mol% for the purpose of improving moldability and heat resistance. Specifically, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, diethylene glycol, and tri. Ethylene glycol, polyalkylene glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, hydroquinone, bisphenol, spiroglycol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, isosorbide Among these, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,3-cyclohexanedimethanol are preferable from the viewpoint of moldability.

The crystal melting temperature Tm (A) of the polycyclohexylene dimethylene terephthalate resin (A) is preferably 250 ° C. or higher and 350 ° C. or lower, more preferably 260 ° C. or higher or 340 ° C. or lower, and 270 ° C. or higher or 330 ° C. or higher. The temperature is more preferably 280 ° C or higher or 320 ° C or lower. As long as the crystal melting temperature Tm (A) of the polycyclohexylene dimethylene terephthalate resin (A) is within the range, the polycyclohexylene dimethylene terephthalate resin (A) is excellent in the balance between heat resistance and melt moldability.
The crystal melting temperature Tm (A) of the polycyclohexylenedimethylene methylene terephthalate resin (A) shall be measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC) according to JIS K7121 (2012). Can be done.

The amount of heat of crystal fusion ΔHm (A) of the polycyclohexylenedimethylene methylene terephthalate resin (A) is preferably 25 J / g or more and 55 J / g or less, and more preferably 30 J / g or more or 50 J / g or less. It is more preferably 35 J / g or more or 45 J / g or less. Within the range of ΔHm (A), the polycyclohexylene methylene terephthalate resin (A) has appropriate crystallinity excellent in heat resistance, melt moldability, and stretchability.
The amount of heat of crystal melting ΔHm (A) of the polycyclohexylenedimethylene methylene terephthalate resin (A) shall be measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC) according to JIS K7121 (2012). Can be done.

The glass transition temperature Tg (A) of the polycyclohexylene dimethylene terephthalate resin (A) is more preferably 60 ° C. or higher and 150 ° C. or lower, and further preferably 70 ° C. or higher or 120 ° C. or lower. If the glass transition temperature Tg (A) of the polycyclohexylene dimethylene terephthalate resin (A) is within the range, the balance between heat resistance and melt moldability is excellent.
The glass transition temperature Tg (A) of the polycyclohexylene methylene terephthalate resin (A) has a strain of 0.1%, a frequency of 10 Hz, and a temperature rise rate of 3 using a temperature dispersion measurement of dynamic viscoelasticity according to JIS K7198A. It can be evaluated by the peak of the main dispersion of the loss tangent (tan δ) measured at ° C / min.

<Polyarylate resin (B)>
The present resin composition contains a polyarylate resin (B) having a higher glass transition temperature measured according to JIS K7198A than the polycyclohexylene methylene terephthalate resin (A).
The polycyclohexylene methylene terephthalate resin is a polycondensate of an aromatic dicarboxylic acid and a divalent phenol.

The dicarboxylic acid component (b-1) constituting the polyarylate resin (B) is not particularly limited as long as it is a divalent aromatic carboxylic acid, but it is a mixture of a terephthalic acid component and an isophthalic acid component. Is preferable.
The mixing ratio of the terephthalic acid component and the isophthalic acid component is preferably terephthalic acid / isophthalic acid = 99/1 to 1/99 mol%, more preferably 90/10 to 10/90 mol%. It is more preferably 80/20 to 20/80 mol%, particularly preferably 70/30 to 30/70 mol%, and particularly preferably 60/40 to 40/60 mol%. By containing terephthalic acid and isophthalic acid as the dicarboxylic acid component (b-1) in such a range, the polyarylate resin (B) is excellent in heat resistance and melt moldability.

The polyarylate resin (B) may be copolymerized with an acid component other than terephthalic acid and isophthalic acid as a dicarboxylic acid component. Specifically, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 3,3'- Aromatic dicarboxylic acids such as diphenyldicarboxylic acid and 4,4'-diphenylether dicarboxylic acid, cyclohexanedicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Examples thereof include aliphatic dicarboxylic acids such as. The copolymerization ratio is preferably less than 10 mol% so as not to impair the heat resistance of the polyarylate resin (B).

The bisphenol component (b-2) constituting the polyarylate resin (B) is not particularly limited as long as it is a divalent phenol, but it may be any of the bisphenol A component, the bisphenol TMC component, or the bisphenol A. It is preferable to include any of bisphenol. In general, a polyarylate resin having excellent melt moldability (fluidity) can be obtained by containing a bisphenol A component. On the other hand, by containing the bisphenol TMC component, the glass transition temperature is improved and the polyarylate resin (B) having excellent heat resistance is obtained. When it is desired to balance the melt moldability and the heat resistance, both the bisphenol A component and the bisphenol TMC component are used. In this case, the ratio of the bisphenol A component and the bisphenol TMC component is preferably in the range of bisphenol A / bisphenol TMC = 99/1 to 1/99 mol%, and is preferably 90/10 to 10/90 mol%. More preferably, it is more preferably 80/20 to 20/80 mol%, particularly preferably 70/30 to 30/70 mol%, and particularly preferably 60/40 to 40/60 mol%. .. By setting the ratio of the bisphenol A component and the bisphenol TMC component within such a range, the polyarylate resin (B) having an excellent balance between heat resistance and melt moldability can be obtained.

The polyarylate resin (B) contains bisphenol A (2,2-bis (4-hydroxyphenyl) propane) and bisphenol TMC (1,1-bis (4-hydroxyphenyl) -3) as bisphenol components (b-2). , 3,5-trimethylcyclohexane) may be copolymerized with bisphenol components. Specifically, bisphenol AP (1,1-bis (4-hydroxyphenyl) -1-phenylethane), bisphenol AF (2,2-bis (4-hydroxyphenyl) hexafluoropropane), bisphenol B (2, 2-Bis (4-hydroxyphenyl) butane), bisphenol BP (bis (4-hydroxyphenyl) diphenylmethane), bisphenol C (2,2-bis (3-methyl-4-hydroxyphenyl) propane), bisphenol E (1) , 1-bis (4-hydroxyphenyl) ethane), bisphenol F (bis (4-hydroxyphenyl) methane), bisphenol G (2,2-bis (4-hydroxy-3-isopropylphenyl) propane), bisphenol M ( 1,3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene), bisphenol S (bis (4-hydroxyphenyl) sulfone), bisphenol P (1,4-bis (2- (4-hydroxy)) Phenyl) -2-propyl) benzene), bisphenol PH (5,5'-(1-methylethylidene) -bis [1,1'-(bisphenyl) -2-ol] propane), bisphenol Z (1,1) -Bis (4-hydroxyphenyl) cyclohexane) and the like. The copolymerization ratio is preferably less than 10 mol% so as not to impair the heat resistance of the polyarylate resin (B).

The polyarylate resin (B) used in the present invention has a terephthalic acid component as a dicarboxylic acid component (b-1) from the viewpoint of enhancing compatibility with polycyclohexylene methylene terephthalate and obtaining a resin composition having excellent transparency. It is preferable to select either a bisphenol A component or a bisphenol TMC component, or a mixture of bisphenol A and bisphenol, as the mixture of the bisphenol component and the isophthalic acid component as the bisphenol component (b-2).

It is important that the polyarylate resin (B) used in the present invention has a higher glass transition temperature than the polycyclohexylenedimethylene methylene terephthalate resin (A). The difference in the glass transition temperature is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, further preferably 80 ° C. or higher, particularly preferably 90 ° C. or higher, and particularly preferably 100 ° C. or higher. It is especially preferable to have it.
The glass transition temperature of the polyarylate resin (B) is preferably 150 ° C. or higher and 350 ° C. or lower, more preferably 160 ° C. or higher or 340 ° C. or lower, and further preferably 170 ° C. or higher or 330 ° C. or lower. , 180 ° C. or higher or 320 ° C. or lower is particularly preferable, and 190 ° C. or higher or 300 ° C. or lower is particularly preferable. When the glass transition temperature of the polyarylate resin (B) satisfies the above, the present resin composition having an improved glass transition temperature and excellent melt moldability can be obtained.

The polyarylate resin (B) used in the present invention may be blended with a polycarbonate resin for the purpose of improving melt moldability. Since the polyarylate resin (B) and the polycarbonate resin show a compatibility system, by blending the polycarbonate resin with the polyarylate resin (B), the glass of the polyarylate resin (B) is maintained in transparency and mechanical properties. The transition temperature can be lowered, and as a result, the melt formability can be improved.
When the polyallylate resin (B) and the polycarbonate resin are blended, the mixing ratio thereof is preferably polyallylate resin (B) / polycarbonate resin = 99/1 to 50/50% by mass, and 98/2 = 60/40. It is more preferably 97/3 to 70/30% by mass, more preferably 96/5 to 80/20% by mass, and particularly preferably 96/5 to 80/20% by mass. As long as the mixing ratio of the polyarylate resin (B) and the polycarbonate resin is within the range, the melt moldability can be improved while maintaining the heat resistance of the polyarylate resin (B).

<Manufacturing method of polyester resin composition>
The method for producing the polyester resin composition of the present invention (hereinafter referred to as "method for producing the present resin composition") will be described, but the following description is an example of the method for producing the present resin composition, and the following description is an example of the method for producing the present resin composition. The composition is not limited to the present resin composition produced by such a production method.

In the method for producing the present resin composition according to an example of the embodiment of the present invention, the dicarboxylic acid component (a-1) contains 90 mol% or more of terephthalic acid units, and the diol component (a-2) contains 1,4-cyclohexanedi. 260 ° C. or higher and 350 ° C. or lower at a ratio of 1 part by mass or more and 50 parts by mass or less of the polyarylate resin (B) to 100 parts by mass of the polycyclohexylene methylene terephthalate resin (A) containing 90 mol% or more of methanol units. It is a method for producing a polyester resin composition which is melt-kneaded with.

In the method for producing the present resin composition, a part of each of the polycyclohexylene dimethylene terephthalate resin (A) and the polyarylate resin (B) undergoes an ester exchange reaction to obtain the polycyclohexylene dimethylene terephthalate resin (A). It is considered that the interfacial tension between the polyarylate resin (B) is significantly reduced and compatible with each other to obtain a polyester resin composition having excellent transparency and heat resistance.

The method for kneading the above resin is not particularly limited, but in order to obtain the present resin composition as easily as possible, it is preferably produced by melt-kneading using an extruder.
Further, in order to uniformly mix the polycyclohexylene methylene terephthalate resin (A) and the polyarylate resin (B), it is preferable to melt-knead them using a twin-screw extruder in the same direction.
The kneading temperature must be equal to or higher than the glass transition temperature of all the resins used, and for crystalline resins, to be equal to or higher than the crystal melting temperature of the resins. When the kneading temperature is as high as possible with respect to the glass transition temperature and crystal melting temperature of the resin to be used, the ester exchange reaction of a part of the resin is likely to occur and the compatibility is likely to be improved, but the kneading temperature is higher than necessary. This is not preferable because the resin is decomposed. From this, the kneading temperature is 260 ° C. or higher and 350 ° C. or lower, preferably 270 ° C. or higher and 340 ° C. or lower, more preferably 280 ° C. or higher and 330 ° C. or lower, and particularly preferably 290 ° C. or higher and 320 ° C. or lower. As long as the kneading temperature is high, the compatibility and melt moldability can be improved without causing decomposition of the resin.

The obtained resin composition can be molded by a general molding method, for example, extrusion molding, injection molding, blow molding, vacuum molding, pressure molding, press molding or the like to produce a biaxially stretched film. In each molding method, the apparatus and processing conditions are not particularly limited.

<Polyester-based biaxially stretched film and its manufacturing method>
Hereinafter, a polyester-based biaxially stretched film made of the present resin composition (hereinafter, may be referred to as “the present film”) will be described. The above resin composition can be molded by a general molding method, for example, extrusion molding, injection molding, blow molding, vacuum molding, pressure molding, press molding or the like to produce a biaxially stretched film. In each molding method, the apparatus and processing conditions are not particularly limited.
This film is preferably produced, for example, by the following method.

A film that is substantially amorphous and not oriented from the present resin composition described above (hereinafter, may be referred to as “unstretched film”) is produced by an extrusion method. For the production of this unstretched film, for example, an extrusion method is adopted in which the raw material is melted by an extruder, extruded from a flat die or an annular die, and then rapidly cooled to form a flat or annular unstretched film. I can do things. At this time, depending on the case, a laminated structure using a plurality of extruders may be used.

Next, the above-mentioned unstretched film is usually subjected to at least 1.1 to one direction in the flow direction (longitudinal direction) of the film and in the direction perpendicular to the flow direction (horizontal direction) from the viewpoint of stretching effect, film strength and the like. It is stretched 5.0 times, preferably in the range of 1.1 to 5.0 times in each of the vertical and horizontal directions.

As the biaxial stretching method, conventionally known stretching methods such as tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, and tubular simultaneous biaxial stretching can be adopted. For example, in the case of the tenter-type sequential biaxial stretching method, the unstretched film is heated to a temperature range of Tg to Tg + 50 ° C. with the glass transition temperature of the present resin composition as Tg, and is longitudinally oriented by a roll-type longitudinal stretching machine. It can be manufactured by stretching 1.1 to 5.0 times in the lateral direction using a tenter type transverse stretching machine within a temperature range of Tg to Tg + 50 ° C. can. In the case of the tenter type simultaneous biaxial stretching method or the tubular type simultaneous biaxial stretching method, for example, in the temperature range of Tg to Tg + 50 ° C., the film is stretched 1.1 to 5.0 times in each axial direction at the same time in the vertical and horizontal directions. Can be manufactured by.

The biaxially stretched film stretched by the above method is continuously heat-fixed. Dimensional stability at room temperature can be imparted by heat fixing. In this case, the treatment temperature is preferably selected in the range of the crystal melting temperature Tm-1 to 50 ° C. of the present resin composition. If the heat fixing temperature is within the above range, heat fixing is sufficiently performed, stress during stretching is relaxed, sufficient heat resistance and mechanical properties are obtained, and there are no troubles such as breakage or whitening of the film surface. The film is obtained.

In the present invention, in order to relieve the stress of crystallization shrinkage due to heat fixing, relaxation is sufficiently performed in the range of 0 to 15%, preferably 3 to 10% in the width direction during heat fixing. Since the film is uniformly relaxed in the width direction, the shrinkage rate in the width direction is uniform and a film having excellent room temperature dimensional stability can be obtained. Further, since the film is relaxed according to the shrinkage of the film, there is no film tarmi, no fluttering in the tenter, and no breakage of the film.

The thickness of the biaxially stretched film of the present invention is preferably 1 to 200 μm, more preferably 5 to 150 μm. By setting it to 1 μm or more, the film strength is kept within the practical range.

When the biaxially stretched film of the present invention is heat-treated at 200 ° C. for 30 minutes, the heat shrinkage rate is preferably 2% or less in both the vertical direction (MD) and the horizontal direction (TD). As long as the heat shrinkage of the biaxially stretched film of the present invention is within such a range, it has sufficient heat resistance to be used as a film.

The haze value of the biaxially stretched film of the present invention is preferably 5% or less, more preferably 4% or less, further preferably 3% or less, and particularly preferably 2% or less. It is particularly preferable that it is 1% or less. If the haze value of the biaxially stretched film of the present invention is within such a range, it has sufficient transparency for use as a film.
The haze value in the present invention can be calculated by the following formula.
[Haze] = ([Diffusion transmittance] / [Total light transmittance]) × 100

Examples are shown below, but these do not limit the invention in any way.

(1) Glass transition temperature Using a viscoelastic spectrometer DVA-200 (manufactured by IT Measurement Control Co., Ltd.), strain 0.1%, frequency 10 Hz, temperature rise rate 3 ° C / according to JIS K7244 (1999). The peak temperature of the main dispersion of the loss tangent (tan δ) was measured using the temperature dispersion measurement of dynamic viscoelasticity in minutes. Those having a single peak and having a peak temperature of 110 ° C. or higher and 300 ° C. or lower were evaluated as acceptable (◯), and those outside this range were evaluated as rejected (x).

(2) Crystal melting temperature, crystal melting enthalpy, crystallization temperature at lower temperature The obtained cast film was heated at a heating rate of 10 using Diamond DSC (manufactured by Perkin Elmer Japan) in accordance with JIS K7121 (2012). The crystal melting temperature and crystal melting enthalpy in the heating process were measured at ° C / min. Those having a crystal melting enthalpy of 25 J / g or more and 50 J / g or less were evaluated as acceptable (◯), and those outside this range were evaluated as rejected (x). After raising the temperature to a temperature 30 ° C. higher than the crystal melting temperature, the temperature of the crystallization peak when the temperature was lowered at 10 ° C./min was measured, and the crystallization rate was evaluated from the difference from the crystal melting temperature. Those having a difference between the crystal melting temperature and the temperature lowering crystallization temperature of 40 ° C. or higher and 80 ° C. or lower were evaluated as acceptable (◯), and those outside this range were rejected (x).

(3) Formability Regarding the cast film, those that could be stretched without any problem when biaxially stretched were evaluated as acceptable (◯), and those that were broken were evaluated as rejected (×).

(4) Heat Shrinkage Rate A biaxially stretched film was heated at 200 ° C. for 30 minutes using a heat treatment oven baking test device (manufactured by Daiei Kagaku Seisakusho Co., Ltd.), and the shrinkage rate after heating was measured. Those with a shrinkage rate of 2% or less were evaluated as acceptable (◯), and those with a shrinkage rate of more than 2% were evaluated as rejected (×).

(5) Haze haze meter NDH-5000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) was used to measure the total light transmittance and diffusion transmittance based on JIS K7136 (2000), and the haze was calculated by the following formula. bottom.
[Haze] = ([Diffusion transmittance] / [Total light transmittance]) × 100
Those with a haze of 5% or less were regarded as acceptable (○), and those with a haze of more than 5% were regarded as rejected (×).

[Polycyclohexylenedimethylene methylene terephthalate resin (A)]
(A) -1: SKYPURA0502
(Manufactured by SK Chemical Co., Ltd., dicarboxylic acid component: terephthalic acid = 100 mol%, diol component: 1,4-cyclohexanedimethanol = 100 mol%, Tm (A) = 286 ° C., ΔHm (A) = 42J / g, Tg (A) = 104 ° C.)

[Polyarylate resin (B)]
(B) -1: U polymer U-100
(Manufactured by Unitika Ltd., dicarboxylic acid component: terephthalic acid / isophthalic acid = 50/50 mol%, bisphenol component: bisphenol A = 100 mol%, Tg (B) = 210 ° C.)

(B) -2: U polymer T-240AF
(Manufactured by Unitica, dicarboxylic acid component: terephthalic acid / isophthalic acid = 50/50 mol%, bisphenol component: bisphenol A / bisphenol TMC = 60/40 mol%, Tg (B) = 244 ° C.)

(B) -3: U polymer T-200
(Manufactured by Unitika Ltd., dicarboxylic acid component: terephthalic acid / isophthalic acid = 50/50 mol%, bisphenol component: bisphenol TMC = 100 mol%, Tg (B) = 286 ° C.)

(B) -4: U polymer T-1000
(Unitika Ltd., U polymer T-200 / polycarbonate resin = 90/10% by mass mixture, Tg (B) = 272 ° C.)

(Reference example 1)
Pellet-shaped (A) -1 was added in a ratio of 25 parts by mass to 100 parts by mass, and after dry blending, pellet-shaped (B) -1 was added to a Φ25 mm twin-screw extruder set at 300 ° C. The film was melt-kneaded, extruded as a film from the inside of the T-die, adhered to a cast roll at 20 ° C. and rapidly cooled to obtain a cast film having a thickness of 450 μm. For this cast film, the crystal melting temperature, the amount of heat of crystal melting, the temperature-decreasing crystallization temperature, and the glass transition temperature were evaluated.
Subsequently, the obtained cast film was passed through a longitudinal stretching machine and stretched three times in the longitudinal direction (MD) at 125 ° C. Subsequently, the obtained longitudinally stretched film was passed through a transverse stretching machine (tenter), and stretched three times in the transverse direction (TD) at a preheating temperature of 125 ° C., a stretching temperature of 130 ° C., and a heat fixing temperature of 260 ° C. The heat shrinkage and haze of the obtained biaxially stretched film were measured. The results are shown in Table 1.

(Example 2)
Reference Example 1 except that (B) -2 was used instead of (B) -1, the molding temperature was 320 ° C, the longitudinal stretching temperature was 132 ° C, the preheating temperature was 132 ° C, and the transverse stretching temperature was 142 ° C. Samples were prepared and evaluated in the same manner. The results are shown in Table 1.

(Example 3)
Reference Example 1 except that (B) -3 was used instead of (B) -1, the molding temperature was 330 ° C, the longitudinal stretching temperature was 140 ° C, the preheating temperature was 140 ° C, and the transverse stretching temperature was 150 ° C. Samples were prepared and evaluated in the same manner. The results are shown in Table 1.

(Example 4)
Reference Example 1 except that (B) -4 was used instead of (B) -1, the molding temperature was 330 ° C, the longitudinal stretching temperature was 138 ° C, the preheating temperature was 138 ° C, and the transverse stretching temperature was 148 ° C. Samples were prepared and evaluated in the same manner. The results are shown in Table 1.

(Reference example 5)
(A) -1 was added at a ratio of 10 parts by mass to 100 parts by mass, and the longitudinal stretching temperature was 114 ° C., the preheating temperature was 114 ° C., and the transverse stretching temperature was 124 ° C. Samples were prepared and evaluated in the same manner as in Reference Example 1. The results are shown in Table 1.

(Reference example 6)
Except for the addition of (A) -1 to 100 parts by mass and (B) -1 at a ratio of 40 parts by mass, the longitudinal stretching temperature was 134 ° C, the preheating temperature was 134 ° C, and the transverse stretching temperature was 144 ° C. Samples were prepared and evaluated in the same manner as in Reference Example 1. The results are shown in Table 1.

(Comparative Example 1)
When (A) -1 was used alone and a sample was prepared in the same manner as in Reference Example 1 except that the longitudinal stretching temperature was 104 ° C, the preheating temperature was 104 ° C, and the transverse stretching temperature was 114 ° C, the transverse stretching was performed. A break occurred in the process. The evaluation results are shown in Table 1.

(Comparative Example 2)
When a sample was prepared in the same manner as in Comparative Example 1 except that the film was stretched 2.5 times in the vertical direction (MD) and 2.5 times in the horizontal direction (TD), a biaxially stretched film was obtained without any problem. Was done. The evaluation results are shown in Table 1.

(Comparative Example 3)
Except for the addition of (A) -1 to 100 parts by mass of (B) -1 at a ratio of 100 parts by mass, the longitudinal stretching temperature was 157 ° C, the preheating temperature was 157 ° C, and the transverse stretching temperature was 167 ° C. Samples were prepared and evaluated in the same manner as in Reference Example 1. The results are shown in Table 1.

In Reference Example 1 and Examples 2 to 4, 25 parts by mass of a polyarylate resin having a different bisphenol component or a polyarylate resin containing polycarbonate was added to 100 parts by mass of the polycyclohexylene methylene terephthalate resin (A). ing. It can be seen that the obtained resin composition has an improved glass transition temperature as compared with the polycyclohexylenedimethylene methylene terephthalate resin (A) alone, and is more excellent in heat resistance. Further, it can be seen that this resin composition can produce a biaxially stretched film without any particular problem, and the obtained biaxially stretched film is excellent in transparency and heat resistance during heating.
In Reference Example 5, the mixing ratio of the polyarylate resin (B) to 100 parts by mass of the polycyclohexylene methylene terephthalate resin (A) is 10 parts by mass. A resin composition showing excellent transparency and stretchability, although the effect of improving the glass transition temperature is small and the heat resistance is slightly lowered because the compounding ratio of the polyarylate resin (B) is smaller than that of Reference Example 1. Has been obtained.
In Reference Example 6, the compounding ratio of the polyarylate resin (B) to 100 parts by mass of the polycyclohexylene methylene terephthalate resin (A) is 40 parts by mass. Since the compounding ratio of the polyarylate resin (B) is larger than that of Reference Example 1, the crystallinity of the resin composition is lowered, and the heat resistance is slightly lowered, but excellent transparency and stretchability are obtained. The resin composition shown is obtained.
In Comparative Examples 1 and 2, the polycyclohexylenedimethylene methylene terephthalate resin (A) is used alone. Since the difference between the crystal melting temperature and the temperature-decreasing crystallization temperature is small, it can be seen that this resin composition is a resin composition having high crystallinity and a high crystallization rate. In Comparative Example 1, since a sheet having high crystallinity was obtained in the quenching process with the casting roll, it is considered that the sheet was broken when it was stretched at the same magnification as that of the example. On the other hand, in Comparative Example 2, although the stretching ratio is lower than that of Examples and Comparative Example 1, stretching is possible, but since the resin composition does not contain polyarylate resin, the glass transition temperature of the resin composition is low, which is obtained. The heat shrinkage rate of the axially stretched film is large. That is, the heat resistance is reduced.
In Comparative Example 3, the mixing ratio of the polyarylate resin (B) to 100 parts by mass of the polycyclohexylene methylene terephthalate resin (A) is 100 parts by mass. It can be seen that this resin composition is a resin composition having a low crystallization rate and a low degree of crystallization because the difference between the crystal melting temperature and the temperature-decreasing crystallization temperature is large and the amount of heat for crystal melting is small. The biaxially stretched film using the resin composition does not sufficiently crystallize during heat fixation during production, and even if it does occur, the absolute crystallinity is low, so that the heat shrinkage rate is large. That is, it is considered that the heat resistance has decreased.

Claims (5)

Polycyclohexylene methylene terephthalate resin (A) containing 90 mol% or more of terephthalic acid unit as a dicarboxylic acid component (a-1) and 90 mol% or more of 1,4-cyclohexanedimethanol unit as a diol component (a-2). 1 part by mass or more and 40 parts by mass or less of the polyallylate resin (B) having a higher glass transition temperature measured according to JIS K7198A than the polycyclohexylenemethylene terephthalate resin (A) with respect to 100 parts by mass. A polyester resin composition containing a proportion of the polyallylate resin (B) and a bisphenol TMC component. Polycyclohexylene methylene terephthalate resin (A) containing 90 mol% or more of terephthalic acid unit as the dicarboxylic acid component (a-1) and 90 mol% or more of 1,4-cyclohexanedimethanol unit as the diol component (a-2). 1 part by mass or more and 50 parts by mass or less of the polyallylate resin (B) having a higher glass transition temperature measured according to JIS K7198A than the polycyclohexylene methylene terephthalate resin (A) with respect to 100 parts by mass. The polyarylate resin (B) contains a bisphenol TMC component and is heated to a temperature 30 ° C. higher than the crystal melting temperature by using a differential scanning calorimeter (DSC) at a heating rate of 10 ° C./min. A polyester resin composition in which the difference between the crystal melting temperature and the temperature-decreasing crystallization temperature is 40 ° C. or higher and 80 ° C. or lower when the temperature is lowered at 10 ° C./min. The polyester resin composition according to claim 1 or 2 , which has a single glass transition temperature. A polyester-based biaxially stretched film comprising the polyester resin composition according to any one of claims 1 to 3. Polycyclohexylene methylene terephthalate resin (A) containing 90 mol% or more of terephthalic acid unit as the dicarboxylic acid component (a-1) and 90 mol% or more of 1,4-cyclohexanedimethanol unit as the diol component (a-2). A method for producing a polyester resin composition, which comprises melt-kneading a polyarylate resin (B) containing a bisphenol TMC component at a ratio of 1 part by mass or more and 40 parts by mass or less at 260 ° C. or higher and 350 ° C. or lower with respect to 100 parts by mass. ..

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