JP5166706B2 - Resin composition and sheet using the same - Google Patents

Description

  The present invention relates to a resin composition and a sheet using the same, and more particularly to a resin composition excellent in moldability, transparency, and whitening resistance, and a sheet using the same. It is.

Conventionally, vinyl chloride resin films have been used in large amounts in decorative sheets used for furniture, doors, door frames, waistboards, baseboards, window frames, and other surface materials. The vinyl chloride resin decorative sheet is laminated on a heating drum of a doubling machine, with a transparent vinyl chloride resin film and a printed colored vinyl chloride resin film superimposed on each other and thermocompression bonded. It was manufactured by embossing. However, since vinyl chloride resins have problems caused by poor incineration conditions, there has been a demand for decorative sheets to replace vinyl chloride resins because of recent social demands for environmental problems.
Therefore, it has been studied to use an amorphous polyester resin film instead of the vinyl chloride resin film.

For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2001-200166) discloses a diol composed of a dicarboxylic acid component composed of terephthalic acid, 20-35 mol% 1,4-cyclohexanedimethanol and 65-80 mol% ethylene glycol. 1 to 17 parts by weight of an acrylic silicone rubber modifier and 0.5 to 3 parts by weight of a lubricant with respect to 100 parts by weight of a resin component mainly composed of an amorphous polyester resin composed of Polyester resin compositions have been proposed. By using this resin composition, it is said that a calender sheet excellent in calendar roll peelability and thin in thickness and excellent in surface smoothness can be obtained even if the production speed is increased.
However, the resin composition described in Patent Document 1 is clogged with the mesh installed on the strainer at the time of calender molding, or thickness fluctuation occurs at both ends with respect to the central part of the calender sheet. As a result, the roll peelability was not obtained, and there was room for improvement in calendar moldability.

JP 2001-200166 A

  Accordingly, an object of the present invention is to provide a resin composition excellent in moldability, transparency and whitening resistance, and a sheet using the same.

The invention according to claim 1 includes: (i) a dicarboxylic acid component comprising terephthalic acid; and (ii) ethylene glycol 60.5-72.5 mol%, diethylene glycol 2.5-4 mol%, and 1,4-cyclohexane. Diol component consisting of 26 to 38 mol% of dimethanol (provided that the total of the ethylene glycol, diethylene glycol and 1,4-cyclohexanedimethanol is 100 mol%, and the 1,4-cyclohexanedimethanol is trans 65 to 75 And a polyester resin (a) composed of 70 to 99% by mass; and an acrylic silicone rubber modifier (b) 1 to 30% by mass. a resin composition characterized by comprising.
Invention of Claim 2 is the resin composition of Claim 1 whose number average molecular weights by GPC measurement (RI detector) of the said polyester-type resin (a) are 16000-24000. .
The invention according to claim 3 is a linear fatty acid having 28 to 32 carbon atoms and / or a derivative wax (c) of 0.2 to 10 with respect to 100 parts by mass of the resin composition according to claim 1 or 2. It is a resin composition characterized by blending parts by mass.
The invention according to claim 4 is a resin composition for a calendered sheet, comprising the resin composition according to any one of claims 1 to 3.
The invention according to claim 5 is a calender sheet obtained by calendering the resin composition for calendered sheets according to claim 4.

  According to the present invention, the constituent diol component of the polyester-based resin (a), particularly the abundance of diethylene glycol and the trans-cis ratio of 1,4-cyclohexanedimethanol are specified, so that molding is possible at a low calendering temperature; The thickness of both ends of the molded sheet can be controlled; there is little clogging of the mesh installed on the strainer at the time of calendar molding; calendar molding such as good roll peelability (preventing stickiness to the metal roll at take-off) It is possible to provide a resin composition having excellent properties, transparency and whitening resistance, and a sheet using the same.

Hereinafter, the present invention will be described in more detail.
Polyester resin (a)
The polyester-based resin (a) used in the present invention comprises (i) a dicarboxylic acid component composed of terephthalic acid, (ii) ethylene glycol 60.5-72.5 mol%, diethylene glycol 1.5-6 mol% and 1 Diol component comprising 26 to 38 mol% of 1,4-cyclohexanedimethanol (provided that the total of the ethylene glycol, diethylene glycol and 1,4-cyclohexanedimethanol is 100 mol%, and the 1,4-cyclohexanedimethanol is A resin composed of 65 to 75 mol% of trans and 25 to 35 mol% of cis.

In order to prepare a polyester containing the diethylene glycol moiety in a predetermined ratio, for example, a predetermined amount of diethylene glycol is used as a diol component. However, when ethylene glycol is used instead of diethylene glycol, a diethylene glycol moiety is formed by the condensation reaction. Usually, in a polyester containing an ethylene terephthalate part, a diethylene glycol part is formed by the condensation reaction of the ethylene glycol in the production process. The content of the diethylene glycol moiety varies depending on the polyester production method, the reaction conditions, the catalyst used, and the like.
In general, the polyester resin (A) in the present invention generally has a larger amount of diethylene glycol than the amount of diethylene glycol moiety by-produced when producing a polyester resin having a 1,4-cyclohexanedimethanol modification amount of around 31 mol%. Contains part. Therefore, in the present invention, in order to contain the above-mentioned predetermined amount of diethylene glycol, it is already known in the field of beverage bottles and bottle shrink films usually made of crystalline polyester, but depending on the content, as a diol component Usually, in addition to ethylene glycol, a further required amount of diethylene glycol is used. Alternatively, the amount of diethylene glycol by-produced from ethylene glycol can also be controlled by optimizing the polyester production conditions and catalyst.
In the polyester-based resin (a) in the present invention, the content of diethylene glycol is controlled by optimizing the production conditions and catalyst of the polyester and using the amount of diethylene glycol by-produced from ethylene glycol, in addition to using the required amount of diethylene glycol. There is a way to control.
Any of the polyester resins (a) in the present invention can be produced by a conventional method. For example, (copolymerization) polyester is prepared using a direct esterification method in which a dicarboxylic acid and a diol are directly reacted; a transesterification method in which a dimethyl ester of a dicarboxylic acid and a diol are reacted. The preparation may be carried out by either a batch method or a continuous method.

The content of diethylene glycol is 1.5 to 6 mol%, preferably 2.5 to 4 mol%.
Although Provista manufactured by Eastman Chemical Co. contains trimellitic anhydride instead of diethylene glycol as the third component, it is not preferable for the purpose of the present invention.

  The polyester resin (a) is a polyester having a crystallization half time from a molten state of at least 5 minutes, preferably at least 12 minutes. Crystallization half time is measured using a Perkin-Elmer model DSC-2 differential scanning calorimeter. A 15.0 mg sample is sealed in an aluminum pan and heated at 290 ° C. for 2 minutes at a rate of about 320 ° C./min. The sample is then immediately cooled in the presence of helium to a predetermined isothermal crystallization temperature at a rate of about 320 ° C./min (20 ° C./min if the apparatus is not possible). The crystallization half time is determined as the time interval from reaching the isothermal crystallization temperature to the point of the crystallization peak on the DSC curve.

When diethylene glycol is out of the range of 1.5 to 6.0 mol%, the calender molding temperature becomes too high, the thickness controllability at both ends at the time of calender sheet molding is inferior, and the strainer mesh replacement frequency increases. Problems such as inferior peelability occur. If it exceeds 6 mol%, problems such as too high a calendering temperature, poor thickness controllability at both ends during calendering, increased strainer mesh replacement frequency, and poor roll peelability occur. In addition, moldability also deteriorates when extrusion molding is performed.
Further, when ethylene glycol is outside the above range, crystallization of the polyester resin occurs and flexibility is impaired. When 1,4-cyclohexanedimethanol is outside the above range, crystallization of the polyester resin occurs and is flexible. The properties are impaired, which is not preferable.
In the amount relationship between ethylene glycol and 1,4-cyclohexanedimethanol, the crystallinity is the lowest (the crystallization time is extremely long) within the above range. This increases the flexibility of the sheet. In addition, moldability is improved when extrusion molding is performed.

In the present invention, the 1,4-cyclohexanedimethanol needs to be composed of 65 to 75 mol% of trans and 25 to 35 mol% of cis. If the transformer is less than 65 mol% or more than 75%, the calender molding temperature becomes too high, the thickness controllability at both ends during calender sheet molding, the strainer mesh replacement frequency increases, the roll peelability is inferior, etc. Problems arise. In addition, when extrusion molding is performed, sag is generated in the die slip, the extrusion moldability is deteriorated, and plate-out is likely to occur during roll molding. Furthermore, the shrinkage rate after molding becomes extremely large.
A method for producing 1,4-cyclohexanedimethanol is known. For example, 1,4-cyclohexanedicarboxylic acid dimethyl ester can be obtained by hydrogenation in the presence of a copper chromium catalyst and then distilled. Methods for adjusting the trans and cis amounts are also known, and are disclosed, for example, in Japanese Patent No. 2537401. In addition, although the production example of 1,4-cyclohexanedimethanol whose trans amount exceeds 90% is described in the publication, such 1,4-cyclohexanedimethanol is used for the purpose of the present invention. I can't.

The polyester resin (a) used in the present invention preferably has a number average molecular weight of 16000 to 24000 as measured by GPC (RI detector) (performed under the following measurement conditions). When the number average molecular weight is within the above range, the calendar moldability is further improved.
Measuring device name: HPLC VP manufactured by Shimadzu Corporation
Column used: Shodex K806L (8 mmφ × 300 mm) × 2 Solvent: Special grade for chloroform liquid chromatography Sample concentration: 0.2% (w / v)
Flow rate: 1 ml / min
Detector: RI
Injection volume: 100 μL
Measurement temperature: 35 ° C

  As described above, only terephthalic acid is used as the dicarboxylic acid component in the present invention. For example, when it contains 1 mol% or more of other dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylate, The object of the present invention cannot be achieved.

Acrylic silicone rubber modifier (b)
Next, the acrylic silicone rubber modifier (b) used in the present invention will be described.
The acrylic silicone rubber modifier (b) is obtained by graft polymerization of a vinyl monomer on a composite rubber composed of an acrylic polymer and a polyorganosiloxane. For example, “Metabrene S2001” manufactured by Mitsubishi Rayon Co., Ltd. , "Metabrene SX006", which is commercially available can be used.

The resin composition of the present invention comprises (a) component 70 to 99% by mass; (b) component 1 to 30% by mass.
Preferably, (a) component 85-96 mass%; (b) component 4-15 mass%.

In the present invention, various additives may be used to further improve the calendar moldability.
Additives suitable for use in the present invention are known in the calendering art and include waxes, slip agents or mixtures thereof. Examples of such additives include fatty acid amides such as stearamide; metal salts of organic acids such as calcium stearate and zinc stearate; fatty acids and esters such as stearic acid, oleic acid and palmitic acid; paraffin wax; Hydrocarbon waxes such as polyethylene wax and polypropylene wax; chemically modified polyolefin wax; ester sax such as carnauba; glycerol mono- and distearate; talc and acrylic copolymers (eg, Rohm & Haas ) From Paraloid K175). Of these, glycerol monostearate is preferable.

Apart from the above, in the present invention, it is particularly preferable to use the following linear fatty acid having 28 to 32 carbon atoms and / or derivative wax (c) thereof. By using this component (c), the calendar moldability is further improved.
(C) As a component, it can be the simple substance of C28-C32 linear fatty acid or its derivative (s), or a mixture, for example. When the carbon number is in the range of 28 to 32, no flaws due to poor dispersion of the additive are observed, and the roll peelability is improved. Examples of the derivatives include saponified and esterified linear fatty acids having 28 to 32 carbon atoms. The esterified product is preferably a product obtained by esterifying a linear fatty acid having 28 to 32 carbon atoms with glycols. The esterified product using such glycols has a structure represented by the following formula (1).

  In the formula, R represents a linear portion of a fatty acid, and Q represents an alkylene group having 2 or 3 carbon atoms. The esterified product of the formula (1) has two molecules of fatty acid bonded via the Q group, and this form is also included in the component (c) in the present invention.

  Particularly preferred component (c) in the present invention is a mixture of montanic acid esterified with ethylene glycol or butylene glycol, and most preferably a mixture of montanic acid partially esterified with butylene glycol and the remainder saponified with calcium hydroxide. It is. As such an optimal component (c), a commercially available product can be used, for example, lycowax OP (melting point 75 ° C.) of a partially saponified ester of montanic acid manufactured by Clariant Japan.

  (C) The compounding ratio of a component is 0.2-10 mass parts with respect to 100 mass parts of said resin compositions of this invention, Preferably it is 0.5-5 mass parts. (C) When the mixture ratio of a component is 0.2 mass part or more, generation | occurrence | production of the fluff resulting from aggregation of (b) component and a dispersion | distribution defect can be suppressed. Moreover, the clogging of the mesh installed in the strainer and the roll peelability are also improved during calendar molding. By being 10 parts by mass or less, stickiness due to blowing to the sheet surface is less likely to occur.

  As a method for producing the resin composition used in the present invention, each of the above components is individually prepared, kneaded using a normal kneading apparatus such as a Henschel mixer, a tumbler, etc., and a single screw extruder, twin screw extruder Banbury. A method of forming a composition by using a device such as a mixer that is used for normal shaping can be employed. In addition, the resin composition of the present invention, if necessary, an antioxidant, a heat stabilizer, a light resistance improver, a UV absorber, a lubricant, a plasticizer, a release agent, An antistatic agent, a slidability improver, a colorant, and the like can be added.

  A method for producing a calendar sheet using the resin composition of the present invention will be described. The type of calendar molding machine is not particularly limited. For example, there is no restriction | limiting in particular in the calendar apparatus to be used, For example, an upright type 3 roll, an upright type 4 roll, an L type 4 roll, a reverse L type 4 roll, a Z type roll etc. can be mentioned. Further, the calendar processing conditions are not particularly limited. For example, the temperature of the calender roll is preferably in the range of 130 to 250 ° C.

  The thickness of the calendar sheet of the present invention is, for example, 30 to 1000 μm, preferably 50 to 500 μm.

Moreover, the resin composition of this invention can also be used for extrusion molding based on a well-known means.
In this case, the thickness of the extruded sheet is, for example, 30 to 1000 μm, preferably 50 to 500 μm.

  Each of the sheets can be laminated with another thermoplastic resin sheet. As another thermoplastic resin, an amorphous polyester resin is preferable, but a crystalline polyester resin may be added to the amorphous polyester resin. Apart from this, each of the sheets may be laminated with the sheet made of the component (a) in the present invention.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further, this invention is not restrict | limited to the following example.

In the following example, any of the following various materials was used.
(1) Polyester resin (a-1)
Glycol component: 66.0 mol% ethylene glycol (EG), 31.0 mol% 1,4-cyclohexanedimethanol (CHDM) and 3.0 mol% diethylene glycol (DEG) (1,4-cyclohexanedimethanol is trans 70 Mol% and cis 30 mol%)
Dicarboxylic acid component: terephthalic acid (TPA)
Polyester composed of.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 21,000.
In addition, the composition ratio of each of the above components is ¹³ C-NMR (nuclear magnetic resonance apparatus (NMR) GX-400 manufactured by JEOL), and about 40 mg of a sample is dissolved in deuterated chloroform in a 5 mm diameter sample tube. It was measured and confirmed as a measurement sample (the same applies to the following).

(2) Polyester resin (a-2)
Glycol component: ethylene glycol 63.0 mol%, 1,4-cyclohexanedimethanol 31.0 mol% and diethylene glycol 6.0 mol% (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis )
Dicarboxylic acid component: Polyester composed of terephthalic acid.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 20500.

(3) Polyester resin (a-3)
Glycol component: 66.5 mol% ethylene glycol, 31.0 mol% 1,4-cyclohexanedimethanol and 2.5 mol% diethylene glycol (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis) )
Dicarboxylic acid component: Polyester composed of terephthalic acid.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 20200.

(4) Polyester resin (a-4)
Glycol component: ethylene glycol 65.0 mol%, 1,4-cyclohexanedimethanol 31.0 mol% and diethylene glycol 4.0 mol% (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis) )
Dicarboxylic acid component: Polyester composed of terephthalic acid.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 20800.

(5) Polyester resin (a-5)
Glycol component: 67.5 mol% ethylene glycol, 31.0 mol% 1,4-cyclohexanedimethanol and 1.5 mol% diethylene glycol (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis) )
Dicarboxylic acid component: Polyester composed of terephthalic acid.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 21,000.

(6) Comparative polyester resin (a′-1)
Glycol component: ethylene glycol 68.0 mol%, 1,4-cyclohexanedimethanol 31.0 mol% and diethylene glycol 1.0 mol% (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis) )
Dicarboxylic acid component: Polyester composed of terephthalic acid.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 21,000.

(7) Comparative polyester resin (a′-2)
Glycol component: 62.8 mol% ethylene glycol, 31.0 mol% 1,4-cyclohexanedimethanol and 6.2 mol% diethylene glycol (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis )
Dicarboxylic acid component: Polyester composed of terephthalic acid.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 20800.

(8) Comparative polyester resin (a'-3)
Glycol component: ethylene glycol 66.0 mol%, 1,4-cyclohexanedimethanol 31.0 mol% and diethylene glycol 3.0 mol% (1,4-cyclohexanedimethanol is composed of 80 mol% trans and 20 mol% cis) )
Dicarboxylic acid component: terephthalic acid (TPA)
Polyester composed of.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 21,000.

(9) Comparative polyester resin (a′-4)
Glycol component: ethylene glycol 66.0 mol%, 1,4-cyclohexanedimethanol 31.0 mol% and diethylene glycol 3.0 mol% (1,4-cyclohexanedimethanol is composed of 60 mol% trans and 40 mol% cis) )
Dicarboxylic acid component: terephthalic acid (TPA)
Polyester composed of.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 21,000.

(10) Acrylic silicone rubber modifier (b)
Manufacturing company: Mitsubishi Rayon Co., Ltd. Product name: Metabrene SX006
Composition: Core: Silicone / acrylic polymer, Shell: Acrylonitrile / styrene polymer

(11) C28-C32 linear fatty acid and / or derivative wax (c)
Manufacturer: Clariant Japan Product Name: Lycowax OP (Montanic acid partially saponified ester. Saponified portion is calcium salt, melting point 75 ° C)

(Examples 1-11 and Comparative Examples 1-10)
(Calendar moldability)
Various compositions having the formulation shown in Table 1 were melt-kneaded using a Banbury mixer and calendered to obtain a sheet having a thickness of 100 μm. As the calendar molding machine, an inverted L shape was used.
The calendar moldability at this time was examined from the viewpoint of temperature. Specifically, the temperature of the calender roll is gradually increased from a low temperature, and the lowest temperature at which rough skin, no air mark, and high smoothness of the sheet appearance are obtained is set as the evaluation temperature for calendering. . The calender molding machine used was a four-roll machine, and all roll temperatures were the same. The calendar molding temperature was classified according to the following evaluation criteria.
A: 165 ° C. to 175 ° C., ◯: over 175 ° C. to 185 ° C., Δ: over 185 ° C. to 195 ° C., x: over 195 ° C. to 205 ° C.
The controllability of the thickness at both ends of the calendar sheet was examined. Specifically, the calendering temperature is the minimum temperature condition where rough skin, no air mark, and high smooth appearance can be obtained, and the thickness of both ends when the thickness of the sheet center is accurately adjusted to 100 μm. It was measured. At this time, it classified according to the following evaluation criteria according to the degree of thickness fluctuation with respect to the central portion.
A: Less than ± 0 to 3 μm, ○: Less than ± 3 to 5 μm, Δ: Less than ± 5 to 10 μm, ×: More than ± 10 μm.
In addition, the frequency of changing the screen (100 mesh wire mesh) of the strainer part in this molding process was examined.
Further, the roll peelability was examined as ◯: uniformly peeled from the roll, Δ: inferior to the smoothness of the sheet obtained without being peeled uniformly from the roll, and X: stuck to the roll and not peeled, and investigated as sheet production impossible.
Furthermore, the transparency of the calendar sheet (thickness 100 μm) was measured as a haze value in accordance with JIS K7105.
Measuring device: Evaluation was performed by measuring with a direct reading haze meter manufactured by Toyo Seiki Seisakusho.
In the evaluation of transparency, a haze value of 10% or less was evaluated as ◯, a haze value of less than 60% was evaluated as Δ, and a haze value of 60% or more was evaluated as ×.
Further, the whitening property of the calendar sheet was evaluated by the following test methods and evaluation criteria.
A calendar sheet with a thickness of 0.1 mm (thickness: 100 μm) is attached to two stainless steel plates (6 cm x 5 cm, 1 mm thickness) that are in contact with each other with their longitudinal sides parallel, and folded at 90 ° and folded. The degree of whitening of the surface was visually observed and evaluated according to the following criteria.
A: Whitening is not recognized. ○: Slight whitening is observed. X: Big whitening is recognized.
The results are shown in Table 1.

(Extrudability)
Various compositions having the formulation shown in Table 1 were extruded to obtain a sheet having a thickness of 100 μm. As the extruder, a single shaft, a diameter of 90 mm, and L / D = 28 were used. The extrusion temperature condition was 230 ° C.
The surface properties of the extruded sheet were examined. Specifically, after the extrusion, the surface of the sheet was observed due to the occurrence of die slip.
(Double-circle): Extrusion molding does not generate | occur | produce a stripe for 8 hours or more. ○: Minor streaking occurred in extrusion molding of 5 or more to less than 8 hours. (Triangle | delta): Stretching generation | occurrence | production in 2-5 hours or less extrusion molding. X: Evaluated as the occurrence of stringing in less than 2 hours of extrusion molding.
The results are shown in Table 1. In addition, (c) component is not mix | blended with the resin composition which evaluates extrusion moldability.

From the results in Table 1, in each example using the composition of the present invention, molding can be performed at a lower calender molding temperature than in the comparative example; the thickness of both ends of the calendered sheet can be controlled; It can be seen that the mesh placed on the strainer is less clogged; the roll releasability is good, and the calendar formability is excellent, and the transparency and whitening resistance are excellent. Moreover, it turns out that it is excellent also in extrusion moldability.
Examples 4, 5, 10 and 11 are reference examples.

  According to the present invention, it is possible to provide a resin composition excellent in moldability and excellent in transparency and whitening resistance, and a sheet using the same.

Claims (5)

(I) a dicarboxylic acid component composed of terephthalic acid, and (ii) ethylene glycol 60.5-72.5 mol%, diethylene glycol 2.5-4 mol%, and 1,4-cyclohexanedimethanol 26-38 mol%. Diol component (however, the total of the ethylene glycol, diethylene glycol and 1,4-cyclohexanedimethanol is 100 mol%, and the 1,4-cyclohexanedimethanol is trans 65-75 mol% and cis 25-35 mol%. And a polyester resin (a) 70 to 99% by mass; and an acrylic silicone rubber modifier (b) 1 to 30% by mass. .   The number average molecular weight by GPC measurement (RI detector) of the said polyester-type resin (a) is 16000-24000, The resin composition of Claim 1 characterized by the above-mentioned. A linear fatty acid having 28 to 32 carbon atoms and / or a derivative wax (c) thereof is blended in an amount of 0.2 to 10 parts by mass with respect to 100 parts by mass of the resin composition according to claim 1 or 2. Resin composition. Comprising the resin composition according to any one of claims 1 to 3 calender molding sheet for a resin composition. A calendar sheet obtained by calendering the resin composition for a calendered sheet according to claim 4 .