JP2014117919A - Resin composition and utilization of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of molding a molded body of a cyclic olefin polymer excellent in transparent property and optical characteristics while suppressing supply defect of powder when resin powder of the cyclic olefin polymer is put into a molding machine and generation of foreign matter in the molded body.SOLUTION: The resin powder of the cyclic olefin polymer having equal to or more than 50 wt.% of component content whose loose bulk density is less than 0.3 g/cc, and grain size is equal to or less than 0.5 mm is pressurized and compressed to be molded under the temperature condition less than its molten temperature, then it is cracked if it is necessary, and filtered if it is necessary, and it is recovered. Thereby, powder lump having equal to or less than 1 wt.% of component content whose loose bulk density is in a range of 0.3 to 0.6 g/cc, and grain size is equal to or less than 0.5 mm is obtained and the lump is subjected to molding processing by using a heat molten molding machine.

Description

  The present invention relates to a method for molding a powdered resin.

A method of melting a powder of a cyclic olefin polymer such as a copolymer of ethylene and a cyclic olefin using an extruder and pelletizing using a pelletizer (Patent Document 1, etc.) is employed. In addition, in the pelletization of a copolymer of ethylene and a cyclic olefin, the copolymer powder heated in the cylinder is melted by the heat of the cylinder, but is also subjected to shearing when it is caught in the screw. Cyclohexane-insoluble fine particles are generated in the resin pellets obtained by shearing, which causes problems as an optical material. In order to solve this problem, it has been proposed to heat the resin in advance so that the resin is not subjected to excessive shearing (Patent Document 2).
In addition, in styrenic resins having a high syndiotactic structure, the resin powder is heated to a glass transition temperature or higher in order to prevent deterioration of the resin quality due to melting of the resin in pellet molding, that is, giving a thermal history. A method has been proposed in which a dry compression molding is performed at a temperature equal to or lower than the melting point, and the resulting molding is crushed to obtain a resin granule having the same handling properties as pellets (Patent Document 3).

JP-A-2-191602 WO94 / 017128 pamphlet WO2002 / 070220

Under such prior art, the present inventors, when the resin powder of the cyclic olefin polymer is put into an extrusion molding machine, it becomes difficult to supply to the molding machine or molding itself due to the floating of the powder. Even if it was possible, it was confirmed that an oxide resin foreign matter was generated, and it was easy to obtain a product inferior to the transparency and optical characteristics that are the characteristics of the cyclic olefin polymer molded product.
Therefore, the present inventors have not only prevented the supply failure to the molding machine but also caused the burnt failure of the molded product by forming the resin powder of the cyclic olefin polymer into a flake shape by pressure compression molding before molding. The present inventors have found that it can be greatly reduced and have completed the present invention.

Thus, according to the present invention, a resin powder of a cyclic olefin polymer having a loose bulk density of less than 0.3 g / cc and a sieve particle size of 0.5 mm or less and a component content of 50% by weight or more is obtained under a temperature condition below its melting temperature. After compression molding under pressure, the loose bulk density obtained by pulverization is 0.3 g / cc or more and 0.6 g / cc or less, and the sieve particle size is 0.5 mm or less and the component content is 1% by weight or less. A method of forming a powder lump with a hot melt molding machine is provided.
The cyclic olefin polymer is preferably a hydrogenated cyclic olefin ring-opening polymer having a repeating unit derived from a norbornene monomer, and the cyclic olefin polymer is derived from a norbornene monomer having a melting point. It is more preferable that it is a cyclic olefin ring-opening polymer hydrogenated product having a repeating unit.
Moreover, in the said shaping | molding method, it is preferable to include the process of adding and mixing 0.05-2 weight part of antioxidant with respect to 100 weight part of resin powder of a cyclic olefin polymer, before carrying out pressure compression molding.
Moreover, according to this invention, the molded object obtained by the shaping | molding method mentioned above is provided.
In the molding method, the hot melt molding machine is preferably a film molding machine including a T die. The molded body obtained by such a molding method is a film.
In the molding method described above, the hot melt molding machine is preferably a biaxial extrusion molding machine. The molded body obtained by such a molding method is a strand-shaped resin molded body or a pellet-shaped resin molded body. Moreover, a film is obtained by shape | molding this pellet-shaped resin molded object with a film forming machine provided with T-die.

  A cyclic olefin polymer having a loose bulk density of less than 0.3 g / cc, a sieve particle size of 0.5 mm or less and a component content of 50% by weight or more (hereinafter simply referred to as “cyclic olefin polymer”). ) Has a melting point, which is obtained by polymerizing a monomer containing a norbornene monomer as at least a polymerizable monomer. The norbornene monomer is preferably a polycyclic norbornene monomer.

<Cyclic olefin polymer>
The method for obtaining the cyclic olefin polymer is not particularly limited. For example, a method described in JP-A-2006-52333, a norbornene-based monomer is subjected to ring-opening polymerization in the presence of a specific catalyst, Next, a hydrogenated product of a cyclic olefin ring-opening polymer having a melting point obtained by hydrogenation can be mentioned. According to this method, a cyclic olefin ring-opening polymer having syndiotactic stereoregularity is obtained, and hydrogenation thereof can be used to efficiently obtain the target cyclic olefin ring-opening polymer hydrogenated product. it can. Further, as described in JP-A-2-191602, an α-olefin obtained by polymerizing an α-olefin such as ethylene and a norbornene-based monomer in the presence of a catalyst and hydrogenating as necessary. Examples include copolymers with cyclic olefins. The present invention is particularly effective for a hydrogenated product of a cyclic olefin ring-opening polymer having a melting point because it tends to become a fine powder when dried.

  A hydrogenated product of a cyclic olefin ring-opening polymer having a melting point suitably used in the present invention is obtained by using a polycyclic norbornene monomer having three or more rings as at least a part of the monomer. It is preferable. The polycyclic norbornene monomer may be a norbornene compound having a norbornene skeleton and one or more ring structures condensed to the norbornene skeleton in the molecule. From the viewpoint of improving the crystallinity of the cyclic olefin ring-opening polymer hydrogenated product and particularly improving the heat resistance of the resulting molded product, it is 50% by weight or more based on the whole polycyclic norbornene monomer. Those containing dicyclopentadiene are preferably used, and dicyclopentadiene is particularly preferably used alone.

In addition, polycyclic norbornene monomers include endo isomers and exo isomers, both of which can be used as monomers, and one isomer can be used alone. Alternatively, an isomer mixture in which endo and exo isomers are present in an arbitrary ratio can be used. However, from the viewpoint of improving the crystallinity of the cyclic olefin ring-opening polymer hydrogenated product and particularly improving the heat resistance of the resulting resin composition, it is preferable to increase the ratio of one stereoisomer, For example, the ratio of endo-form or exo-form is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. In addition, it is preferable that the stereoisomer which makes a ratio high is an end body from a viewpoint of synthetic | combination ease.
A monomer other than the polycyclic norbornene monomer may be copolymerized with the polycyclic norbornene monomer. Monomers that can be copolymerized with polycyclic norbornene monomers include bicyclic norbornene compounds, monocyclic olefins, cyclic dienes, and derivatives thereof that do not have a ring structure condensed to a norbornene skeleton. .

The cyclic olefin polymer is recovered as a solid content by solid solution separation by adding a poor solvent (usually a polar solvent such as acetone or ethanol) to the reaction solution.
The recovered cyclic olefin polymer is dried by a conventional method to form a resin powder. The resin powder of less than 0.3 g / cc and a sieve particle size of 0.5 mm or less having a component content of 50% by weight or more is liable to cause molding failure due to scattering in a molding machine. Shows remarkable effect.

In the cyclic olefin polymer, various compounding agents (compounding agents usually used in the resin industry) can be used singly or in combination of two or more depending on the use and storage environment, and can be used for various applications.
The various compounding agents are not particularly limited as long as they are usually used in thermoplastic resin materials, such as antioxidants, ultraviolet absorbers, light stabilizers, near infrared absorbers, dyes and pigments. Examples thereof include compounding agents such as a colorant, a plasticizer, an antistatic agent, a fluorescent whitening agent, and other resins.
Examples of the antioxidant include phosphorus antioxidants, phenol antioxidants, sulfur antioxidants, and the like.

Specific examples of antioxidants include, for example, phosphorus antioxidants such as triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite. Tris (2,4-di-t-butylphenyl) phosphite, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphat Monophosphite compounds such as phenanthrene-10-oxide; 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecylphosphite), 4,4′-isopropylidene-bis diphosphite compounds such as (phenyl - - di-alkyl _(C 12 _{-C 15)} phosphite); -[3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetrakis-t-butyldibenzo [d, f] [1.3.2] di Oxaphosphepine, 6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -2,4,8,10-tetrakis-t-butyldibenzo [d, f] [1 3.2] Compounds such as dioxaphosphine can be mentioned.

  Examples of phenolic antioxidants include pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) proonyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3,5 -A compound such as trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene.

  Examples of sulfur-based antioxidants include dilauryl-3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, laurylstearyl-3,3. '-Thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate, 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] Examples include compounds such as undecane.

The amount of the antioxidant is usually 0.05 to 2 parts by weight, preferably 0.05 to 1.5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the cyclic olefin polymer. It is. If the amount of antioxidant is less than this, the heat resistance stability of the (deleted) fiber reinforced resin composition of the present invention may be insufficient, and even if it is added excessively beyond this, the resin composition molding This is not preferable because the hue of the body and the rate of light reduction deteriorate.
In the present invention, these various compounding agents are blended with a resin powder of a cyclic olefin polymer having a loose bulk density of less than 0.3 g / cc and a sieve particle size of 0.5 mm or less and a component content of 50% by weight or more. Usually, it is before pressure compression, and it is preferable that various compounding agents are also powder because they are easily mixed uniformly.

<Pressure compression molding>
According to the molding method of the present invention, first, various blends are added to the cyclic olefin polymer having a loose bulk density of less than 0.3 g / cc and a sieve particle size of 0.5 mm or less and a component content of 50% by weight or more as required. After the agent is added, pressure compression molding is performed at a temperature lower than the melting temperature of the cyclic olefin polymer. In the present invention, the melting temperature of the cyclic olefin polymer is the glass transition temperature and / or melting point, and when it has a plurality of glass transition temperatures and / or melting points, the highest temperature is the melting temperature of the present invention. . By molding at a temperature lower than the melting temperature, fusion of the resin can be prevented.
As the pressure compression molding machine used for pressure compression molding, a compressor used in the chemical industry is preferably employed, and a tableting machine or the like can also be used. The compressor is a batch type compressor such as a press compressor that press-compresses powder into a plate shape, or an extruder equipped with a die or a screen, and the powder is extruded into a strand shape by a screw. A roll compressor that obtains a strip-shaped compact by pressing it between an extrusion compressor (usually, then cutting the strand-shaped compact into an arbitrary size) or a roll between relatively rotating rolls and forming it with the inter-roll pressure. Such a continuous compressor is mentioned. Among these, a continuous compressor is preferable from the viewpoint of productivity, and a roll compressor is particularly preferable from the viewpoint of obtaining a powder lump having a high upper pressure limit and a higher loose bulk density due to the structure of the device.

Pressure-compressing a cyclic olefin polymer having a loose bulk density of less than 0.3 g / cc, a sieve particle size of 0.5 mm or less, and a component content of 50% by weight or more, with various compounding agents added as necessary. A loose lump with a loose bulk density of 0.3 g / cc to 0.6 g / cc is obtained. The method of adjusting the loose bulk density and sieve particle size of the powder mass to this range by pressure compression may be performed by adjusting the pressure applied to the resin powder that has entered the pressure compression molding machine. It is preferable to pressurize under a temperature condition lower by at least C.
In addition, considering the filling efficiency of the lump into the hot melt molding machine, it is necessary that the component content with a sieve particle size of 0.5 mm or less is 1 wt% or less, but the sieve particle size is 0.5 mm or less When the amount of the component is more than 1% by weight, the amount of the component having a too small sieve particle size can be suppressed by sieving.
The sieving method may be performed using a classifier, and examples thereof include a method using an airflow classifier and a vibration sieving classifier.

Furthermore, depending on the size of the molding machine, a lump with a too large sieve particle size may not be suitable for filling. In such a case, it is preferable to crush a powder lump having a too large sieve particle size to an appropriate size by adding a crushing step.
The pulverization may be performed using a pulverizer, and examples thereof include a method using a known device such as a cutter mill, a hammer mill, a biaxial pulverizer, a pin mill pulverizer, and a rotary blade pulverizer.

<Melt molding>
The thus obtained powder lump having a sieve particle size of 0.5 mm or less and a component content of 1% by weight or less is melt-molded by a hot melt molding machine. Examples of the hot melt molding method include known methods such as injection molding, sheet molding, blow molding, injection blow molding, inflation molding, T-die molding, press molding, extrusion molding and the like. Secondary processing molding methods such as molding can also be employed. As an example, a method of kneading a predetermined material using a kneader such as a heating roll, a kneader, a Banbury mixer, an extruder, cooling, pulverizing, and further performing molding by transfer molding, injection molding, compression molding, or the like is an example. Can be mentioned.
In T-die molding, generally, a molten resin melt-kneaded by an extruder or the like passes through a T-die connected to the extruder to give a film-like molded body.
Moreover, the strand-shaped molded object obtained from a twin-screw extruder turns into the pellet-shaped molded object cut by the pelletizer after cooling with water cooling etc.
The pellet-shaped molded body can be similarly melt-molded by using this in place of the powder lump according to the present invention, and the pellet-shaped molded body is extruded with, for example, a molten resin melt-kneaded by an extruder or the like. A film-like molded body can also be obtained through a T-die connected to the machine.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited only to these examples.
In the following examples and comparative examples, “part” or “%” is based on weight unless otherwise specified.

The measuring methods for various physical properties are as follows.
(1) Molecular weight (weight average molecular weight and number average molecular weight) of cyclic olefin ring-opening polymer
Using a gel permeation chromatography (GPC) system HLC-8220 (manufactured by Tosoh Corporation), an H-type column (manufactured by Tosoh Corporation) was measured at 40 ° C. using tetrahydrofuran as a solvent, and was determined as a polystyrene equivalent value.
(2) Hydrogenation rate in cyclic olefin ring-opening polymer hydrogenated product
^It calculated | required by < ¹ > H-NMR measurement.
(3) Melting point of cyclic olefin ring-opening polymer hydrogenated product Using a differential scanning calorimeter (DSC), the temperature was raised at a temperature elevation of 10 ° C./min.
(4) Ratio of racemo dyad of cyclic olefin ring-opening polymer hydrogenated product Using orthodichlorobenzene-d ₄ as a solvent, ¹³ C-NMR measurement was performed at 150 ° C., and 43.35 ppm signal derived from meso dyad , Based on the intensity ratio of the 43.43 ppm signal from Racemo Dyad.
(5) When a sample is naturally dropped into a 100 cc bulk density measuring cup for a loose bulk density powder physical property measuring instrument (“Powder Tester TP-X”, manufactured by Hosokawa Micron Corporation), and a 100 cc capacity is put into the cup. The loose bulk density (g / cc) was measured by measuring the sample weight.

(6) Number of foreign objects in the pellet molded product 1 g of the pellet sample was sandwiched between two stainless steel sheets that had been mirror-finished by electropolishing of 150 mm × 150 mm × 0.5 mm, and a vacuum press molding machine (“IMC-19E4”). , Manufactured by Imoto Seisakusho Co., Ltd.) together with the stainless steel thin plate. Thereafter, in order to obtain a thin film-shaped composition molded body, it was heated after being evacuated and vacuum press-molded under conditions of a temperature of 300 ° C., a pressure of 1.0 MPa, and a pressurization time of 5 minutes, and a diameter of about 110 mm × A thin circular film having a thickness of about 100 μm was prepared. Ten locations on the film were randomly selected, and 10 thin film square samples of 10 mm × 10 mm were cut out, and then the entire area on one side of each thin film square sample was digital microscope (“KH-7700”, Hilox Corporation) Manufactured), the number of foreign matters having a side length of 10 μm or more was counted, and an average value of 10 thin-film square samples was obtained as a result.
(7) Number of foreign substances in film molded product After randomly selecting 10 internal parts of the film obtained by hot melt extrusion molding and cutting out 10 10 mm × 10 mm thin film square samples, one side of each thin film square sample The area was observed with a digital microscope (“KH-7700”, manufactured by Hilox) at a magnification of 100, the number of foreign objects having a side length of 20 μm or more was counted, and the average value of 10 thin-film square samples was obtained as a result. did.
(8) HAZE measurement of film HAZE measurement was performed by cutting a film obtained by hot melt extrusion molding into a square thin film sample of 120 mm × 120 mm, and then using a HAZE meter (“NDH5000”, Nippon Denshoku). (Manufactured by Kogyo Co., Ltd.).
(9) Measurement of Light Transmittance of Film Light transmittance measurement was performed by cutting a film obtained by hot melt extrusion molding into a 120 mm × 120 mm square thin film sample, and then using a spectrophotometer (“U -4100 ", manufactured by Hitachi High-Technologies Corporation), the light transmittance at a wavelength of 400 nm in the thickness direction of the film was measured.

[Synthesis Example 1]
After fully drying, a pressure-resistant reaction vessel made of nitrogen-substituted glass was charged with 40 parts of a 75% cyclohexane solution of dicyclopentadiene (endo content 99% or more) (30 parts as the amount of dicyclopentadiene). 738 parts of cyclohexane and 3.3 parts of 1-hexene were added and heated to 50 ° C. Meanwhile, 4.6 parts of a 19 wt% diethylaluminum ethoxide / n-hexane solution was added to a solution of 1.1 parts of tetrachlorotungstenphenylimide (tetrahydrofuran) complex in 56 parts of toluene and stirred for 10 minutes. A catalyst solution was prepared. This catalyst solution was added to the reactor to initiate the ring-opening polymerization reaction. Thereafter, while maintaining 50 ° C., 40 parts of a 75% dicyclopentadiene / cyclohexane solution was added 9 times every 5 minutes, and then the reaction was continued for 2 hours. Next, a small amount of isopropanol was added to stop the polymerization reaction, and then the polymerization reaction solution was poured into a large amount of isopropanol to solidify the ring-opened polymer.
The solidified polymer was recovered by filtration. The obtained ring-opening polymer was dried at 40 ° C. under reduced pressure for 20 hours. The yield of the polymer was 296 parts (yield = 99%). Further, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of this polymer are 10,100 and 17,200, respectively, and the molecular weight distribution (Mw / Mn) obtained therefrom is 1.70. It was.
60 parts of the resulting ring-opening polymer and 261 parts of cyclohexane were added to a pressure-resistant reaction vessel and stirred. After the polymer was dissolved in cyclohexane, 0.039 part of chlorohydridocarbonyltris (triphenylphosphine) ruthenium was added to 40 parts of toluene. The dissolved hydrogenation catalyst solution was added, and a hydrogenation reaction was performed at a hydrogen pressure of 4 MPa and 160 ° C. for 5 hours. The hydrogenation reaction solution was poured into 839 parts of isopropyl alcohol to completely precipitate the polymer, thereby obtaining a slurry of a crystalline cyclic olefin ring-opening polymer hydrogenated product having a solid content concentration of 5%.
Subsequently, the ring-opened polymer hydrogenated product slurry was solid-liquid separated by filtration and then dried at 120 ° C. under reduced pressure for 24 hours to obtain a ring-opened polymer hydrogenated product powder. The yield of the polymer hydride powder was 59 parts (yield = 98%). The loose bulk density, hydrogenation rate, racemo dyad ratio, and melting point were measured. The loose bulk specific gravity was 0.19, the hydrogenation rate was 99% or more, and the racemo dyad ratio was 79%, the melting point. Was 260 ° C.

[Synthesis Example 2]
A ring-opened polymer hydrogenated powder was obtained in the same manner as in Synthesis Example 1 except that 0.052 part of chlorohydridocarbonyltris (triphenylphosphine) ruthenium and a hydrogenation reaction temperature of 180 ° C. were obtained. The yield of the polymer hydride powder was 59 parts (yield = 98%). The loose bulk density, hydrogenation rate, racemo dyad ratio and melting point were measured. The loose bulk specific gravity was 0.26, the hydrogenation rate was 99% or more, and the racemo dyad ratio was 76%. Was 262 ° C.

[Example 1]
<Pressure compression molding>
To 100 parts of the crystalline cyclic olefin ring-opening polymer hydrogenated powder obtained in Synthesis Example 1, powdered antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4 '-Hydroxyphenyl) propionate] methane, trade name “Irganox (registered trademark) 1010”, manufactured by BASF Japan Ltd.) 0.5 part was mixed, followed by pressure compression molding machine (Brigket with vacuum degassing mechanism “BGS-IV” “Shinto Kogyo Co., Ltd.) was used to obtain a strip-shaped compression molded product. The operating conditions for pressure compression molding are listed below.
・ Roll pocket shape: corrugated roll (R = 3)
・ Roll rotation speed: 20rpm
・ Roll pressure: 15kN
Subsequently, the strip-shaped compression molded product was pulverized using a pulverizer (flakes crusher “FC-200 type” manufactured by Hosokawa Micron Co., Ltd.) equipped with a mesh screen having an inner diameter of 5 mm to obtain a flaky powder lump. When the size of the powdered soul was fractionated and measured with a sieve, 10 mm <was 0%, 0.5 mm> was 0.6%, and the loose bulk density was 0.32 g / cc.
<Creation of pellet molding>
The obtained flake-like powder lump was put into a twin-screw extruder (TEM-37B, manufactured by Toshiba Machine Co., Ltd.) equipped with four die holes having an inner diameter of 3 mmφ, and formed into a strand-like formed body by hot melt extrusion molding. Then, it cut | judged with the strand cutter so that it might become a cylindrical pellet shape of diameter 3mmphi x length 3mm, and the pellet-shaped hot-melt-extrusion molded object was obtained. The operating conditions of the twin screw extruder are listed below.
-Barrel set temperature: 270 ° C to 280 ° C
・ Die setting temperature: 210 ℃
・ Screw speed: 145rpm
・ Feeder rotation speed: 50 rpm
At this time, the molding speed in the hot melt extrusion molding was 12 kg / h at the maximum. Moreover, when the number of the foreign materials in the obtained pellet was measured, it was 1 piece / cm ² .
<Creation of film molding>
Subsequently, the obtained pellets were converted into a film having a thickness of 100 μm and a width of 120 mm with a hot melt extrusion film forming machine equipped with a T-die (“Measuring Extruder Type Me-20 / 2800 V3”, manufactured by Optical Control Systems). A film molded body was obtained by a method of winding on a roll at a speed of minutes. The operating conditions of the film forming machine are listed in the following list.
・ Barrel temperature setting: 280 ℃ ～ 290 ℃
-Die temperature: 240 ° C
-Screw rotation speed: 30rpm
When the obtained film was measured for HAZE, light transmittance, and number of foreign substances, HAZE was 0.3, light transmittance was 90.7%, and the number of foreign substances was 3 / cm ² .

[Example 2]
It implemented similarly to Example 1 except having changed the operating conditions of pressure compression molding into the following.
・ Roll rotation speed: 7.2rpm
・ Roll pressure: 70kN
The size of the obtained flake-like powder lump was measured with a sieve and measured, and 10 mm <was 0%, 0.5 mm> was 0.6% in shape, and the loose bulk density was 0.46 g / cc. there were.
Thereafter, the maximum molding speed in hot melt extrusion molding was 15 kg / h, and the number of foreign matters in the obtained pellets was measured and found to be 0 / cm ² .
Furthermore, when the HAZE, the light transmittance, and the number of foreign matters of the obtained film were measured by the subsequent hot melt extrusion film forming, the HAZE was 0.2, the light transmittance was 90.9%, and The number of foreign matters was 1 / cm ² .

Example 3
It implemented similarly to Example 1 except having changed the operating conditions of pressure compression molding into the following.
・ Roll rotation speed: 9.6 rpm
・ Roll pressure: 53kN
The size of the obtained flake-like powder lump was measured by sieving and measured, and 10 mm <was 0%, 0.5 mm> was 0.4%, and the loose bulk density was 0.44 g / cc. there were.
Thereafter, the maximum molding speed in hot melt extrusion molding was 16 kg / h, and the number of foreign matters in the obtained pellets was measured and found to be 0 / cm ² .
Furthermore, when the obtained film was measured for HAZE, light transmittance, and number of foreign substances by hot melt extrusion film forming, HAZE was 0.3, light transmittance was 90.9%, and The number of foreign matters was 0 / cm ² .

Example 4
It implemented similarly to Example 1 except having changed the operating conditions of pressure compression molding into the following.
・ Roll rotation speed: 11.4rpm
・ Roll pressure: 30kN
The size of the obtained flake-like powder lump was measured with a sieve and measured, and 10 mm <was 0%, 0.5 mm> was 0.6% in shape, and the loose bulk density was 0.38 g / cc. there were.
Thereafter, the maximum molding speed in hot melt extrusion molding was 15 kg / h, and the number of foreign matters in the obtained pellets was measured and found to be 1 / cm ² .
Furthermore, when the obtained film was measured for HAZE, light transmittance, and number of foreign substances by hot melt extrusion film forming, HAZE was 0.3, light transmittance was 90.9%, and The number of foreign matters was 2 / cm ² .

Example 5
The flaky powder lump obtained in Example 1 was put into a hot melt extrusion film forming machine without passing through the pellet formed body to obtain a film formed body.
When the obtained film was measured for HAZE, light transmittance, and number of foreign substances, HAZE was 0.6, light transmittance was 90.6%, and the number of foreign substances was 5 / cm ² .

[Comparative Example 1]
It implemented similarly to Example 1 except having changed the operating conditions of pressure compression molding into the following.
・ Roll rotation speed: 30rpm
・ Roll pressure: 10kN
The size of the obtained flake-like powder lump was measured with a sieve and measured, and 10 mm <was 0%, 0.5 mm> was 2.0% in shape, and the loose bulk density was 0.25 g / cc. there were.
Thereafter, the maximum molding speed in hot melt extrusion molding was 10 kg / h, and the number of foreign matters in the obtained pellets was measured and found to be 153 / cm ² .
Furthermore, when the obtained film was measured for HAZE, light transmittance, and number of foreign materials by hot melt extrusion film forming, HAZE was 1.1, light transmittance was 89.4%, and The number of foreign matters was 181 / cm ² .

[Comparative Example 2]
The powder mixture prepared in Synthesis Example 1 having a loose bulk specific gravity of 0.19 g / cc: 100 parts and a powdered antioxidant: 3.0 parts in advance was mixed without pressure compression molding. This was carried out in the same manner as in Example 1 except that it was put into a twin screw extruder to obtain a pellet molded body.
In hot melt extrusion molding with a twin screw extruder, the problem of raw material supply failure occurs due to the phenomenon of raw material powder flowing back due to the effect of expanded air generated at the moment when the mixed powder raw material is supplied into the molding machine and heated to a high temperature. did. The extrusion molding speed was 3 kg / h at the maximum, and the number of foreign matters in the obtained pellet was measured and found to be 191 / cm ² .
Further, a film molded body was obtained by the subsequent hot melt extrusion film molding, but the bleeding phenomenon of the antioxidant on the film surface was observed. When the obtained film was measured for HAZE, light transmittance, and the number of foreign substances, the HAZE was 2.3, the light transmittance was 83.4%, and the number of foreign substances was 201 / cm ² .

[Comparative Example 3]
The same as in Comparative Example 1, except that the powder mass produced by the pressure compression molding of Comparative Example 1 was put into a hot melt extrusion film forming machine without being put into a twin screw extruder and a film molded body was formed. Implemented.
When the film obtained by hot melt extrusion film formation was measured for HAZE, light transmittance, and number of foreign matters, HAZE was 1.8, light transmittance was 87.7%, and the number of foreign matters was 223 pieces / cm. ² .

[Comparative Example 4]
The powder mixture prepared in Synthesis Example 2 with a loose bulk specific gravity of 0.26 g / cc: 100 parts is mixed with powdered antioxidant: 0.5 part in advance, and the mixed powder is put into a twin screw extruder. The same procedure as in Comparative Example 2 was performed except that a pellet molded body was obtained.
The maximum molding speed in the hot melt extrusion molding was 10 kg / h, and the number of foreign matters in the obtained pellets was measured and found to be 180 / cm ² .
Furthermore, when the obtained film was measured for HAZE, light transmittance, and number of foreign matters by hot melt extrusion film forming, HAZE was 1.3, light transmittance was 88.6%, and The number of foreign matters was 193 / cm ² .

  The results of the above examples and comparative examples are collectively shown in Table 1.

  From the results of Examples 1 to 5 and Comparative Examples 1 to 4, the cyclic olefin polymer resin powder was subjected to pressure compression molding, loose bulk density: 0.3 to 0.6 g / cc, sieve particle size: 10 mm or more. In the case where hot melt molding is performed using a raw material in the form of a lump having a component of 0% and 0.5 mm or less and a component of less than 1%, the resulting pellet-like molded product and the generation of foreign matter in the film molded product are suppressed, and It is clear that a molded article having superior performance in terms of performance such as HAZE and light transmittance can be obtained.

Claims (10)

A resin powder of a cyclic olefin polymer having a loose bulk density of less than 0.3 g / cc and a sieve particle size of 0.5 mm or less and a component content of 50% by weight or more was compression-compressed under temperature conditions below the melting temperature. After that, it is crushed as necessary, sieved as necessary, and then recovered to obtain a loose bulk density of 0.3 g / cc to 0.6 g / cc, and a sieve particle size of 0.5 mm or less. A method of forming a powder lump having a component content of 1% by weight or less with a hot melt molding machine. The molding processing method according to claim 1, wherein the cyclic olefin polymer is a hydrogenated cyclic olefin ring-opening polymer having a repeating unit derived from a norbornene monomer. The molding processing method according to claim 1, wherein the cyclic olefin polymer is a hydrogenated product of a cyclic olefin ring-opening polymer having a repeating unit derived from a norbornene monomer having a melting point. The molding method according to claim 1, further comprising the step of adding and mixing 0.05 to 2 parts by weight of an antioxidant with respect to 100 parts by weight of the resin powder of the cyclic olefin polymer before the pressure compression molding. The molded object obtained by the shaping | molding processing method in any one of Claims 1-4. The molding method according to claim 1, wherein the hot melt molding machine is a film molding machine including a T die. A film obtained by the forming method according to claim 6. The molding method according to claim 1, wherein the hot melt molding machine is a biaxial extrusion molding machine. A strand-shaped resin molded body or a pellet-shaped resin molded body obtained by the molding method according to claim 8. A film obtained by molding a pellet-shaped resin molding obtained by the molding method according to claim 8 with a film molding machine including a T-die.