JP2017124520A - Melting method of molding material, and production method of resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a melting method of a molding material containing a crystalline alicyclic structure, and to provide a production method of a resin molding in which a molten resin obtained by the method is molded.SOLUTION: In a melting method of a molding material containing a crystalline alicyclic structure-containing resin, an extruder having a cylinder, a screw contained in the cylinder, a hopper to feed the molding material into the cylinder, a temperature regulator (I) to regulate temperature in the cylinder, and a temperature regulator (II) to regulate temperature of the screw is used, and in which the molding material is fed into the cylinder under a predetermined condition, and the molding material in the cylinder is melted under a predetermined condition; and in a production method of a resin molding, a molten resin obtained by the method is molded.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for melting a molding material containing a crystalline alicyclic structure-containing resin, and a method for producing a resin molded body for molding a molten resin obtained by this method.

Many crystalline polymers have an ordered molecular arrangement, exhibit a melting point, and have a partial crystal structure, and are generally hard and have high rigidity.
Among these, crystalline alicyclic structure-containing resins are recently attracting attention as raw materials for various resin molded products because they are excellent in physical properties such as heat resistance, mechanical strength, and solvent resistance.
For example, Patent Documents 1 and 2 disclose crystalline dicyclopentadiene having syndiotactic stereoregularity by using a tungsten complex having an imide group having a substituent having a specific structure on a nitrogen atom as a polymerization catalyst. It is described that a ring-opened polymer hydride is obtained.
Further, Patent Document 3 describes that a film made of a crystalline norbornene monomer ring-opening polymer hydride is preferably used in the food field, the medical field, the display field, and the like.

JP 2005-89744 A JP 2006-52333 A JP 2009-197201 A

As a method for producing a resin molded body, there are an injection molding method, an extrusion molding method, and the like in which a molding material is melted and the obtained molten resin is molded into a predetermined shape.
In these molding methods, by using a molding material containing a crystalline alicyclic structure-containing resin (hereinafter sometimes referred to as “molding material (A)”), heat resistance, mechanical strength, and resistance A resin molded body having excellent solvent properties can be produced.

However, when a molded resin (A) is produced using a molding material (A), the molding material (A) is not sufficiently melted, and the molten resin cannot be stably extruded or injected. For this reason, a resin molded body having a desired shape may not be obtained.
Therefore, there has been a demand for a method capable of sufficiently melting a molding material containing a crystalline alicyclic structure-containing resin and stably producing a resin molding having a desired shape.

  The present invention has been made in view of the above circumstances, a method of sufficiently melting a molding material containing a crystalline alicyclic structure-containing resin, and a molten resin obtained by this method, It aims at providing the method which can manufacture the resin molding which has the target shape stably.

  In order to solve the above-mentioned problems, the present inventor diligently studied a method for melting the molding material (A). As a result, 1) When the molding material (A) is charged into the extruder, if the temperature of the molding material (A) is too high, the molding materials (A) adhere to each other, and the molding material (A) is placed in the extruder. 2) It is found that it is difficult to stably melt the molding material 2) In order to sufficiently melt the molding material (A), it is important to appropriately control the temperature in the extruder, and the present invention is It came to be completed.

Thus, according to the present invention, the following methods [1] to [3] for melting a molding material and [4] a method for producing a resin molded body are provided.
[1] A cylinder, a screw accommodated in the cylinder, a hopper for introducing molding material into the cylinder, a temperature adjusting device (I) for adjusting the temperature in the cylinder, and adjusting the temperature of the screw And a method of melting a molding material containing a crystalline alicyclic structure-containing resin using an extruder equipped with a temperature control device (II).
Based on the total length of the screw, when the position in the cylinder is expressed with the point corresponding to the root of the screw as the 0% point and the point corresponding to the tip of the screw as the 100% point, the molding material enters the cylinder through the hopper. Is placed in the region from the 0% point to the 7% point, and the temperature in the region from the 9% point to the 30% point in the cylinder is not less than the melting point of the molding material and not more than 350 ° C. Based on the total length, when the screw part is expressed with the screw root at the 0% point and the screw tip at the 100% point, the temperature in the region from the 0% point to the 30% point of the screw is the melting point of the molding material. The temperature of the molding material charged into the hopper is 350 ° C or less and the glass transition temperature of the molding material is -30 ° C or more and the glass transition temperature of the molding material is -10 ° C or less. It characterized the door, melting method of the molding material.
[2] The molding material melting method according to [1], wherein the temperature in the region from the 0% point to the 7% point in the cylinder is 50 ° C. or less.
[3] The molding according to [1] or [2], wherein the temperature in the hopper is not less than (temperature of the molding material charged into the hopper −10 ° C.) or more (temperature of the molding material charged into the hopper + 10 ° C.) or less. Material melting method.
[4] A method for producing a resin molded body, comprising molding the molten resin obtained by the method according to any one of [1] to [3].

  According to the present invention, a method of sufficiently melting a molding material containing a crystalline alicyclic structure-containing resin, and molding a molten resin obtained by this method, a resin molded body having a desired shape is stabilized. A method that can be manufactured automatically is provided.

It is a schematic diagram of the cross section of the extruder which can be used for this invention.

  Hereinafter, the present invention will be described in detail by dividing into 1) a molding material melting method and 2) a resin molded body manufacturing method.

1) Molding Material Melting Method The molding material melting method of the present invention includes a cylinder, a screw accommodated in the cylinder, a hopper for feeding the molding material into the cylinder, and a temperature inside the cylinder. The molding material containing the crystalline alicyclic structure-containing resin is melted using an extruder equipped with a temperature control device (I) and a temperature control device (II) for adjusting the temperature of the screw. A method in which the molding material is a hopper when the position in the cylinder is expressed with the point corresponding to the root of the screw as the 0% point and the point corresponding to the tip of the screw as the 100% point based on the total length of the screw. The place to be put into the cylinder through the cylinder is in the region from the 0% point to the 7% point, and the temperature in the region from the 9% point to the 30% point in the cylinder is 35 or more than the melting point of the molding material. The area of the screw from 0% point to 30% point when the screw part is expressed with the root of the screw as the 0% point and the screw tip as the 100% point, based on the total length of the screw. Is a melting point of the molding material and 350 ° C. or less,
The temperature of the molding material put into the hopper is (glass transition temperature of molding material -30 ° C) or more and (glass transition temperature of molding material -10 ° C) or less.

(Extruder)
The extruder used in the present invention includes a cylinder, a screw accommodated in the cylinder, a hopper for feeding molding material into the cylinder, a temperature adjusting device (I) for adjusting the temperature in the cylinder, And a temperature adjusting device (II) for adjusting the temperature of the screw.

FIG. 1 shows a schematic diagram of a cross section of an extruder that can be used in the present invention.
The extruder (10) shown in FIG. 1 includes a cylinder (1), a screw (2), a hopper (3), a temperature adjusting device (I) (not shown) for adjusting the temperature in the cylinder, and the screw temperature. A temperature control device (II) (not shown) for adjusting the temperature is provided.

  In the present invention, on the basis of the total length of the screw, a specific position in the cylinder is represented with a point corresponding to the root of the screw as a 0% point and a point corresponding to the tip of the screw as a 100% point. Similarly, on the basis of the total length of the screw, a specific portion of the screw is represented with the root of the screw being the 0% point and the tip of the screw being the 100% point.

In the extruder (10), the place where the molding material is put into the cylinder (1) through the hopper (3) (that is, the connection place between the hopper (3) and the cylinder (2)) is from the 0% point. It is within the area of 7% point. That is, in the method of the present invention, the molding material is not put into a place exceeding the 7% point in the cylinder (a place closer to the discharge port of the extruder than the 7% point).
If the molding material is introduced to a location exceeding the 7% point in the cylinder, the molding materials may adhere to each other, and it may be difficult to stably melt the molding material.

The temperature adjusting device (I) has a role of adjusting the temperature in the cylinder.
The temperature adjusting device (I) is not particularly limited as long as the cylinder can be maintained at a target temperature. As the temperature control device (I), for example, a heating device including heating means such as an electric resistance heating mechanism, an induction heating mechanism, an oil heating mechanism, a steam heating mechanism, and a cooling device including cooling means such as an air cooling mechanism and a water cooling mechanism And the like.

The temperature adjusting device (II) has a role of adjusting the temperature of the screw.
Temperature control apparatus (II) will not be specifically limited if a screw can be maintained at the target temperature. The temperature control device (II) usually has a cooling device. As a cooling device, what cools the screw surface by sending refrigerants, such as air, oil, and water, into a screw is mentioned.

[Molding material]
The molding material used in the present invention contains a crystalline alicyclic structure-containing resin. That is, in the present invention, the molding material (A) is used as the molding material.

The crystalline alicyclic structure-containing resin is a polymer having an alicyclic structure in the molecule and obtained by polymerizing a cyclic olefin and having crystallinity (hereinafter referred to as “polymer (α) ”).
“Crystalline alicyclic structure-containing resin” refers to an alicyclic structure-containing resin having a melting point of 180 ° C. or higher by differential scanning calorimetry.
In the present invention, “crystallinity” is a property inherent to the resin derived from the stereoregularity of the polymer chain. However, the alicyclic structure-containing resin used in the present invention is usually prepared under measurement sample preparation conditions ( Since the melting point is observed regardless of whether or not the sample is heat-treated, the “crystalline alicyclic structure-containing resin” can be defined as described above.

  Examples of the polymer (α) include a dicyclopentadiene ring-opening polymer hydride having syndiotactic stereoregularity described in International Publication No. 2012/033076, and an isotactic described in JP-A No. 2002-249553. Well-known ones such as dicyclopentadiene ring-opened polymer hydride having stereoregularity, norbornene ring-opened polymer hydride described in JP-A-2007-16102 can be used.

The melting point of the polymer (α) is preferably 180 to 350 ° C, more preferably 200 to 320 ° C, and particularly preferably 220 to 300 ° C.
A molding material containing the polymer (α) having a melting point in this range has good moldability. Moreover, it becomes easy to obtain the molded object which is excellent in heat resistance by using this molding material.

  As the polymer (α), it is easy to obtain a molded product superior in heat resistance, and therefore a dicyclopentadiene ring-opened polymer hydride having syndiotactic stereoregularity (hereinafter referred to as “polymer (α1)”). Is preferred).

The degree of stereoregularity of the polymer (α1) is not particularly limited, but the polymer (α1) has a degree of stereoregularity because the obtained molding material is more suitable as a molding material for a molded article having excellent heat resistance. Higher ones are preferred.
Specifically, the ratio of racemo dyad to the repeating unit obtained by ring-opening polymerization of dicyclopentadiene and then hydrogenating is preferably 51% or more, and more preferably 60% or more. 70% or more is particularly preferable.
The higher the ratio of racemo dyad, that is, the higher the syndiotactic stereoregularity, the more dicyclopentadiene ring-opening polymer hydride having a higher melting point.
The ratio of racemo dyad can be measured and quantified by ¹³ C-NMR spectrum analysis. Specifically, ¹³ C-NMR measurement was performed using ortho-dichlorobenzene-d4 as a solvent and an inverse-gated decoupling method applied at 150 ° C., and the 127.5 ppm peak of orthodichlorobenzene-d4 was used as a reference shift. The ratio of racemo dyad can be determined from the intensity ratio of the 43.35 ppm signal derived from meso dyad and the 43.43 ppm signal derived from racemo dyad.

  The polymer (α1) is obtained by performing ring-opening polymerization using dicyclopentadiene as a main monomer and hydrogenating at least part of the carbon-carbon double bonds present in the resulting ring-opening polymer. Can do.

  In dicyclopentadiene, there are stereoisomers of endo and exo, both of which can be used as monomers in the present invention. Moreover, only one isomer may be used alone, or an isomer mixture in which an endo isomer and an exo isomer are present in an arbitrary ratio may be used. In the present invention, since the obtained molding material is more suitable as a molding material of a molded body having excellent heat resistance, 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 still more preferably 95% or more. In addition, since the synthesis | combination is easy, it is preferable that the ratio of an end body is high.

When synthesizing the polymer (α1), only dicyclopentadiene may be used as a monomer, or a monomer mixture composed of dicyclopentadiene and other monomers copolymerizable with this may be used. Good.
Examples of other monomers include norbornenes other than dicyclopentadiene, cyclic olefins, and dienes.
When other monomers are used, the amount used is preferably 10% by weight or less, more preferably 5% by weight or less, based on the total amount of monomers.

  The ring-opening polymerization catalyst used for synthesizing the polymer (α1) is not particularly limited as long as it allows ring-opening polymerization of dicyclopentadiene to obtain a ring-opening polymer having syndiotactic stereoregularity. Preferred examples of the ring-opening polymerization catalyst include those containing a metal compound represented by the following formula (1).

In formula (1), M is a metal atom selected from group 6 transition metal atoms in the periodic table, and R ¹ may have a substituent at at least one of the 3, 4, and 5 positions. A good phenyl group or —CH ₂ R ³ (R ³ is a group selected from a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent). R ² is a group selected from an alkyl group which may have a substituent and an aryl group which may have a substituent, and X has a halogen atom and a substituent. L is a group selected from an optionally substituted alkyl group, an optionally substituted aryl group and an alkylsilyl group, and L is an electron-donating neutral ligand. a is 0 or 1, and b is an integer of 0-2.

  M is a transition metal atom (chromium, molybdenum, tungsten) belonging to Group 6 of the periodic table, preferably molybdenum or tungsten, and more preferably tungsten.

The number of carbon atoms of the phenyl group which may have a substituent at at least ^one of the 3, 4, and 5 positions of R ¹ is not particularly limited, but is usually 6 to 20, preferably 6 to 15. .
Examples of the substituent include alkyl groups such as methyl group and ethyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy groups such as methoxy group, ethoxy group and isopropoxy group;
In addition, substituents present in at least two positions of the 3, 4, and 5 positions may be bonded to each other to form a ring structure.
Examples of the phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions include an unsubstituted phenyl group; a 4-methylphenyl group, a 4-chlorophenyl group, a 3-methoxyphenyl group, 4- Monosubstituted phenyl groups such as cyclohexylphenyl group and 4-methoxyphenyl group; disubstituted groups such as 3,5-dimethylphenyl group, 3,5-dichlorophenyl group, 3,4-dimethylphenyl group and 3,5-dimethoxyphenyl group Phenyl group; trisubstituted phenyl group such as 3,4,5-trimethylphenyl group, 3,4,5-trichlorophenyl group; 2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl-2-naphthyl 2-naphthyl group which may have a substituent such as a group;

In the group represented by —CH ₂ R ³ in R ¹ , R ³ is a group selected from a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent. Represents.
Although carbon number of the alkyl group which may have a substituent of R < ³ > is not specifically limited, Usually, 1-20, Preferably it is 1-10. This alkyl group may be linear or branched.
Examples of the substituent include a phenyl group optionally having a substituent such as a phenyl group and a 4-methylphenyl group; an alkoxyl group such as a methoxy group and an ethoxy group; and the like.
Examples of the alkyl group which may have a substituent for R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, a benzyl group, And neophyll groups.

Of R ^3, the carbon number of the aryl group which may have a substituent is not particularly limited, usually, 6 to 20, preferably 6 to 15.
Examples of the substituent include alkyl groups such as methyl group and ethyl group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy groups such as methoxy group, ethoxy group and isopropoxy group;
Examples of the aryl group of R ³ which may have a substituent include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 4-methylphenyl group, and a 2,6-dimethylphenyl group.
Among these, the group represented by R ³ is preferably an alkyl group having 1 to 20 carbon atoms.

Examples of the halogen atom for X include a chlorine atom, a bromine atom, and an iodine atom.
As the alkyl group which may have a substituent of X and the aryl group which may have a substituent, the alkyl group which may have a substituent and the substituent of R ³ respectively. The thing similar to what was shown as an aryl group which may have is mentioned.
Examples of the alkylsilyl group of X include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and the like.
Moreover, when the metal compound shown by Formula (1) has two or more X, these may couple | bond together and may form the ring structure.

As the alkyl group which may have a substituent of R ² and the aryl group which may have a substituent, an alkyl group which may have a substituent and a substituent of R ³ respectively. The thing similar to what was shown as an aryl group which may have this is mentioned.

  Examples of the electron donating neutral ligand of L include an electron donating compound containing an atom of Group 14 or Group 15 of the periodic table. Specific examples thereof include phosphines such as trimethylphosphine, triisopropylphosphine, tricyclohexylphosphine, and triphenylphosphine; ethers such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, and tetrahydrofuran; trimethylamine, triethylamine, pyridine, Amines such as lutidine; and the like. Among these, ethers are preferable.

As the metal compound represented by the formula (1), a tungsten compound having a phenylimide group (a compound in which M in the formula (1) is a tungsten atom and R ¹ is a phenyl group) is preferable, and tetrachlorotungsten phenylimide ( Tetrahydrofuran) complexes are more preferred.

The method for synthesizing the metal compound represented by the formula (1) is not particularly limited. For example, the method described in JP-A-5-345817 can be mentioned. That is, an oxyhalide of a Group 6 transition metal, a phenyl isocyanate which may have a substituent at at least one of the 3, 4, and 5 positions, or a monosubstituted methyl isocyanate, and electron donation The target metal compound can be synthesized by mixing a neutral neutral ligand (L) and, if necessary, an alcohol, a metal alkoxide, and a metal aryloxide.
After the synthesis of the metal compound, the reaction solution may be used as it is as a catalyst solution for the ring-opening polymerization reaction, or after isolation and purification of the metal compound by a known purification treatment such as crystallization, You may use for ring-opening polymerization reaction.

The ring-opening polymerization catalyst may be composed only of the metal compound represented by the formula (1), or may be a combination of the metal compound represented by the formula (1) and an organometallic reducing agent. By using a combination of the metal compound represented by the formula (1) and the organometallic reducing agent, the polymerization activity is improved.
Examples of the organometallic reducing agent include organometallic compounds belonging to Groups 1, 2, 12, 13 and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms.
Examples of the organometallic compound include organic lithium such as methyl lithium, n-butyl lithium, and phenyl lithium; organic magnesium such as butyl ethyl magnesium, butyl octyl magnesium, dihexyl magnesium, ethyl magnesium chloride, n-butyl magnesium chloride, and allyl magnesium bromide. Organic zinc such as dimethyl zinc, diethyl zinc and diphenyl zinc; trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, diethyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum ethoxide, diisobutyl aluminum isobutoxide, ethyl aluminum di Organic aluminum such as ethoxide, isobutylaluminum diisobutoxide Um; tetramethyl tin, tetra (n- butyl) tin, organic tin such as tetraphenyl tin; and the like.
Among these, organoaluminum or organotin is preferable.

The ring-opening polymerization reaction is usually performed in an organic solvent. The organic solvent used is not particularly limited as long as it can dissolve or disperse the ring-opening polymer or its hydride under predetermined conditions and does not inhibit the ring-opening polymerization reaction or the hydrogenation reaction. .
Examples of the organic solvent include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexa Alicyclic hydrocarbons such as hydroindene and cyclooctane; Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; Chlorobenzene and dichlorobenzene Halogen-containing aromatic hydrocarbons such as: nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; ethers such as diethyl ether and tetrahydrofuran; Solvent mixture; and the like.
Among these, as the organic solvent, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and ethers are preferable.

The ring-opening polymerization reaction can be started by mixing the monomer, the metal compound represented by the formula (1), and, if necessary, an organometallic reducing agent. The order in which these components are added is not particularly limited. For example, a solution containing the metal compound represented by the formula (1) and the organometallic reducing agent may be added to and mixed with the solution containing the monomer, or the monomer containing the organometallic reducing agent may be added to the solution containing the organometallic reducing agent. And a solution containing the metal compound represented by the formula (1) may be added and mixed, or a solution containing the metal compound represented by the formula (1) may be added to the solution containing the monomer and the organometallic reducing agent. And may be mixed.
When adding each component, the whole quantity of each component may be added at once, and may be added in multiple times. Moreover, you may add continuously over a comparatively long time (for example, 1 minute or more).

  The concentration of the monomer at the start of the ring-opening polymerization reaction is not particularly limited, but is usually 1 to 50% by weight, preferably 2 to 45% by weight, and more preferably 3 to 40% by weight. If the concentration of the monomer is too low, the productivity may decrease. If it is too high, the solution viscosity after the ring-opening polymerization reaction is too high, and the subsequent hydrogenation reaction may be difficult.

  The amount of the metal compound represented by the formula (1) used in the ring-opening polymerization reaction is such that the molar ratio of (metal compound: monomer) is usually from 1: 100 to 1: 2,000,000, preferably 1: 500. ˜1,000,000, more preferably in an amount of 1: 1,000 to 1: 500,000. If the amount of the metal compound is too large, it may be difficult to remove the metal compound after the reaction. If the amount is too small, sufficient polymerization activity may not be obtained.

  When using an organometallic reducing agent, the amount used is preferably 0.1 to 100 mol, more preferably 0.2 to 50 mol, relative to 1 mol of the metal compound represented by formula (1), 0.5 ˜20 mol is particularly preferred. If the amount of the organometallic reducing agent used is too small, the polymerization activity may not be sufficiently improved, and if it is too much, side reactions may easily occur.

An activity regulator may be added to the polymerization reaction system. By using the activity regulator, the ring-opening polymerization catalyst can be stabilized, the reaction rate of the ring-opening polymerization reaction and the molecular weight distribution of the polymer can be adjusted.
The activity regulator is not particularly limited as long as it is an organic compound having a functional group. Examples of the activity regulator include oxygen-containing compounds, nitrogen-containing compounds, and phosphorus-containing compounds.
Examples of the oxygen-containing compound include ethers such as diethyl ether, diisopropyl ether, dibutyl ether, anisole, furan and tetrahydrofuran; ketones such as acetone, benzophenone and cyclohexanone; esters such as ethyl acetate;
Nitrogen-containing compounds include nitriles such as acetonitrile and benzonitrile; amines such as triethylamine, triisopropylamine, quinuclidine and N, N-diethylaniline; pyridine, 2,4-lutidine, 2,6-lutidine, 2- pyridines such as t-butylpyridine; and the like.
Examples of the phosphorus-containing compound include phosphines such as triphenylphosphine, tricyclohexylphosphine, triphenylphosphate, and trimethylphosphate; phosphine oxides such as triphenylphosphine oxide; and the like.
An activity regulator can be used individually by 1 type or in combination of 2 or more types. The amount of the activity regulator to be added is not particularly limited, but is usually selected from 0.01 to 100 mol% with respect to the metal compound represented by the formula (1).

A molecular weight modifier may be added to the polymerization reaction system in order to adjust the molecular weight of the ring-opening polymer. Examples of molecular weight modifiers include α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; aromatic vinyl compounds such as styrene and vinyltoluene; ethyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether, acetic acid Oxygen-containing vinyl compounds such as allyl, allyl alcohol and glycidyl methacrylate; halogen-containing vinyl compounds such as allyl chloride; nitrogen-containing vinyl compounds such as acrylamide; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1 , 6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene and other nonconjugated dienes; 1,3-butadiene, 2-methyl-1,3-butadiene, 2, 3-dimethyl-1,3-butadiene, 1,3-penta Ene, conjugated dienes such as 1,3-hexadiene; and the like.
A molecular weight regulator can be used individually by 1 type or in combination of 2 or more types. The amount of the molecular weight modifier to be added may be appropriately determined according to the target molecular weight, but is usually selected in the range of 0.1 to 50 mol% with respect to dicyclopentadiene.

  Although there is no restriction | limiting in particular in superposition | polymerization temperature, Usually, it is the range of -78- + 200 degreeC, Preferably it is the range of -30- + 180 degreeC. The polymerization time is not particularly limited and depends on the reaction scale, but is usually in the range of 1 minute to 1000 hours.

  The weight average molecular weight (Mw) of the dicyclopentadiene ring-opening polymer is not particularly limited, but is usually 1,000 to 1,000,000, preferably 2,000 to 500,000. By subjecting the ring-opening polymer having such a weight average molecular weight to a hydrogenation reaction, a polymer (α1) having an excellent balance between molding processability and heat resistance can be obtained. The weight average molecular weight of the ring-opening polymer can be adjusted by adjusting the amount of the molecular weight modifier used during polymerization.

The molecular weight distribution (Mw / Mn) of the dicyclopentadiene ring-opening polymer is not particularly limited, but is usually 1.0 to 4.0, preferably 1.5 to 3.5. By subjecting the ring-opening polymer having such a molecular weight distribution to a hydrogenation reaction, a polymer (α1) excellent in molding processability can be obtained. The molecular weight distribution of the ring-opening polymer can be adjusted by the monomer addition method and the monomer concentration during the polymerization reaction.
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the dicyclopentadiene ring-opened polymer are polystyrene-converted values measured by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.

  By the ring-opening polymerization reaction, a dicyclopentadiene ring-opening polymer having syndiotactic stereoregularity can be obtained. If the reaction conditions are appropriately set in the hydrogenation reaction performed after the ring-opening polymerization reaction, the tacticity of the ring-opening polymer is not normally changed by the hydrogenation reaction. The subject polymer (α1) can be obtained by subjecting the cyclopentadiene ring-opened polymer to a hydrogenation reaction. The degree of syndiotactic stereoregularity of the ring-opening polymer can be adjusted by selecting the type of ring-opening polymerization catalyst.

  The hydrogenation reaction of the ring-opening polymer can be performed by supplying hydrogen into the reaction system in the presence of a hydrogenation catalyst. As a hydrogenation catalyst, a well-known homogeneous catalyst and a heterogeneous catalyst can be used as a hydrogenation catalyst of an olefin compound.

  Homogeneous catalysts include transition metal compounds such as cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium, etc. Catalyst comprising a combination of alkali metal compounds; dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, chlorohydridocarbonylbis (tricyclohexylphosphine) ruthenium, bis (tricyclohexylphosphine) benzilidineruthenium (IV ) Noble metal complex catalysts such as dichloride and chlorotris (triphenylphosphine) rhodium;

  As heterogeneous catalysts, metal catalysts such as nickel, palladium, platinum, rhodium, ruthenium; nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina, etc. And a solid catalyst in which the metal is supported on a carrier such as carbon, silica, diatomaceous earth, alumina, titanium oxide or the like.

The hydrogenation reaction is usually performed in an inert organic solvent. Examples of the inert organic solvent include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decahydronaphthalene; tetrahydrofuran, ethylene glycol dimethyl ether, and the like. Ethers; and the like.
The inert organic solvent may be the same as or different from the solvent used in the ring-opening polymerization reaction. Alternatively, the hydrogenation catalyst may be added as it is to the ring-opening polymerization reaction solution to carry out the hydrogenation reaction.

The reaction conditions for the hydrogenation reaction vary depending on the hydrogenation catalyst used, but the reaction temperature is usually -20 to + 250 ° C, preferably -10 to + 220 ° C, more preferably 0 to + 200 ° C. If the reaction temperature is too low, the reaction rate may be too slow, and if the reaction temperature is too high, side reactions may occur.
The hydrogen pressure is usually 0.01 to 20 MPa, preferably 0.05 to 15 MPa, and more preferably 0.1 to 10 MPa. If the hydrogen pressure is too low, the reaction rate may be too slow. If the hydrogen pressure is too high, a special device such as a high pressure reactor is required.
Although reaction time will not be specifically limited if a desired hydrogenation rate is achieved, Usually, it is 0.1 to 10 hours.
After the hydrogenation reaction, the target polymer (α1) may be recovered according to a conventional method.

  The hydrogenation rate in the hydrogenation reaction (the ratio of hydrogenated main chain double bonds) is not particularly limited, but is preferably 98% or more, more preferably 99% or more. The higher the hydrogenation rate, the better the heat resistance of the polymer (α1).

  In the present invention, the crystalline alicyclic structure-containing resin can be used alone or in combination of two or more.

The molding material (A) may contain components other than the crystalline alicyclic structure-containing resin.
Components other than crystalline alicyclic structure-containing resins include antioxidants, UV absorbers, light stabilizers, near infrared absorbers, colorants such as dyes and pigments, plasticizers, antistatic agents, and fluorescent whitening And compounding agents such as other resins. Among these, it is preferable that the molding material (A) contains an antioxidant.

  Examples of the antioxidant include a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant.

  Examples of phenolic antioxidants include 3,5-di-t-butyl-4-hydroxytoluene, dibutylhydroxytoluene, 2,2′-methylenebis (6-t-butyl-4-methylphenol), 4,4 ′. -Butylidenebis (3-t-butyl-3-methylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), α-tocophenol, 2,2,4-trimethyl-6-hydroxy -7-t-butylchroman, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, and the like.

  Examples of phosphorus antioxidants include distearyl pentaerythritol diphosphite, bis (2,4-ditertiarybutylphenyl) pentaerythritol diphosphite, tris (2,4-ditertiarybutylphenyl) phosphite, tetrakis (2 , 4-ditertiary butylphenyl) 4,4′-biphenyl diphosphite, trinonylphenyl phosphite and the like.

  Examples of sulfur-based antioxidants include distearyl thiodipropionate and dilauryl thiodipropionate.

  Content of the said compounding agent can be suitably determined according to the objective. When molding material (A) contains the said compounding agent, the content is normally less than 50 weight% with respect to molding material (A), Preferably it is 40 weight% or less.

The manufacturing method of a molding material (A) is not specifically limited, It can manufacture according to a well-known method.
For example, a crystalline alicyclic structure-containing resin and other components are melt-kneaded in an extruder, the resulting molten resin is extruded into a strand shape, the strand is cooled, and then cut into a predetermined size. Thus, the molding material (A) can be produced.

  The magnitude | size of a molding material (A) is not specifically limited, It is the same as the magnitude | size of the conventional resin pellet. The diameter (major axis) of the molding material (A) is usually 1.5 to 3.5 mm, and the height of the molding material (A) (substantially cylindrical body height) is usually 1.5 to 3.5 mm. It is.

[Melting method]
The method of the present invention is a method in which the molding material (A) is melted using the extruder, and the region in the cylinder from the 9% point to the 30% point (hereinafter referred to as “region (i)”). 1 is in the range of B to C in the cylinder in FIG. 1 and is not lower than the melting point of the molding material (A) and not higher than 350 ° C. It is sometimes referred to as “region (ii).” The temperature of the screw A to C in FIG.1 is not lower than the melting point of the molding material (A) and not higher than 350 ° C., and the temperature of the molding material charged into the hopper is , (Glass transition temperature of molding material (A) -30 ° C.) or more and (Glass transition temperature of molding material (A) -10 ° C.) or less.

Region (i) is a region from the 9% point to the 30% point in the cylinder. The temperature of the region (i) is not lower than the melting point of the molding material (A) and not higher than 350 ° C., preferably not lower than the melting point of the molding material (A) and not higher than 320 ° C. If the temperature of the region (i) is too low, the molding material (A) cannot be sufficiently melted, and it becomes difficult to stably extrude the molten resin.
Note that the temperature of the region (i) is “x ° C. or more and y ° C. or less” means that all locations in the region (i) are x ° C. or more and y ° C. or less. The same applies to the area (ii) and the area (iii).

  Region (ii) is the region from the 0% point to the 30% point of the screw. The temperature of the region (ii) is not lower than the melting point of the molding material (A) and not higher than 350 ° C., preferably not lower than the melting point of the molding material (A) and not higher than 320 ° C. If the temperature of the region (ii) is too low, the molding material (A) cannot be sufficiently melted, and it becomes difficult to stably extrude the molten resin.

The temperature of the molding material (A) charged into the hopper is not less than (the glass transition temperature of the molding material (A) −30 ° C.) or more (the glass transition temperature of the molding material (A) −10 ° C.), preferably the molding material. (A) Glass transition temperature −20 ° C. or more (molding material (A) glass transition temperature −10 ° C. or less.
If the temperature of the molding material (A) put into the hopper is too low, the molding material (A) may not be sufficiently melted in the extruder. On the other hand, if the temperature of the molding material put into the hopper is too high, the molding materials (A) may adhere to each other and the molding material (A) may not be stably melted in the extruder.

Usually, the molding material (A) charged into the hopper is subjected to a drying process until just before the injection. Although drying conditions are not specifically limited, For example, a drying process can be performed by heating for 1 to 12 hours at the temperature at the time of throwing a molding material into a hopper.
Moreover, it is preferable to adjust the temperature in a hopper to the same extent as the temperature of the molding material (A) at the time of injection | throwing-in. For example, the temperature in the hopper is preferably (temperature of the molding material charged into the hopper−10 ° C.) or more and (temperature of molding material charged into the hopper + 10 ° C.) or less.

Further, the temperature in the region from 0% to 7% in the cylinder (hereinafter sometimes referred to as “region (iii)”) is preferably 50 ° C. or less.
When the temperature of the region (iii) is 50 ° C. or lower, it is possible to avoid the molding materials (A) charged in the cylinder from being attached to each other.

As described above, in the method of the present invention, the molding material (A) is kept at a relatively low temperature within a range that does not adversely affect the melting until the melting of the molding material (A) starts in the extruder. To be. Thereby, since mutual adhesion of the molding material (A) is suppressed, the molding material (A) can be stably melted in the extruder.
In the method of the present invention, since the temperature of the region (i) and the region (ii) is set sufficiently high, even a molding material containing a crystalline alicyclic structure-containing resin is placed in the cylinder. After charging, it can be sufficiently melted at an early stage.
As a result, according to the method of the present invention, the molten resin obtained by melting the molding material (A) can be stably discharged from the extruder.

  When a molding material containing a crystalline resin such as the molding material (A) is used, the crystallinity is increased by subjecting the molding material to be injected into the cylinder to a crystallization treatment, so A method of preventing wearing is also conceivable. However, according to the method of the present invention, the molding material can be sufficiently melted without performing such a special treatment. For this reason, the method of the present invention is preferably used when the crystallinity of the molding material is relatively low.

Whether or not the crystallization degree of the molding material is high can be determined by measuring the crystallization heat generation amount of the molding material.
The amount of heat generated by crystallization is the amount of heat generated when crystallization of the crystalline alicyclic structure-containing resin in the molding material proceeds. The crystallization exotherm can be determined from the peak area of the exothermic peak accompanying the crystallization promotion by using a differential scanning calorimeter to raise the temperature of the measurement sample at 10 ° C./min.

As described above, the molding material preferably used in the method of the present invention has a relatively low crystallinity, for example, a crystallization heat generation amount exceeding 10 mJ / mg.
When the molding material in such a state is melted by a normal method, it may be difficult to stably discharge the molten resin from the extruder. According to the method of the present invention, this problem is solved, and a sufficiently melted molten resin can be stably produced.

2) Manufacturing method of resin molding The manufacturing method of the resin molding of this invention shape | molds the molten resin obtained by the method of this invention.

The molding method is not particularly limited, and can be appropriately selected according to the shape of the resin molded body.
Examples of the molding method include an injection molding method, a sheet molding method, a blow molding method, an injection blow molding method, an inflation molding method, a T-die molding method, a press molding method, and an extrusion molding method.
Although it does not specifically limit as a resin molding, A light reflector, an insulating material, an optical film, a connector, a food packaging material, a bottle, a pipe, gears, a fiber, a nonwoven fabric, etc. are mentioned.

Since the manufacturing method of the resin molding of this invention shape | molds the molten resin obtained by the method of this invention, it can manufacture a resin molding stably.
For example, when the resin molding of the present invention is a resin film, a resin film with small thickness variation and high film thickness accuracy can be produced.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to these examples. In the following, “parts” and “%” are based on weight unless otherwise specified.

In Examples and Comparative Examples, various physical properties were measured according to the following methods.
(1) Molecular weight of dicyclopentadiene ring-opened polymer (weight average molecular weight and number average molecular weight)
The molecular weight of the dicyclopentadiene ring-opened polymer is a gel permeation chromatography (GPC) system HLC-8320 (manufactured by Tosoh Corporation), an H-type column (manufactured by Tosoh Corporation), and tetrahydrofuran at 40 ° C. using tetrahydrofuran as a solvent. It measured and calculated | required as a polystyrene conversion value.

(2) Hydrogenation rate in hydrogenation reaction ¹ H-NMR measurement was performed at 145 ° C. using an orthodichlorobenzene-d4 solvent to obtain the hydrogenation rate in the hydrogenation reaction.

(3) Ratio of racemo dyad of hydride of dicyclopentadiene ring-opening polymer ¹³ C-NMR measurement was carried out using ortho-dichlorobenzene-d4 as a solvent at 150 ° C. by applying an inverted-gate decoupling method, and dicyclopentadiene. The ratio of racemo dyad in the ring-opening polymer hydride was determined. Specifically, based on the intensity ratio of the 43.35 ppm signal derived from meso dyad and the 43.43 ppm signal derived from racemo dyad, with a 127.5 ppm peak of orthodichlorobenzene-d4 as a reference shift, The percentage of racemo dyads was determined.

(4) Glass transition temperature and melting point of molding material Based on JIS-7121-1987, the glass transition temperature and melting point of the molding material were measured.

(5) Extrusion stability The stability of extrusion of a molten resin when a resin film was produced in Examples or Comparative Examples was evaluated according to the following criteria.
○: (Standard deviation of motor current value during continuous driving for 60 minutes) ≦ 0.5
×: (Standard deviation of motor current value during continuous driving for 60 minutes)> 0.5

(6) Film thickness accuracy The film thickness accuracy was calculated by the following equation by scanning the film thickness in the TD direction.

[Production Example 1]
In a metal pressure-resistant reaction vessel purged with nitrogen inside, 154.5 parts of cyclohexane, 42.8 parts of cyclohexane solution (concentration 70%) of dicyclopentadiene (end content 99% or more) (30 parts as dicyclopentadiene) 1-hexene 1.9 parts was added and the whole was heated to 53 ° C.
On the other hand, in a solution obtained by dissolving 0.014 part of tetrachlorotungstenphenylimide (tetrahydrofuran) complex in 0.70 part of toluene, 0.061 part of n-hexane solution of diethylaluminum ethoxide (concentration 19%). And stirred for 10 minutes to prepare a catalyst solution. This catalyst solution was added to the reactor and a ring-opening polymerization reaction was performed at 53 ° C. for 4 hours to obtain a solution containing a dicyclopentadiene ring-opening polymer.

To 200 parts of the solution containing the obtained dicyclopentadiene ring-opened polymer, 0.037 part of 1,2-ethanediol was added as a terminator and stirred at 60 ° C. for 1 hour to stop the polymerization reaction. Thereafter, 1 part of a hydrotalcite-like compound (product name “KYOWARD (registered trademark) 2000”, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, heated to 60 ° C., and stirred for 1 hour. 0.4 parts of filter aid (product name “Radiolite (registered trademark) # 1500” manufactured by Showa Chemical Industry Co., Ltd.) is added, and PP pleated cartridge filter (product name “TCP-HX”, manufactured by ADVANTEC Toyo Co., Ltd.) is used. The adsorbent was filtered off to obtain a solution containing a dicyclopentadiene ring-opening polymer.
A part of this solution was used to measure the molecular weight of the dicyclopentadiene ring-opened polymer. The weight average molecular weight (Mw) was 28,100, the number average molecular weight (Mn) was 8,750, the molecular weight distribution (Mw / Mn) was 3.21.

100 parts cyclohexane and 0.0043 parts chlorohydridocarbonyltris (triphenylphosphine) ruthenium are added to 200 parts solution (polymer content 30 parts) containing dicyclopentadiene ring-opening polymer after purification treatment, and hydrogen The hydrogenation reaction was carried out at 6 MPa and 180 ° C. for 4 hours. The reaction liquid was a slurry liquid in which a solid content was deposited.
The reaction solution was centrifuged to separate the solid and the solution, and the solid was dried under reduced pressure at 60 ° C. for 24 hours to obtain 28.5 parts of a dicyclopentadiene ring-opened polymer hydride.
The hydrogenation rate of the unsaturated bond in the hydrogenation reaction was 99% or more, and the glass transition temperature of the dicyclopentadiene ring-opened polymer hydride was 98 ° C. and the melting point was 262 ° C. The proportion of racemo dyads was 89%. The crystallization temperature was 130 ° C.

[Production Example 2]
To 100 parts of the dicyclopentadiene ring-opening polymer hydride obtained in Production Example 1, an antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] was added. After mixing 0.8 part of methane, product name “Irganox (registered trademark) 1010” (manufactured by BASF Japan), the mixture is put into a twin screw extruder (TEM-37B, manufactured by Toshiba Machine Co., Ltd.) and melted by heat. After obtaining a strand-shaped molded body by extrusion molding, this was chopped with a strand cutter to obtain a molding material. The molding material had a glass transition temperature of 93 ° C. and a melting point of 265 ° C.
The operating conditions of the twin screw extruder are shown below.
-Barrel set temperature: 270-280 ° C
・ Die setting temperature: 250 ℃
・ Screw speed: 145rpm
・ Feeder rotation speed: 50 rpm

[Examples 1 and 2 and Comparative Examples 1 to 3]
Using the molding material obtained in Production Example 2, a molding process was performed targeting a film having a width of 120 mm and a thickness of 100 μm. The conditions common to Examples 1 and 2 and Comparative Examples 1 to 3 are as follows, and the other conditions are those described in Table 1.
-Molding machine: hot melt extrusion film forming machine equipped with a T-die (product name “Measuring Extruder Type Me-20 / 2800V3”, manufactured by Optical Control Systems)
-Die temperature: 270 ° C
-Screw rotation speed: 30rpm
-Film winding speed: 1 m / min

  The measurement results and evaluation results in Examples 1 and 2 and Comparative Examples 1 to 3 are shown in Table 1.

The following can be seen from Table 1.
In Examples 1 and 2, the molten resin can be stably extruded. As a result, a resin film excellent in film thickness accuracy can be manufactured.
On the other hand, in Comparative Examples 1 to 3, the molten resin cannot be stably extruded, and the thickness of the resin film varies.

1. Cylinder 2. Screw 3. Hopper 10. Extruder A. 0% point 9% point C.I. 30% point 100% point

Claims (4)

A cylinder, a screw accommodated in the cylinder, a hopper for feeding molding material into the cylinder, a temperature adjusting device (I) for adjusting the temperature in the cylinder, and a temperature for adjusting the screw A method of melting a molding material containing a crystalline alicyclic structure-containing resin using an extruder equipped with a temperature control device (II),
Based on the total length of the screw, when the position in the cylinder is represented with the point corresponding to the root of the screw as the 0% point and the point corresponding to the tip of the screw as the 100% point,
The place where the molding material is put into the cylinder through the hopper is in the region from the 0% point to the 7% point,
The temperature of the region from the 9% point to the 30% point in the cylinder is not lower than the melting point of the molding material and not higher than 350 ° C.,
Based on the total length of the screw, when the screw part is expressed with the root of the screw as the 0% point and the tip of the screw as the 100% point,
The temperature of the region from 0% point to 30% point of the screw is not lower than the melting point of the molding material and not higher than 350 ° C,
A method for melting a molding material, characterized in that the temperature of the molding material charged into the hopper is (glass transition temperature of molding material -30 ° C) or more and (glass transition temperature of molding material -10 ° C) or less.   The method for melting a molding material according to claim 1, wherein the temperature in the region from the 0% point to the 7% point in the cylinder is 50 ° C or lower.   The method for melting a molding material according to claim 1 or 2, wherein the temperature in the hopper is (temperature of molding material charged into hopper-10 ° C) or higher (temperature of molding material charged into hopper + 10 ° C) or lower.   A method for producing a resin molded body, comprising molding the molten resin obtained by the method according to claim 1.

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