JP6528631B2 - MOLDING MATERIAL, MOLDED BODY, AND METHOD FOR MANUFACTURING MOLDING MATERIAL - Google Patents

Description

  The present invention is a molding material capable of stably producing a molded article having excellent heat resistance, mechanical strength and solvent resistance and having a good appearance, a molded article obtained using this molding material, and the above The present invention relates to a method for producing a molding material having characteristics.

Crystalline polymers have an ordered molecular arrangement, exhibit a melting point, and often have a partial crystal structure, and are generally considered to be hard and have high rigidity.
Among them, crystalline alicyclic structure-containing resins are attracting attention in recent years as raw materials for various resin moldings 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, as a polymerization catalyst, a tungsten complex having an imide group having a substituent having a specific structure on a nitrogen atom. 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-opened polymer hydride as a raw material is suitably used in the food field, the medical field, the display field and the like.

JP 2005-89744 A Unexamined-Japanese-Patent No. 2006-52333 JP, 2009-197201, A

  As a method for producing a resin molded body, an injection molding method, an extrusion molding method, and the like are known, in which a molding material made of a pellet assembly is melted and the obtained molten resin is molded into a predetermined shape. A molding material used in these methods is produced by melt-kneading a raw resin in an extruder, extruding the obtained molten resin in a strand, cooling the strand, and cutting it into a predetermined size. Can.

In these methods, heat resistance can be obtained by using a molding material (hereinafter sometimes referred to as “molding material (α)”) composed of an aggregate of pellets containing a crystalline alicyclic structure-containing resin. A resin molded product excellent in mechanical strength and solvent resistance can be manufactured.
However, when a molded product is produced using the molding material (α), extrusion or injection of the molten resin can not be stably performed, or appearance defects may occur in the obtained molded product. there were.
Therefore, there has been a demand for a molding material (α) that can stably produce a molded article having a good appearance.

  The present invention has been made in view of the above-described circumstances, and is a molding material capable of stably producing a molded article having excellent heat resistance, mechanical strength and solvent resistance and having a good appearance. An object of the present invention is to provide a molded body obtained by using this molding material and a method for producing a molding material having the above-mentioned characteristics.

In order to solve the above-mentioned subject, the present inventor diligently studied about a molding material (alpha). As a result, 1) A molding material (α) in which the shape of the pellet is substantially cylindrical, the pellet has a crystallization calorific value of 10 mJ / mg or less, and the average flatness of the aggregate of pellets is 0.35 or less By using it, it is possible to stably manufacture a molded product having excellent heat resistance, mechanical strength and solvent resistance and having a good appearance, and 2) to significantly change the shape of a specific raw material pellet By efficiently increasing the degree of crystallization of the raw material pellets, a molding material capable of stably producing a molded article having excellent heat resistance, mechanical strength and solvent resistance and having a good appearance can be efficiently produced. It has been found that the present invention can be completed.
In the present specification, “crystallization of crystalline resin in pellet” may be described as “crystallization of pellet”.

Thus, according to the present invention, there are provided methods for producing the following molding materials [1] to [3], moldings [4] and [5], and molding materials [6] to [8].
[1] A molding material comprising an aggregate of substantially cylindrical product pellets, containing a crystalline alicyclic structure-containing resin, wherein the crystallization calorific value of the product pellets is 10 mJ / mg or less, A molding material characterized in that an average flatness of an assembly of product pellets is 0.35 or less.
[2] The molding material according to [1], wherein the alicyclic structure-containing resin is a hydride of dicyclopentadiene ring-opened polymer.
[3] The assembly of the product pellets is obtained by heating an assembly of raw material pellets having a crystallization calorific value of 20 to 35 mJ / mg, which contains a crystalline alicyclic structure-containing resin, The molding material as described in [1] or [2].
[4] A molded body obtained by molding the molding material according to any one of the above [1] to [3].
[5] The molded article according to [4], which is a film-like molded article having a haze of 1.0% or less.
[6] A method for producing a molding material comprising an aggregate of product pellets, which is a substantially columnar raw material pellet containing a crystalline alicyclic structure-containing resin and having a crystallization calorific value of 20 to 35 mJ / mg. It has a crystallization step of converting the aggregate into an aggregate of substantially cylindrical product pellets having a crystallization calorific value of 10 mJ / mg or less, and in the crystallization step, an aggregate of product pellets from the aggregate of raw material pellets The manufacturing method of a molding material characterized by an average dimensional change rate at the time of changing to -10.0 to 0%.
[7] The crystallization step is a step of heating the aggregate of the raw material pellets to a temperature of (crystallization temperature −10 ° C.) or more and less than the melting point of the alicyclic structure-containing resin, [6] The manufacturing method of the molding material as described in-.
[8] The method for producing a molding material as described in [6] or [7], wherein the alicyclic structure-containing resin is a hydride of dicyclopentadiene ring-opened polymer.

  According to the present invention, a molding material capable of stably producing a molded article having excellent heat resistance, mechanical strength and solvent resistance and having a good appearance, and a molded article obtained using this molding material And a method of producing a molding material having the above characteristics.

  Hereinafter, the present invention will be described in detail in terms of 1) a molding material and a molded body, and 2) a manufacturing method of the molding material.

1) Molding Material The molding material of the present invention comprises an aggregate of substantially cylindrical product pellets containing a crystalline alicyclic structure-containing resin, and the calorific value of the product pellets is 10 mJ. / Mg or less, and the average flatness of the product pellet assembly is 0.35 or less.

[Product pellet]
The product pellet which comprises the said assembly contains crystalline alicyclic structure containing resin.
A crystalline alicyclic structure-containing resin is a polymer obtained by polymerizing a cyclic olefin, having an alicyclic structure in the molecule, and having crystallinity (hereinafter, “polymer (α) There is a thing called ").
"Crystalline alicyclic structure-containing resin" refers to an alicyclic structure-containing resin having a melting point of 180 ° C. or higher as measured by differential scanning calorimetry.
In the present invention, “crystalline” is a property inherent to the resin derived from the stereoregularity of the polymer chain, but the alicyclic structure-containing resin used in the present invention is usually under the condition for preparing the measurement sample ( The “crystalline alicyclic structure-containing resin” can be defined as described above because the melting point is observed regardless of the presence or absence of the heat treatment to the sample.

  As the polymer (α), a dicyclopentadiene ring-opened polymer having syndiotactic stereoregularity described in International Publication WO 2012/033076 pamphlet, an isotactic polymer described in JP-A-2002-249553. Known compounds 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., particularly preferably 220 to 300 ° C.
Molding materials using a polymer (α) having a melting point in this range have good moldability. Moreover, the molded object which is excellent in heat resistance becomes is easy to be obtained by using this molding material.

  As the polymer (α), a dicyclopentadiene ring-opened polymer hydride having syndiotactic stereoregularity (hereinafter referred to as “polymer (α1)” because the molding material of the present invention can be efficiently produced. May be preferred).

Although the degree of stereoregularity of the polymer (α1) is not particularly limited, the polymer (α1) has a degree of stereoregularity because the resulting molding material is more suitable as a molding material of a molded article having excellent heat resistance. Higher is preferred.
Specifically, the ratio of racemo dyad to repeating units obtained by ring-opening polymerization of dicyclopentadiene and subsequent hydrogenation is preferably 51% or more, more preferably 60% or more And 70% or more is particularly preferable.
The higher the ratio of racemo dyads, that is, the higher the syndiotactic stereoregularity, the more the dicyclopentadiene ring-opened polymer hydride having a higher melting point.
The ratio of racemo dyads can be measured and quantified by ¹³ C-NMR spectroscopy. Specifically, ¹³ C-NMR measurement is performed by applying inverse-gated decoupling method at 150 ° C. using ortho-dichlorobenzene-d4 as a solvent, and a peak at 127.5 ppm of ortho-dichlorobenzene-d4 is used as a reference shift, The ratio of racemo dyads can be determined from the intensity ratio of the 43.35 ppm signal from meso dyad and the 43.43 ppm signal from racemo dyad.

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

  Although dicyclopentadiene has stereoisomers of endo form and exo form, both of them can be used as monomers in the present invention. In addition, only one isomer may be used alone, or an isomer mixture in which an endo form and an exo form are present in any ratio may be used. In the present invention, it is preferable to increase the ratio of one stereoisomer because the resulting molding material is more suitable as a molding material for a molded article having excellent heat resistance. For example, the proportion of endo or exo is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more. In addition, since the synthesis is easy, it is preferable that the proportion of the endo form is high.

When the polymer (α1) is synthesized, only dicyclopentadiene may be used as a monomer, or another monomer copolymerizable with dicyclopentadiene may be used. Other monomers include norbornenes other than dicyclopentadiene, cyclic olefins, dienes and the like.
When other monomers are used, the amount thereof 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 in synthesizing the polymer (α1) is not particularly limited as long as it can ring-opening-polymerize dicyclopentadiene to obtain a ring-opened polymer having syndiotactic stereoregularity. As a preferable ring-opening polymerization catalyst, what contains the metal compound shown by following formula (1) is mentioned.

In the formula (1), M is a metal atom selected from transition metal atoms of Group 6 of the periodic table, and R ¹ may have a substituent at at least one of positions 3, 4 and 5 Or a preferred phenyl group or -CH ₂ R ³ (wherein 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 an electron donating neutral ligand, and is a group selected from an alkyl group which may be substituted, an aryl group which may have a substituent, and an alkylsilyl group. a is 0 or 1 and b is an integer of 0-2.

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

The carbon number of the phenyl group which may have a substituent at at least one of positions 3, 4 and 5 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 and ethyl; halogen atoms such as fluorine, chlorine and bromine; and alkoxy groups such as methoxy, ethoxy and isopropoxy.
In addition, substituents present at at least two positions of 3, 4 and 5 may be bonded to each other to form a ring structure.
As a phenyl group which may have a substituent at at least one position of 3, 4 and 5 positions, unsubstituted phenyl group; 4-methylphenyl group, 4-chlorophenyl group, 3-methoxyphenyl group, 4- Monosubstituted phenyl groups such as cyclohexylphenyl group and 4-methoxyphenyl group; disubstituted 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 and 3,4,5-trichlorophenyl group; 2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl-2-naphthyl group And 2-naphthyl group which may have a substituent such as group;

In the group represented by -CH ₂ R ³ of 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
The carbon number of the optionally substituted alkyl group of R ³ is not particularly limited, but is usually 1 to 20, preferably 1 to 10. The alkyl group may be linear or branched.
Examples of the substituent include a phenyl group which may have a substituent such as phenyl group and 4-methylphenyl group; and an alkoxyl group such as methoxy group and ethoxy group.
The alkyl group which may have a substituent as R ³ is methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, benzyl group, Neophil group etc. are mentioned.

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

As a halogen atom of X, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
Examples of the alkyl group which may have a substituent, and the aryl group which may have a substituent of X include an alkyl group which may have a substituent and a substituent which each may have a substituent of R ^3. The same groups as those described as the optionally substituted aryl group may be mentioned.
Examples of the alkylsilyl group of X include a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group.
Moreover, when the metal compound shown by Formula (1) has 2 or more X, these may mutually couple | bond and may form ring structure.

As the alkyl group which may have a substituent or the aryl group which may have a substituent, of R ² , the alkyl group which may have a substituent of R ³ , a substituent, respectively And the same as those described as the optionally substituted aryl group.

  The electron donating neutral ligand of L includes an electron donating compound containing an atom of Group 14 or Group 15 of the periodic table. Specific examples thereof include phosphines such as trimethyl phosphine, triisopropyl phosphine, tricyclohexyl phosphine and triphenyl phosphine; ethers such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane and tetrahydrofuran; trimethylamine, triethylamine, pyridine, And amines such as lutidine and the like. Among these, ethers are preferable.

The metal compound represented by the formula (1) is preferably 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), and tetrachlorotungsten phenylimide (a compound Tetrahydrofuran) complexes are more preferred.

The synthesis method of the metal compound represented by the formula (1) is not particularly limited. For example, the method described in Unexamined-Japanese-Patent No. 5-345817 is mentioned. That is, an oxyhalide of a Group 6 transition metal, phenyl isocyanates which may have a substituent at at least one of the 3, 4, and 5 positions, or monosubstituted methyl isocyanates; 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 ring-opening polymerization reaction, or after the metal compound is isolated and purified by a known purification treatment such as crystallization, the obtained metal compound is It may be subjected to a 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. The polymerization activity is improved by using the metal compound represented by the formula (1) in combination with the organometallic reducing agent.
As an organometallic reducing agent, the organometallic compound of periodic table group 1, 2, 12, 13, 14 which has a C1-C20 hydrocarbon group is mentioned.
Examples of the organometallic compounds include organolithiums such as methyllithium, n-butyllithium and phenyllithium; organomagnesiums such as butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, allylmagnesium bromide and the like Organic zinc such as dimethyl zinc, diethyl zinc, 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 and 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 carried out 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. .
As an organic solvent, aliphatic hydrocarbons such as pentane, hexane and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexa Alicyclic hydrocarbons such as hydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogen-based aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; chlorobenzene and dichlorobenzene Halogenated aromatic hydrocarbons such as N, N-containing hydrocarbons such as nitromethane, nitrobenzene, acetonitrile etc .; Ethers such as diethyl ether, tetrahydrofuran etc. 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 initiated by mixing the monomer, the metal compound represented by the formula (1), and, if necessary, the organometallic reducing agent. The order in which these components are added is not particularly limited. For example, a solution containing a metal compound represented by the formula (1) and an organometallic reducing agent may be added to and mixed with a solution containing a monomer, or a solution containing an organometallic reducing agent may be mixed with a monomer 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) is added to a solution containing the monomer and the organometallic reducing agent You may mix and mix.
When adding each component, the whole quantity of each component may be added at once, and may be divided and added in multiple times. Alternatively, they may be added continuously over a relatively 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 be lowered. If it is too high, the solution viscosity after the ring-opening polymerization reaction may be 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 1: 100 to 1: 2,000,000, preferably 1: 500. The amount is 1 to 1,000,000, more preferably 1: 1,000 to 1: 500,000. When the amount of the metal compound is too large, it may be difficult to remove the metal compound after the reaction, and when it is too small, sufficient polymerization activity may not be obtained.

  When an organometallic reducing agent is used, the amount thereof used is preferably 0.1 to 100 mol, more preferably 0.2 to 50 mol, per 1 mol of the metal compound represented by the formula (1). -20 moles are particularly preferred. If the amount of the organic metal reducing agent used is too small, the polymerization activity may not be sufficiently improved, and if it is too large, 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, and 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 oxygen-containing compounds 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;
Examples of 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, triphenyl phosphate and trimethyl phosphate; phosphine oxides such as triphenyl phosphine oxide; and the like.
The activity modifiers can be used alone or in combination of two or more. The amount of the activity modifier to be added is not particularly limited, but generally, it may be selected between 0.01 and 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-opened polymer. As molecular weight modifiers, α-olefins such as 1-butene, 1-pentene, 1-hexene, 1-octene, etc .; aromatic vinyl compounds such as styrene, vinyl toluene; 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 Non-conjugated dienes such as 2,6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene; 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 modifier 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 suitably determined in accordance with the target molecular weight, but generally, it may be selected in the range of 0.1 to 50 mol% with respect to dicyclopentadiene.

  The polymerization temperature is not particularly limited, but is usually in the range of −78 to + 200 ° C., preferably in the range of −30 to + 180 ° C. 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-opened polymer is not particularly limited, but is usually 1,000 to 1,000,000, preferably 2,000 to 500,000. By subjecting a ring-opened polymer having such a weight average molecular weight to a hydrogenation reaction, a polymer (α1) excellent in the balance between moldability and heat resistance can be obtained. The weight average molecular weight of the ring-opened polymer can be adjusted by adjusting the amount of the molecular weight modifier to be used at the time of polymerization.

The molecular weight distribution (Mw / Mn) of the dicyclopentadiene ring-opened polymer is not particularly limited, but is usually 1.0 to 4.0, preferably 1.5 to 3.5. By subjecting a ring-opening polymer having such a molecular weight distribution to a hydrogenation reaction, a polymer (α1) excellent in moldability can be obtained. The molecular weight distribution of the ring-opening polymer can be adjusted by the addition method of the monomer at the time of the polymerization reaction or the concentration of the monomer.
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the dicyclopentadiene ring-opened polymer are polystyrene equivalent 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 to be performed after the ring-opening polymerization reaction, the tacticity of the ring-opening polymer does not usually change due to the hydrogenation reaction. The target polymer (α1) can be obtained by subjecting a cyclopentadiene ring-opening 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 carried out by supplying hydrogen into the reaction system in the presence of a hydrogenation catalyst. As the hydrogenation catalyst, known homogeneous catalysts or heterogeneous catalysts can be used as hydrogenation catalysts for olefin compounds.

  Examples of 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 consisting of a combination of alkali metal compounds; dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, chlorohydridocarbonylbis (tricyclohexylphosphine) ruthenium, bis (tricyclohexylphosphine) benzylidine ruthenium (IV) And the like) noble metal complex catalysts such as dichloride and chlorotris (triphenylphosphine) rhodium;

  Heterogeneous catalysts include metal catalysts such as nickel, palladium, platinum, rhodium and ruthenium; nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina etc And solid catalysts obtained by supporting the metal on a carrier such as carbon, silica, diatomaceous earth, alumina, titanium oxide and the like.

The hydrogenation reaction is usually carried out in an inert organic solvent. As an inert organic solvent, 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; etc. are mentioned.
The inert organic solvent may be the same as or different from the solvent used for the ring-opening polymerization reaction. In addition, a hydrogenation catalyst may be added to the ring-opening polymerization reaction solution as it is to carry out a hydrogenation reaction.

The reaction conditions of 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, more preferably 0.1 to 10 MPa. If the hydrogen pressure is too low, the reaction rate may be too slow, and if the hydrogen pressure is too high, special equipment such as a high pressure resistant reactor is required.
The reaction time is not particularly limited as long as the desired degree of hydrogenation can be achieved, and is usually 0.1 to 10 hours.
After the hydrogenation reaction, the target polymer (α1) may be recovered according to a conventional method.

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

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

The product pellet which comprises the said assembly may contain components other than crystalline alicyclic structure containing resin.
As components other than the crystalline alicyclic structure-containing resin, antioxidants, ultraviolet light absorbers, light stabilizers, near infrared light absorbers, colorants such as dyes and pigments, plasticizers, antistatic agents, fluorescent whitening And additives such as other resins. Among these, the product pellet preferably contains an antioxidant.

  Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and the like.

  As a phenolic antioxidant, 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-tocopherol, 2,2,4-trimethyl-6-hydroxy Examples thereof include -7-t-butylchroman, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane and the like.

  As a phosphorus antioxidant, distearyl pentaerythritol diphosphite, bis (2,4-ditertiary butylphenyl) pentaerythritol diphosphite, tris (2,4-ditertiary butylphenyl) phosphite, tetrakis (2) 4, 4-di-tert-butylphenyl) 4, 4'-biphenyl diphosphite, torinylphenyl phosphite and the like.

  Examples of sulfur-based antioxidants include distearylthiodipropionate, dilaurylthiodipropionate and the like.

  The content of the compounding agent can be appropriately determined in accordance with the purpose. When the product pellet contains the compounding agent, its content is usually less than 50% by weight, preferably 40% by weight or less, based on the product pellet.

The product pellets constituting the assembly have a substantially cylindrical shape.
The substantially cylindrical shape means a shape that can be approximated to a cylindrical shape or a cylindrical shape, and is similar to the shape of a conventional resin pellet obtained by cutting a strand. Examples of the substantially cylindrical shape include a cylindrical shape, an elliptic cylindrical shape, and the like. The surface of these shapes may have irregularities.

The crystallization calorific value of product pellets constituting the assembly is 10 mJ / mg or less, preferably 0 to 10 mJ / mg, more preferably 0 to 5 mJ / mg.
The crystallization calorific value is the amount of heat generated when the crystallization of the crystalline alicyclic structure-containing resin in the product pellet proceeds. The crystallization calorific value can be measured by the method described in the examples using a differential scanning calorimeter.
Product pellets having a crystallization calorific value of more than 10 mJ / mg are those in which crystallization has not sufficiently progressed. When a molded body is manufactured using a molding material composed of such an assembly of product pellets, the molten resin can not be stably discharged from the extruder, and the molded body may not be manufactured stably.
As for the product pellet whose crystallization calorific value is 10 mJ / mg or less, as described later, the pellet (raw material pellet) as the raw material is subjected to crystallization treatment to form a crystalline alicyclic structure-containing resin constituting the raw material pellet It can be obtained by advancing crystallization.

  The size of the product pellet is not particularly limited, and is similar to that of the conventional resin pellet. The diameter (long diameter) of the product pellet is usually 1.5 to 3.5 mm, and the height of the product pellet (approximately cylindrical body) is usually 1.5 to 3.5 mm.

[Assembly of product pellets]
The average flatness of the assembly of product pellets, which is the molding material of the present invention, is 0.35 or less, preferably 0 to 0.25, and more preferably 0 to 0.2.
The average flatness of the assembly of product pellets can be determined by arbitrarily selecting 20 or more product pellets, determining the respective flatness, and then calculating the average value.
The flat ratio of each of the product pellets can be calculated by the following equation after the cross section is approximated to an ellipse and the major diameter (a) and the minor diameter (b) are measured.

  Depending on the conditions of the above-mentioned crystallization treatment, the raw material pellets may be deformed in the process, and the average flatness of the assembly of product pellets may exceed 0.35. When manufacturing a molded object by measuring the molding material which consists of an assembly of such a product pellet on a volume basis, it may become difficult to measure the molding material to be used correctly.

The deformation of the raw material pellet in the above-mentioned crystallization process may be caused, for example, by melting or adhesion of the raw material pellet, or scraping of the raw material pellet.
When a molded product is produced using a molding material containing product pellets in which a shape abnormality has occurred due to melting or mutual adhesion of raw material pellets, the molten resin can not be stably discharged from the extruder, and the molded product is stably manufactured. May not be manufactured.
Further, a molding material containing a product pellet in which a shape abnormality has occurred due to scraping of the raw material pellet usually contains a powdery resin component and the like. The powdery resin component etc. has a moving speed at the time of melting the molding material using an extruder different from that of pellets, so that the resulting molded body may be burnt or the powdery molded body In some cases, a molded product having a good appearance can not be obtained due to mixing.

[Production Method of Product Pellet Assembly]
The assembly of product pellets can be produced, for example, by heating an assembly of raw material pellets containing a crystalline alicyclic structure-containing resin and having a crystallization calorific value of 20 to 35 mJ / mg.

Raw material pellets are a manufacturing material of product pellets. By advancing the crystallization of the crystalline alicyclic structure-containing resin constituting the raw material pellet, a product pellet is obtained.
The crystalline alicyclic structure-containing resin constituting the raw material pellet is the same as that described above.
The raw material pellet may contain components other than the crystalline alicyclic structure-containing resin. This component is similar to that shown above.

The crystallization calorific value of the raw material pellet is 20 to 35 mJ / mg, preferably 25 to 30 mJ / mg.
The molding material of this invention can be efficiently obtained by using the raw material pellet whose crystallization calorific value is in the said range.

An aggregate of raw material pellets can be produced by using a known method for producing resin pellets.
For example, an aggregate of raw material pellets is obtained by melt-kneading a crystalline alicyclic structure-containing resin (or a resin composition thereof) in an extruder, extruding the obtained molten resin into strands, and cooling the strands Thereafter, it can be manufactured by cutting into a predetermined size.

Since the raw material pellet obtained by such a method is not subjected to a process that deforms the shape, its shape is generally cylindrical rather than the shape of the product pellet.
The average flatness of the raw material pellet assembly is usually 0.33 or less, preferably 0 to 0.25.

As long as the product pellet assembly of the present invention can be obtained, the heating method for advancing crystallization of the raw material pellet is not particularly limited.
For example, the aggregate of raw material pellets is placed in a container, and the aggregate of raw material pellets is heated while being stirred by a stirring blade to promote crystallization of the raw material pellets to obtain an aggregate of product pellets. it can.

The shape and the number of revolutions of the stirring blade can be appropriately determined within a range that does not significantly change the shape of the raw material pellet.
If the rotation speed is increased too much, the raw material pellets are easily scraped. For this reason, shape abnormalities are likely to occur in the product pellets, and the average flatness of the assembly of the product pellets tends to be large.

The heating temperature is preferably a temperature of (crystallization temperature-10 ° C) or more and less than the melting point of the alicyclic structure-containing resin constituting the raw material pellet. The heating temperature is usually 120 ° C. or more and less than 180 ° C., preferably 130 ° C. or more and 170 ° C. or less.
The crystallization temperature refers to the exothermic peak temperature associated with the promotion of crystallization when differential scanning calorimetry is performed on the alicyclic structure-containing resin under a temperature elevation condition of 10 ° C./min.
The melting point means that the alicyclic structure-containing resin is completely melted by heating in a differential scanning calorimeter, and then cooled to 25 ° C. under a temperature lowering condition of 10 ° C./min, and then raised by 10 ° C./min The temperature at the endothermic maximum of the crystal melting peak when differential scanning calorimetry is performed up to 320 ° C. under warm conditions.

The heating time is usually 5 minutes to 12 hours, preferably 5 minutes to 2 hours, more preferably 10 to 1 hour.
If heating is performed at too high temperature for a long time, melting and mutual adhesion of raw material pellets are likely to occur. For this reason, shape abnormalities are likely to occur in the product pellets, and the average flatness of the assembly of the product pellets tends to be large.

[Molding material]
The molding material of the present invention comprises an assembly of the product pellets.
Therefore, by using the molding material of the present invention, a molded article having excellent heat resistance, mechanical strength and solvent resistance and having a good appearance can be stably produced.
Since such characteristics are utilized, the molding material of the present invention is molded when producing a light reflector, an insulating material, an optical film, a connector, a food packaging material, a bottle, a pipe, gears, a fiber / nonwoven fabric, etc. It is suitably used as a material.

  In particular, the molding material of the present invention stably discharges the molten resin when brought into its molten state, and since the molten resin is excellent in uniformity, the characteristics of the molding material such as an optical film etc. It is made more effective when producing film-like moldings.

[Molded body]
The molded body of the present invention is obtained by molding the molding material of the present invention.
Therefore, the molded article of the present invention is excellent in heat resistance, mechanical strength, solvent resistance and the like, and has a good appearance.
Examples of the molded article of the present invention include light reflectors, insulating materials, optical films, connectors, food packaging materials, bottles, pipes, gears, fibers, non-woven fabrics and the like.

In particular, when the molded article of the present invention is a film-shaped molded article such as an optical film, the film-shaped molded article has extremely excellent transparency.
For example, the haze of the film-like molding is 1.0% or less, preferably 0.5 or less. The lower limit is not particularly limited and is preferably as small as possible, but is usually 0.1% or more.

2) Method of Producing Molding Material The method of producing a molding material comprising an aggregate of product pellets according to the present invention contains a crystalline alicyclic structure-containing resin and has a crystallization calorific value of about 20 to 35 mJ / mg. And a crystallization step of converting an aggregate of cylindrical raw material pellets into an aggregate of substantially cylindrical product pellets having a crystallization calorific value of 10 mJ / mg or less, and in the crystallization step, the raw material pellet aggregates It is characterized in that the average dimensional change rate is -10.0 to 0% when changing from the above to an assembly of product pellets. The method for producing a molding material of the present invention is preferably a method for producing the above-mentioned "molding material of the present invention".

In the crystallization step in the method for producing a molding material of the present invention, the aggregate of raw material pellets is converted into an aggregate of substantially cylindrical product pellets having a crystallization calorific value of 10 mJ / mg or less.
As an assembly of the raw material pellet used for the method of this invention, the thing similar to the assembly of the raw material pellet in invention of a molding material is mentioned.
In the method for producing a molding material of the present invention, the product pellet refers to one which has undergone the crystallization step.

  In this crystallization step, the average dimensional change rate at the time of changing from an assembly of raw material pellets to an assembly of product pellets is -10.0 to 0%, preferably -5.0 to 0%, more preferably Is -1.0 to 0%.

The average dimensional change rate in the crystallization step can be determined by the following method.
First, 20 or more raw material pellets are selected arbitrarily, the cross section is approximated to an ellipse, the minor axis is measured, and the average value [average value (1)] is calculated.
Next, after performing the crystallization step, 20 or more product pellets are arbitrarily selected, the cross section is approximated to an ellipse, the minor axis is measured, and the average value [average value (2)] is calculated. Do.
The average dimensional change rate can be calculated by the following equation using the obtained average values (1) and (2).

The crystallization step can usually be carried out by heating an aggregate of raw material pellets. The heating method is not particularly limited. For example, in the invention of the molding material, this crystallization step can be carried out by the same method as that described as the heating method at the time of advancing the crystallization of the raw material pellet.
In this crystallization step, in particular, the aggregate of the raw material pellets is preferably heated to a temperature of (crystallization temperature -10 ° C) or more and less than the melting point of the alicyclic structure-containing resin.

  According to the production method of the present invention, it is possible to efficiently produce a molding material capable of stably producing a molded article having excellent heat resistance, mechanical strength and solvent resistance and having a good appearance. . According to the method for producing a molding material of the present invention, the above-mentioned "molding material of the present invention" can be produced efficiently.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. The present invention is not limited to these examples. In the following, "parts" and "%" are by weight unless otherwise specified.

In Examples and Comparative Examples, measurement of various physical properties was performed according to the following method.
(1) Molecular weight (weight-average molecular weight and number-average molecular weight) of dicyclopentadiene ring-opened polymer
The molecular weight of the dicyclopentadiene ring-opening polymer is gel permeation chromatography (GPC) system HLC-8320 (manufactured by Tosoh Corporation) using an H-type column (manufactured by Tosoh Corporation) 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 determine a hydrogenation rate in the hydrogenation reaction.

(3) Melting point of dicyclopentadiene ring-opened polymer hydride A sample heated to 320 ° C. in a nitrogen atmosphere is quenched with liquid nitrogen and heated at 10 ° C./min using a differential scanning calorimeter (DSC). The melting point of the dicyclopentadiene ring-opened polymer hydride was determined.

(4) Ratio of racemo dyad of dicyclopentadiene ring-opened polymer hydride: ¹³ C-NMR measurement is performed by applying inverse-gated decoupling method at 150 ° C. using ortho dichlorobenzene-d 4 as a solvent, dicyclopentadiene The ratio of racemo dyads of the ring-opened polymer hydride was determined. Specifically, based on the peak at 127.5 ppm of ortho-dichlorobenzene-d4 as a reference shift, based on the intensity ratio of the 43.35 ppm signal from the meso dyad and the 43.43 ppm signal from the racemo dyad, The ratio of racemo dyad was determined.

(5) Crystallization calorific value of product pellet In a nitrogen atmosphere, the temperature of the measurement sample is raised at 10 ° C./min using a differential scanning calorimeter (DSC), and the crystal area is observed from the peak area of the exothermic peak accompanying crystallization promotion. The calorific value was determined.

(6) Presence or absence of mutual adhesion in product pellets The product pellets were observed to check the presence or absence of mutual adhesion, and the quality as a molding material was evaluated according to the following criteria.
A: I could not see each other's arrival.
B: Some were able to see each other attached.
C: Attachments were seen in many parts.

(7) Average Flatness of Product Pellet Assembly Twenty product pellets were arbitrarily selected from the product pellet assembly, and their major axis and minor axis were measured to calculate the average flatness of the product pellet assembly.

(8) Average dimensional change rate in crystallization process From the raw material pellet assembly, 20 raw material pellets were arbitrarily selected, the minor axis was measured, and the average value was calculated.
Similarly, 20 product pellets were arbitrarily selected from the product pellet assembly, the minor axis was measured, and the average value was calculated.
Using these average values, the average dimensional change rate in the crystallization step was calculated based on the above equation.

(9) Extrusion stability The extrusion stability of the molten resin when molding a resin film by an extrusion molding method using a molding material composed of a product pellet assembly was evaluated based on the following criteria.
A: The molten resin can be extruded without problems.
B: Disturbance may occur in the discharge amount of the molten resin.
C: It is necessary to stop the production due to a trouble in the discharge of the molten resin.

(10) Haze HAZE measurement uses a HAZE meter (product name “NDH 5000”, manufactured by Nippon Denshoku Kogyo Co., Ltd.) after cutting out the obtained resin film into a square thin film sample of 50 mm × 50 mm at any selected site. And measured.

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

As a terminator, 0.037 part of 1,2-ethanediol was added to 200 parts of a solution containing the obtained ring-opened polymer of dicyclopentadiene, and the mixture was stirred at 60 ° C. for 1 hour to terminate 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, and the mixture was heated to 60 ° C. and stirred for 1 hour. Add 0.4 parts of filter aid (product name "Radiolite (registered trademark) # 1500" manufactured by Showa Chemical Industry Co., Ltd.) and use PP pleated cartridge filter (product name "TCP-HX" manufactured by ADVANTEC Toyo Corp.) Then, the adsorbent was separated by filtration to obtain a solution containing dicyclopentadiene ring-opened polymer.
When the molecular weight of the dicyclopentadiene ring-opened polymer was measured using a part of this solution, the weight average molecular weight (Mw) was 28,100, the number average molecular weight (Mn) was 8,750, and the molecular weight distribution (Mw / Mn) was 3.21.

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

Production Example 2
In 100 parts of the dicyclopentadiene ring-opened polymer hydride obtained in Preparation Example 1, an antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] was used. After mixing 0.8 parts of methane and product name "Irganox (registered trademark) 1010" (manufactured by BASF Japan Ltd.), the mixture is charged into a twin-screw extruder (TEM-37B, manufactured by Toshiba Machine Co., Ltd.) and thermally melted. After a strand-like formed body was obtained by extrusion, it was cut with a strand cutter to obtain a raw material pellet.
The operating conditions of the twin screw extruder are shown below.
Barrel set temperature: 270 to 280 ° C
・ Die setting temperature: 250 ° C
-Screw rotational speed: 145 rpm
・ Feeder rotation number: 50 rpm

Example 1
40 kg of the raw material pellet obtained in Production Example 1 is put in a stirring tank (crystallization unit CR-1 manufactured by Kawata Co., Ltd.), and this is stirred at 140 ° C. for 60 minutes under the condition of rotation speed 10 rpm to crystallize the raw material pellet Conducted to obtain product pellets.

The resulting product pellets were molded under the following conditions to obtain a resin film having a width of 120 mm and a thickness of 200 μm.
Molding machine: Hot melt extrusion film molding machine equipped with a T-die (product name “Measuring Extruder Type Me-20 / 2800V3”, manufactured by Optical Control Systems)
Barrel temperature setting: 280 ° C to 290 ° C
・ Die temperature: 270 ° C
-Screw rotation speed: 30 rpm
Film winding speed: 1 m / min

[Examples 2, 3 and Comparative Examples 1 to 4]
A product pellet assembly was obtained in the same manner as in Example 1 except that the production conditions of the product pellet assembly were changed to those described in Table 1, and a resin film was produced using this.
In Comparative Example 1, an aggregate of raw material pellets was used as a molding material.

  The measurement results and the evaluation results in Examples 1 to 3 and Comparative Examples 1 to 4 are shown in Table 1.

Table 1 shows the following.
By using the molding material of Examples 1-3, a resin film with small haze can be manufactured stably.
On the other hand, in the comparative example 1 using the molding material which consists of the aggregate | assembly of the pellet which has not passed crystallization treatment, although it has a favorable shape, this molding material is inferior to extrusion stability.
In Comparative Example 2, since the heating temperature of the crystallization process is too high, a part of the raw material pellet is melted, and a shape abnormality is observed in the product pellet. This molding material is also inferior in extrusion stability.
In Comparative Example 3, since the rotation speed of the stirring in the crystallization treatment is too high, a part of the raw material pellet is scraped, and a shape abnormality is observed in the product pellet. The resin film obtained using this molding material has a large haze.
In Comparative Example 4, the crystallization of the raw material pellet can not be sufficiently advanced, and as a result, this molding material is inferior in extrusion stability.

Claims (8)

A molding material comprising an aggregate of substantially cylindrical product pellets containing a crystalline alicyclic structure-containing resin,
The calorific value of crystallization of the product pellet is 10 mJ / mg or less,
A molding material characterized in that the average flatness of the assembly of product pellets is 0.35 or less.   The molding material according to claim 1, wherein the alicyclic structure-containing resin is a dicyclopentadiene ring-opened polymer hydride.   The aggregate of the product pellets is obtained by heating an aggregate of raw material pellets having a crystallization calorific value of 20 to 35 mJ / mg, which contains a crystalline alicyclic structure-containing resin. Or the molding material as described in 2. A method for producing a molding material comprising an assembly of product pellets, comprising:
An aggregate of substantially columnar raw material pellets containing a crystalline alicyclic structure-containing resin and having a crystallization calorific value of 20 to 35 mJ / mg, and a substantially columnar product having a crystallization calorific value of 10 mJ / mg or less It has a crystallization process to convert it into aggregates of pellets,
A method of producing a molding material, wherein in the crystallization step, an average dimensional change rate is -10.0 to 0% when changing from an assembly of raw material pellets to an assembly of product pellets. The crystallization process is a collection of the raw material pellet, the alicyclic structure-containing resin, (crystallization temperature -10 ° C.) or higher, a step of heating to a temperature below the melting point, according to claim 4 Manufacturing method of molding material. The manufacturing method of the molding material of Claim 4 or 5 whose said alicyclic structure containing resin is a dicyclopentadiene ring-opened polymer hydride. The manufacturing method of a molded object characterized by shape | molding the molding material obtained by the manufacturing method in any one of Claims 4-6. The molded article is a film-like molded article,
The manufacturing method of the molded object of Claim 7 whose haze of the said film-form molded object is 1.0% or less.