JP2010082849A - Resin composition, resin mold,and method of manufacturing molding by using the resin mold - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition with excellent releasability from a mold in molding and cobwebbing properties, to provide a resin molds excellent in release characterjistics, and to provide a method of manufacturing a molding by using the resin mold. <P>SOLUTION: The shearing viscosity of a thermoplastic resin containing alicyclic structure and a resin composition containing 0.02-0.20 mass pts. of a hydroxyl group-containing ester compound to 100 mass pts. of the resin composition, at 230°C, 10,000/s of shearing speed, is defined as 20-50 Pa s, and an extensional viscosity at an extensional rate of 100/s is defined as 6-20 kPa s. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition excellent in stringiness at the time of molding, which can be used for manufacturing an optical information recording medium, a resin mold made of the resin composition and excellent in peelability, and a method for manufacturing a molded body using the resin mold About.

  In recent years, there has been a significant demand for higher density and larger capacity of optical disks. Currently, a DVD (Digital Versatile Disk) with a recording capacity of about 4.7 GB on a single side, which is about seven times that of a compact disk, is commercially available. Yes.

  In order to increase the density and capacity of an optical disc, it is necessary to increase the linear recording density and the track density. For this purpose, it is necessary to reduce the prepits or the groove pitch. As a method for producing such an optical information recording medium, a resin layer containing a radiation curable resin is sandwiched between a stamper having a concavo-convex pattern on the surface (hereinafter sometimes referred to as a resin mold) and the substrate of the medium. Next, a step of irradiating the resin layer with radiation, then peeling off the stamper, and forming an intermediate layer to which the concave / convex pattern is transferred is provided, and the stamper has at least a surface on which the concave / convex pattern is formed. A method for producing an optical information recording medium composed of a resin composition comprising a cyclic polyolefin has been studied (for example, see Patent Document 1).

However, when the resin mold made of the cyclic polyolefin is molded by injection molding, the mold release property of the resin mold from the mold is not sufficient, and there may be a mold release defect in which the uneven pattern is deformed. .
As a method for improving the releasability problem, a resin composition comprising an alicyclic structure-containing thermoplastic resin and a hydroxyl group-containing ester compound has been studied (for example, see Patent Document 2). However, this resin composition has a problem that stringing is likely to occur at the time of molding, and the yarn adheres to the molded body, resulting in a defective shape and a low yield rate.
JP 2003-85839 A JP 2006-35823 A

  An object of the present invention is to provide a resin composition having good releasability from a mold during molding and a stringing property, a resin mold having excellent peelability, and a method for producing a molded body using the resin mold. .

As a result of earnest research, the present inventors are a resin composition containing an alicyclic structure-containing thermoplastic resin and a hydroxyl group-containing ester compound, and the hydroxyl group-containing ester compound content is based on 100 parts by mass of the resin composition. 0.02 to 0.20 parts by mass, the shear viscosity at 230 ° C. and a shear rate of 10,000 / s is 20 to 50 Pa · s, and the extension viscosity at 230 ° C. and an extension rate of 100 / s is 6 to The present inventors have found that a resin composition of 20 kPa · s exhibits suppression of stringing during molding and good release properties from a mold, and has completed the present invention.
The branching index of the alicyclic structure-containing thermoplastic resin may be in the range of 0.5 to 0.98. The resin composition of the present invention may contain 0.01 to 1.0 part by mass of polyethylene having a viscosity average molecular weight of 1.5 to 3 million with respect to 100 parts by mass of the resin composition. The alicyclic structure-containing thermoplastic resin may be a norbornene-based ring-opening polymer hydride or a norbornene-based addition polymer.

  Furthermore, the present invention provides a resin mold comprising the above resin composition. The method for producing a molded article provided by the present invention comprises: applying a curable resin on a substrate; overlaying the resin mold on the obtained curable resin layer; and curing the curable resin layer, then the resin. A step of peeling and removing the mold, or a step of peeling and removing the resin mold after filling the internal space formed by the resin mold and curing the curable resin.

  The resin composition of the present invention is suitable for a resin mold of an optical information recording medium because the occurrence of stringing at the time of molding is suppressed and good mold release properties are exhibited. Furthermore, the resin mold is suitable for a manufacturing process of an optical information recording medium.

The resin composition of the present invention contains an alicyclic structure-containing thermoplastic resin and a hydroxyl group-containing ester compound, has a shear viscosity of 20 to 60 Pa · s at 230 ° C. and a shear rate of 10,000 / s, and 230 ° C. The extensional viscosity at an extension rate of 100 / s is 6 to 20 kPa · s.
In order to bring the shear viscosity and the extensional viscosity into this range, for example, there are the following two methods.
(1) The branched structure is introduced into the alicyclic structure-containing thermoplastic resin.
(2) High molecular weight polyethylene is contained in the resin composition.

  The alicyclic structure-containing thermoplastic resin used in the present invention has an alicyclic structure in the main chain and / or side chain. From the viewpoint of mechanical strength, heat resistance, etc., an alicyclic structure-containing thermoplastic resin containing an alicyclic structure in the main chain is preferred.

  Specific examples of the alicyclic structure include a saturated cyclic hydrocarbon (cycloalkane) structure and an unsaturated cyclic hydrocarbon (cycloalkene) structure. From the viewpoint of mechanical strength, heat resistance, and the like, Alkene structures are preferred, with cycloalkane structures being most preferred.

  The number of carbon atoms constituting the alicyclic structure is not limited, but is usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15. When the number of carbon atoms is in the above range, the mechanical strength, heat resistance and moldability of the resin composition are highly balanced.

  Specific examples of the alicyclic structure-containing thermoplastic resin include (1) norbornene-based ring-opening polymer hydride, (2) norbornene-based addition polymer, (3) vinyl alicyclic carbonized polymer, and hydrides thereof. Is. Among these, from the viewpoints of heat resistance, mechanical strength, and the like, norbornene-based ring-opening polymer hydrides and norbornene-based addition polymers are preferable.

Specific examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene) and its derivatives (having a substituent in the ring), tricyclo [4.3.01, 6.12,5] deca-3,7-diene (common name dicyclopentadiene) and derivatives thereof, 7,8-benzotricyclo [4.3.0.12,5] dec-3-ene (common name) Methanotetrahydrofluorene: 1,4-methano-1,4,4a, 9a-tetrahydrofluorene) and its derivatives, tetracyclo [4.4.0.12,5.17,10] dodec-3-ene (conventional) Name: tetracyclododecene) and derivatives thereof.
Specific examples of the substituent include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, and an alkylidene group, and the norbornene monomer may have two or more of these substituents. Specific examples of the norbornene-based monomer having a substituent include 8-methoxycarbonyl-tetracyclo [4.4.0.12,5.17,10] dodec-3-ene, 8-methyl-8-methoxycarbonyl- Tetracyclo [4.4.0.12,5.17,10] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.12,5.17,10] dodec-3-ene, and the like. .
These norbornene monomers are used alone or in combination of two or more.

The norbornene-based ring-opening polymer hydride is obtained by polymerizing one or more norbornene-based monomers or other monomers capable of ring-opening copolymerization in the presence of a known ring-opening polymerization catalyst. It is obtained by hydrogenating the carbon-carbon double bond of the norbornene-based ring-opening polymer obtained.
Specific examples of other monomers capable of ring-opening copolymerization with norbornene monomers include monocyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.

  Specific examples of the ring-opening polymerization catalyst include a catalyst comprising a metal halide such as ruthenium or osmium, a nitrate or acetylacetone compound, and a reducing agent; a metal halide or acetylacetone compound such as titanium, zirconium, tungsten or molybdenum; And a catalyst comprising an organoaluminum compound.

  When it is necessary to adjust the molecular weight of the norbornene-based ring-opening polymer, a molecular weight regulator can be added to the reaction system during the ring-opening polymerization. The molecular weight regulator used is not particularly limited, and is a conventionally known molecular weight regulator.

  Hydrogenation is carried out by contacting hydrogen with an alicyclic structure-containing ring-opening polymer in the presence of a hydrogenation catalyst according to a conventional method. The hydrogenation catalyst is described in JP-A-58-43412, JP-A-60-26024, JP-A-64-24826, JP-A-1-138257, JP-A-7-41550, and the like. Hydrogenation catalyst.

  An addition polymer of a norbornene monomer, or an addition polymer of a norbornene monomer and another monomer copolymerizable therewith, these monomers are added to a known addition polymerization catalyst, for example, Polymerization is carried out using a catalyst comprising a titanium, zirconium or vanadium compound and an organoaluminum compound.

Specific examples of other monomers that can be addition copolymerized with norbornene-based monomers include α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and the like. A cycloolefin such as cyclobutene, cyclopentene, cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, and derivatives thereof; 1,4-hexadiene, 4-methyl Non-conjugated dienes such as -1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene. Among these, α-olefins are preferable and ethylene is particularly preferable.
These other monomers capable of addition copolymerization with the norbornene-based monomer can be used alone or in combination of two or more. In the case of addition copolymerization of norbornene monomer and other monomer capable of addition copolymerization, other units capable of addition copolymerization with structural units derived from norbornene monomer in the addition polymer The ratio with the structural unit derived from the body is appropriately selected so that the mass ratio is usually in the range of 30:70 to 99: 1, preferably 50:50 to 97: 3, more preferably 60:40 to 95: 5. Is done.
From the viewpoints of heat resistance, mechanical strength, moldability and the like of the resin composition, an addition copolymer of a norbornene monomer and ethylene is particularly preferable.

  When it is necessary to adjust the molecular weight of the norbornene-based addition polymer, a molecular weight regulator can be added to the addition polymerization reaction system. The molecular weight regulator to be used is not particularly limited, and a conventionally known molecular weight regulator can be used.

  Specific examples of vinyl alicyclic hydrocarbon polymers include polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane and their hydrides; vinyl aromatic systems such as styrene and α-methylstyrene. Random copolymerization of aromatic ring hydrides, vinyl alicyclic hydrocarbon polymers, and vinyl aromatic monomers with other monomers copolymerizable with the monomer. Copolymers, copolymers such as block copolymers, and hydrides thereof. Specific examples of the block copolymer include a diblock, a triblock, a multiblock higher than that, a gradient block copolymer, and the like.

  The hydrogenation reaction is carried out by bringing the alicyclic structure-containing ring-opening polymer into contact with hydrogen in the presence of a hydrogenation catalyst according to a conventional method. Specific examples of the hydrogenation method include the method described in JP-A No. 2001-48924.

It is preferable to use an alicyclic structure-containing thermoplastic resin having a branched structure.
The purpose of introducing a branched structure is to change the balance between shear viscosity and extensional viscosity.
More specifically, when a resin having a branched structure and a resin having the same shear viscosity are compared with a resin having a branched structure, the elongation viscosity of a resin having a moderately branched structure is higher than that of a resin having no branched structure. The stringing of the resin having a moderate amount is suppressed.
The branched structure referred to in the present invention is a structure in which a side chain consisting of repeating monomer units is formed by branching from the middle of the main chain consisting of repeating monomer-derived structural units.

The branch structure can be represented by a branch index.
The branching index is defined by the branching index g = [η] Bra / [η] Lin, and the closer to 1, the fewer branch structures, and the closer to 0, the more branch structures.
[Η] Bra is the intrinsic viscosity of the branched alicyclic structure-containing thermoplastic resin, and [η] Lin is the intrinsic viscosity of the linear alicyclic structure-containing thermoplastic resin having the same weight average molecular weight. Here, the intrinsic viscosity [η] is a value obtained by measuring a sample dissolved in cyclohexane at 60 ° C.

If the branching index is too high (too few branch structures), the effect of increasing the elongational viscosity of the resin composition will be low. If the branching index is too low (too many branching structures), conversely, There is a possibility that the extensional viscosity is lowered.
The branched index of the branched alicyclic structure-containing thermoplastic resin preferably used in the present invention is 0.5 to 0.98, preferably 0.55 to 0.95, more preferably 0.6 to 0.95. is there.

  In order to introduce such a branched structure and adjust the branching index, it is only necessary to contain a monomer having two or more polymerization reaction points in the same molecule when carrying out the polymerization.

A monomer having two or more double bonds in the same molecule is preferred as a monomer having two or more reaction points in the same molecule. Specific examples of the monomer include (A) a monomer having two or more norbornene rings, (B) a monomer having a norbornene ring and a terminal carbon-carbon double bond, and (C) two terminal carbons- A monomer having a carbon double bond; and (D) a monomer having three or more terminal carbon-carbon double bonds.
(A), (B), (D) are preferred when introducing a branched structure into a norbornene-based ring-opening polymer hydride, and (A), (D) when introducing a branched structure into a norbornene-based addition polymer. B), (C), and (D) are preferable, and (C) and (D) are preferable when a branched structure is introduced into a vinyl alicyclic carbonized polymer and a hydride thereof.

(A) Monomer having two or more norbornene rings The monomer having two or more norbornene rings has two or more norbornene rings and is not limited to a specific compound. Specific examples of the monomer having two or more norbornene rings include exo-trans-exo-pentacyclo- [8.2.14, 7.02, 9.03,8] tetradeca-5,11-diene ( Hereinafter, it may be referred to as “NB-dimer”), 4,4a, 4b, 5,8,8a, 9,9a-octahydro-1,4: 5,8-bismethano-1H-fluorene, 1α, 4α : 5α, 8α-dimethano-1,4,4a, 5,8,8a, 9,9a, 10,10a-decahydroanthracene, 5,5'-bi (norborna-2-ene), tetracyclo [6.2 1.13, 6.02, 7] dodecane-4,9-diene, 1,4,4a, 5,8,8a, 9,9a, 10,10a-decahydro-1,4: 5,8: 9 , 10-trimethanoanthracene.

(B) Monomer having a norbornene ring and a terminal carbon-carbon double bond The monomer having a norbornene ring and a terminal carbon-carbon double bond has a terminal double bond in addition to the norbornene ring. Specific examples of the monomer having a norbornene ring and a terminal carbon-carbon double bond are usually alkenyl groups having a double bond at the terminal having 2 to 20, preferably 2 to 10, more preferably 2 to 4 carbon atoms. It is. Specific examples of the alkenyl group include a vinyl group, an allyl group, a 3-butenyl group, a 4-pentenyl group, a 2-methyl-3-butenyl group, and a 5-heptyl group. Among these, a vinyl group and an allyl group are preferable from the viewpoint of fluidity. These specific alkenyl groups may be bonded to the norbornene ring via an arbitrary group, or may be bonded to the norbornene ring via an arbitrary group to form a ring structure. Specific examples of the arbitrary group include an alkylene group, —O—, —S—, —O—CO—, —O—CH ₂ —O—CO—, and phenylene. From the viewpoint of fluidity, the number of elements constituting an arbitrary group is preferably 10 or less, more preferably 5 or less.

  Specific examples of the monomer having a norbornene ring and a terminal carbon-carbon double bond include 5-vinyl-bicyclo [2.2.1] hept-2-ene and 5-allyl-bicyclo [2.2.1]. Hept-2-ene, 5-vinyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 8-vinyl-tetracyclo [4.4.0.12,5.17,10] dodec-3- Ene, 8-allyl-tetracyclo [4.4.0.12,5.17,10] dodec-3-ene, 8-vinyloxycarbonyl-tetracyclo [4.4.0.12,5.17,10] Dodeca-3-ene and the like.

(C) Monomer having two terminal carbon-carbon double bonds Specific examples of the monomer having two terminal carbon-carbon double bonds include 1,5-hexadiene, 1,9-decadiene, 1, 3-divinylcyclohexane, 1,3-divinylbenzene and the like.

(D) Monomer having three or more terminal carbon-carbon double bonds Specific examples of the monomer having three or more terminal carbon-carbon double bonds include 1,2,4-trivinylcyclohexane, 4- (2-propenyl) -1,6-heptadiene, 3-vinyl-1,4-pentadiene, 3-vinyl-1,5-hexadiene, 1,3,5-trivinylbenzene, 1,2,4- Trivinylbenzene, 1,2,4,5-tetravinylbenzene and the like.

The amount of the monomer having two or more polymerization reaction points in the same molecule is usually 0.01 to 1.00 mol%, preferably 0.03 to 0.50 mol%, based on all monomers. More preferably, it is 0.05-0.30 mol%, More preferably, it is 0.08-0.20 mol%.
If the amount of the monomer having two or more polymerization reaction points in the same molecule is too small, the branched structure of the alicyclic structure-containing thermoplastic resin is small and the branching index of the alicyclic structure-containing thermoplastic resin becomes too high. . On the other hand, if the amount of the monomer having two or more polymerization reaction points in the same molecule is too large, the branched structure of the alicyclic structure-containing thermoplastic resin increases, and the branching index of the alicyclic structure-containing thermoplastic resin increases. Is too low.

A method for polymerizing using a monomer having two or more polymerization reaction points in the same molecule is not particularly limited. A specific example of the polymerization method is a method in which a monomer having two or more polymerization reaction points in the same molecule and another monomer are mixed and then polymerization is performed by the same method as described above.

The hydroxyl group-containing fatty acid ester compound used in the present invention is used as a release agent and is an ester compound of a fatty acid having one or more hydroxyl groups in the molecule, and is not limited to a specific compound. Preferred examples of the hydroxyl group-containing fatty acid ester compound has the formula (a): a compound represented by RX _n (hereinafter, compound (a) hereinafter) is.

In the formula (a), R represents a hydrocarbon group that may have a hydroxyl group. In view of the magnitude of the effect of addition, R is preferably a hydrocarbon group having no hydroxyl group.
The hydrocarbon group for R may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. From the viewpoint of chemical stability and difficulty in coloring the molded article, R is preferably a saturated hydrocarbon group.
The carbon number of R is preferably 2 or more, more preferably 3 or more, and preferably 60 or less, more preferably 50 or less.

X represents a hydroxyacyloxy group. Hydroxyacyl group is, k, -O (CO) when was the natural number _{m C m H 2m + 1-} k (OH) k ( however, k ≦ 2 m + 1) is a group represented by.
The number of carbon atoms in X is preferably 13 or more, more preferably 16 or more, and preferably 50 or less.

  The number of hydroxyl groups in X (value of k) is preferably 1 from the viewpoint of the effect of addition. This hydroxyl group may not be bonded to the terminal carbon. Similarly, —COO— in X may not be bonded to the terminal carbon.

n represents a natural number, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, more preferably 7 or less, and particularly preferably 5 or less. When n is 2 or more, the n Xs may be the same or different, but from the viewpoint of ease of production, the n X groups are preferably the same.
In the formula (a), when n is 2 or more, the hydroxyacyloxy group of X may not be bonded to the same carbon in the R group (hydrocarbon group).

When n is 1, and when n is 2 or more and n number of Xs are the same, the compound (a) is a compound having one hydroxyl group in X and R does not have a hydroxyl group. Is the formula (b): C _l H _{2l + 2-n} [O (CO) C _m H _2m OH] _n (where l, m, n represent natural numbers, l + (m + 1) × n ≧ 16) Yes.)

In the formula (b), l is preferably 2 or more, more preferably 3 or more, and preferably 60 or less, more preferably 50 or less.
M in the formula (b) is preferably 12 or more, more preferably 15 or more, and preferably 49 or less.
[L + (m + 1) × n] in the formula (b) is 16 or more, preferably 20 or more, more preferably 24 or more, and preferably 120 or less, more preferably 90 or less, particularly preferably 60 or less. .

  Carbon number of R in formula (a) (l in the formula (b) or carbon number of alcohols), carbon number of X (number in which m is added in the formula (b) plus 1 or hydroxyl group-containing) When the number of carbon atoms of the fatty acid) or the total number of carbon atoms (value of l + (m + 1) × n in l, m, n in the formula (b)) is too small, the hydroxyl group-containing fatty acid ester compound is likely to volatilize. It becomes difficult to use. On the other hand, when there are too many said carbon numbers, the external appearance defect of a molded article increases because of the bleeding of a hydroxyl-containing fatty acid ester compound.

  The compound represented by the formula (a) is a compound having a structure in which a hydroxyl group of an alcohol is ester-bonded with a hydroxyl group-containing fatty acid, and can be produced, for example, by reacting an alcohol with a hydroxyl group-containing fatty acid.

  The alcohol used for the synthesis of the compound represented by the formula (a) is not particularly limited. The number of carbons of the compound (that is, the number of carbons of R in the formula (a) and l in the formula (b)) is preferably 2 or more, more preferably 3 or more, and preferably 60 or less, more Preferably, it is 50 or less, and the number of hydroxyl groups [n in the formula (a) and the formula (b) when R does not have a hydroxyl group] is preferably 2 or more, more preferably 3 or more, And it is preferably 10 or less, more preferably 7 or less, and particularly preferably 5 or less.

  Specific examples of alcohols include glycerol, trimethylolpropane, pentaerythritol, diglycerol, triglycerol, dipentaerythritol, ethylene glycol, stearyl alcohol, 1,6,7-trihydroxy-2,2-di (hydroxythymer) ) -4-oxoheptane, sorbitol, 2-methyl-1,6,7-trihydroxy-2-hydroxymethyl-4-oxoheptane, 1,5,6-trihydroxy-3-oxohexane and the like.

  The hydroxyl group-containing fatty acid used for the synthesis of the compound (a) is preferably a compound having one hydroxyl group and having 13 or more, preferably 16 or more, and preferably 50 or less carbon atoms.

  Specific examples of the hydroxyl group-containing fatty acid include hydroxyheptadecanoic acid, hydroxyoctadecanoic acid (hydroxystearic acid), hydroxyeicosanoic acid, hydroxydocosanoic acid, hydroxyhexacosanoic acid, and hydroxytriacontanoic acid.

  Specific examples of the compound (a) include 12-hydroxystearic acid triglyceride, 12-hydroxystearic acid stearyl alcohol, pentaerythritol-tetra-12-hydroxystearate, ethylene glycol-di-12-hydroxystearate, propylene glycol-di. A compound represented by the above formula (a) wherein R is a hydrocarbon group having no hydroxyl group, such as 12-hydroxystearate; a part of hydroxyl groups of alcohols such as 12-hydroxystearic acid monoglyceride is a hydroxyl group-containing fatty acid And a compound having a structure in which an ester bond is formed (a compound represented by the formula (a) in which R is a hydrocarbon group having a hydroxyl group).

  Kao wax 85P (manufactured by Kao Corporation) and Himakou (manufactured by Kawaken Fine Chemical Co., Ltd.), which are commercially available compounds having a structure in which all hydroxyl groups of alcohols are ester-bonded with a hydroxyl group-containing fatty acid, can also be used as the hydroxyl group-containing fatty acid ester compound.

The compounding quantity of a hydroxyl-containing fatty acid ester compound is 0.02-0.20 mass part with respect to 100 mass parts of resin compositions, Preferably it is 0.03-0.08 mass part.
If the addition amount of the hydroxyl group-containing fatty acid ester compound is too small, a sufficient release effect cannot be obtained. On the other hand, if the addition amount is too large, the heat resistance, chemical resistance and moisture resistance of the alicyclic structure-containing thermoplastic resin are not obtained. There is a risk that characteristics such as sex may not be utilized.

The polyethylene used in the present invention is not limited to a specific polyethylene, but polyethylene having a viscosity average molecular weight in the range of 1,500,000 to 3,000,000 is preferable.
The purpose of adding polyethylene is to change the balance between the shear viscosity and the extensional viscosity of the resin composition.
If the molecular weight of polyethylene is too high, the dispersibility of the resin composition will be poor. On the other hand, if the molecular weight of polyethylene is too low, the influence of polyethylene on the shear viscosity and elongational viscosity of the resin composition will be low, and the shear of the resin composition will be low. It may be difficult to change the balance between viscosity and extensional viscosity.

The compounding quantity of polyethylene is 0.01-1.0 mass part with respect to 100 mass parts of resin compositions.
If the blending amount of polyethylene is too large, the shear viscosity is high, and if it is too small, the extensional viscosity may be low.

  If necessary, other polymers and other various additives (additives usually used in the resin industry) are added alone or in admixture of two or more to the resin composition of the present invention.

The other polymer may be a thermoplastic elastomer having a glass transition temperature of 40 ° C. or lower. Specific examples of the thermoplastic elastomer include emulsion-polymerized or solution-polymerized styrene-butadiene rubber, random or block styrene-butadiene copolymers such as high styrene rubber, hydrogenated products thereof; isoprene rubber, hydrogen thereof Additives; Chloroprene rubbers, hydrogenated products thereof; saturated polyolefin rubbers such as ethylene / propylene copolymers, ethylene / α-olefin copolymers, propylene / α-olefin copolymers; ethylene / propylene / diene copolymers; α-Olefin / diene copolymers, diene copolymers, diene polymers such as isobutylene / isoprene copolymers, isobutylene / diene copolymers, halides thereof, hydrogenated products of halides of diene polymers , These maleic anhydride, glycidyl methacrylate, epoxy Modified products by Shi etc., and the like.
Among these, from the viewpoint of the surface smoothness of the molded product, a hydrogenated product of random or block styrene / butadiene copolymer such as styrene / butadiene / rubber or high styrene rubber is preferable.
The thermoplastic elastomers can be used alone or in combination of two or more. The blending amount of the thermoplastic elastomer is appropriately selected within a range not impairing the object of the present invention, but is usually 1 to 30 parts by mass, preferably 2 to 25 parts by mass with respect to 100 parts by mass of the resin composition. It is.

  Other additives are additives usually used in thermoplastic resin materials, and are not limited to specific additives. Specific examples of other additives include antioxidants, ultraviolet absorbers, light stabilizers, near infrared absorbers, colorants such as dyes and pigments, plasticizers, antistatic agents, and fluorescent brighteners.

  Specific examples of the antioxidant include a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant. Among these, a phenolic antioxidant is preferable, and an alkyl-substituted phenolic antioxidant is particularly preferable. Antioxidants may be used alone or in combination of two or more.

Specific examples of the ultraviolet absorber include a benzotriazole ultraviolet absorber, a benzoate ultraviolet absorber, a benzophenone ultraviolet absorber, an acrylate ultraviolet absorber, and a metal complex ultraviolet absorber.
A specific example of the light stabilizer is a hindered amine light stabilizer.

  Specific examples of near-infrared absorbers include cyanine-based near-infrared absorbers, pyrylium-based infrared absorbers, squarylium-based near-infrared absorbers, croconium-based infrared absorbers, azulenium-based near-infrared absorbers, phthalocyanine-based near-infrared absorbers, dithiols Metal complex-based near-infrared absorbers, naphthoquinone-based near-infrared absorbers, anthraquinone-based near-infrared absorbers, indophenol-based near-infrared absorbers, adi-based near-infrared absorbers, and the like.

The dye is a compound that is uniformly dispersed or dissolved in the alicyclic structure-containing thermoplastic resin, and is not limited to a specific dye. From the viewpoint of compatibility with the alicyclic structure-containing thermoplastic resin used in the present invention, oil-soluble dyes (various CI solvent dyes) are widely used. Specific examples of oil-soluble dyes include various C.I. dyes described in Color Index vol. 3 published by The Society of Diyes and Colorists. I. It is a solvent dye.
Specific examples of the pigment include diarylide pigments, azo lake pigments, condensed azo pigments, benzimidazolone pigments, quinacridone pigments, perylene pigments and anthraquinone pigments.

Specific examples of plasticizers include phosphate triester plasticizers, phthalate ester plasticizers, fatty acid monobasic ester plasticizers, dihydric alcohol ester plasticizers, oxyacid ester plasticizers, and main skeletons. And a hydrocarbon polymer which is liquid at room temperature and has a C—C or C═C structure. Among these, a phosphoric acid triester plasticizer is preferable, and tricresyl phosphate and trixylyl phosphate are particularly preferable.
Specific examples of the antistatic agent include long-chain alkyl alcohols such as stearyl alcohol and behenyl alcohol; fatty acid esters of polyhydric alcohols such as glycerol monostearate and pentaerythritol monostearate. Stearyl alcohol and behenyl alcohol are particularly preferred.

  Although the compounding quantity of these additives is suitably selected in the range which does not impair the objective of this invention, it is 0.001-5 mass parts normally with respect to 100 mass parts of resin compositions, Preferably it is 0.01-1. It is the range of mass parts.

  The resin composition of the present invention contains an alicyclic structure-containing thermoplastic resin and a hydroxyl group-containing ester compound into which the branched structure is introduced, or an alicyclic structure-containing resin composition, polyethylene, and a hydroxyl group-containing ester compound.

The blending method of the resin composition of the present invention is not limited to a specific method. An alicyclic structure-containing thermoplastic resin, a hydroxyl group-containing ester compound, and if necessary, polyethylene or the like may be blended independently, or after blending into an alicyclic structure-containing thermoplastic resin and a hydroxyl group-containing ester compound. You may mix | blend polyethylene etc. with.
The mixing method is a method in which the compounding agent is sufficiently dispersed in the polymer, and is not limited to a specific method. Specific examples of the mixing method include a method of kneading the resin in a molten state with an apparatus such as a mixer, a single-screw kneader, a twin-screw kneader, a roll, a Brabender, an extruder, etc., and solidifying by dissolving and dispersing in an appropriate solvent. For example, the solvent may be removed by casting or direct drying.

  When a biaxial kneader is used, after kneading, it is usually extruded into a rod shape in a molten state, cut into an appropriate length with a strand cutter, and pelletized.

  The resin composition of the present invention is a resin type of optical information recording medium, optical disk, magnetic recording medium, optical fiber, camera lens, overhead projector lens, LBP θ lens, prism, liquid crystal display element (LC D), light diffusion plate , Optical molded products such as light guide plate, polarizing film, retardation film, brightness enhancement film, condensing film; various clean containers such as liquid chemical containers, ampoules, infusion bags, eye drop containers, semiconductor wafer storage containers; syringes It is suitable as a molded member for medical devices such as medical infusion tubes.

  The resin mold of the present invention can be produced by molding the resin composition by a known molding method. Specific examples of the molding method include injection molding, press molding, extrusion blow molding, injection blow molding, multilayer blow molding, connection blow molding, double wall blow molding, stretch blow molding, vacuum molding, and rotational molding. Among these, the injection molding method and the press molding method are preferable because they can reduce the in-plane variation of the concavo-convex shape. A specific example of the press molding method is a method of heating and pressurizing a sheet, a film or the like produced by a melt extrusion method in an uneven mold to be molded.

  The molding conditions vary depending on the molding method and the type of the alicyclic structure-containing thermoplastic resin used. The molding temperature is usually 100 to 400 ° C., preferably 200 to 380 ° C., more preferably 200 to 350 ° C., the molding pressure is usually 0.1 to 100 MPa, preferably 0.5 to 50 MPa, and the heating time is Is usually between a few seconds and tens of minutes.

  The resin mold of the present invention is particularly suitable as a resin stamper for an optical disc that is required to form an uneven shape with high surface accuracy.

  When molding a resin mold using a mold, there is little contamination inside the mold due to adhesion of resin, additives and the like. Therefore, the same resin mold can be mass-produced with good reproducibility using the same mold.

  The manufacturing method of the molding using the resin mold of the present invention is roughly classified into two types. A curable resin is applied on the substrate, the first resin mold of the present invention having an uneven shape on the surface is superimposed on the obtained curable resin layer, and the curable resin layer is cured, and then the first resin mold is cured. The resin mold is peeled off. A molded body having a cured resin layer having an uneven shape on the surface can be produced by the first resin mold.

  The method for producing a molded body using the second resin mold is as follows. The curable resin is filled in the internal space formed by the second resin mold, and after the curable resin is cured, the second resin mold is peeled and removed. A resin molded body having an uneven shape on the surface can be produced by the second resin mold. Specific examples of the second resin mold include (a) a resin mold having an internal space that is integrally molded and filled with a curable resin, and (b) an internal space that is molded in a split manner and filled with a curable resin in combination. A resin mold to be formed; and (c) a resin mold that forms an internal space in combination with a mold.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The present invention is not limited to only these examples. In the following examples and comparative examples, parts and% are based on mass unless otherwise specified.

The measuring methods of various physical properties measured in the following examples and comparative examples are as follows.
(1) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer before the hydrogenation reaction were measured as standard polystyrene conversion values by gel permeation chromatography (GPC) using toluene as an eluent.
The measuring apparatus was GPC-8020 series (DP8020, SD8022, AS8020, CO8020, RI8020) manufactured by Tosoh Corporation. The standard polystyrenes were Tosoh standard polystyrene, Mw = 500, 2630, 10200, 37900, 96400, 427000, 1090000, 5480000, for a total of 8 points.
The sample was prepared by dissolving the measurement sample in toluene so that the sample concentration would be 1 mg / ml, and then filtering with a filter made of porous polytetrafluoroethylene having a pore size of 0.5 μm.
Two TSKgel GMHHR · Hs manufactured by Tosoh Corporation were connected in series as columns, and the measurement was performed under the conditions of a flow rate of 1.0 ml / min, a sample injection amount of 100 μml, and a column temperature of 40 ° C.

(2) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer after the hydrogenation reaction are converted into standard polystyrene by gel permeation chromatography (GPC) using 1,2,4-trichlorobenzene as an eluent. The value was measured at 140 ° C.
The measuring apparatus was HLC811GPC / HT manufactured by Tosoh Corporation.
The standard polystyrene was Tosoh Corporation standard polystyrene, Mw = 988, 2580, 5910, 9010, 18000, 37700, 95900, 186000, 351000, 889000, 1050,000, 2770000, 5110000, 7790,000, 20000000 in total.
The sample was prepared by heating and dissolving the measurement sample in 1,2,4-trichlorobenzene at 140 ° C. so that the sample concentration was 1 mg / ml.
The measurement was performed under the conditions of three TSKgel GMHHR · H (20) HTs manufactured by Tosoh Corporation connected in series, a flow rate of 1.0 ml / min, a sample injection amount of 300 μml, and a column temperature of 140 ° C.

(3) The hydrogenation rate was measured by 1H-NMR using deuterated chloroform as a solvent.

(4) The glass transition temperature Tg was measured based on JIS K 6911 using a differential scanning calorimeter (DSC6220SII manufactured by Nanotechnology).

(5) The melt mass flow rate was measured at 230 ° C. and a 2.16 kg load in accordance with JIS K 7210.

(6) The light transmittance is obtained by dissolving the pellets in cyclohexane to a concentration of 10%, placing the obtained solution in a quartz cell with a 10 mm optical path, and measuring the light transmittance at a wavelength of 365 nm with a spectrophotometer (manufactured by JASCO Corporation). V-570).
The light transmittance needs to be 50% or more.

(7) The shear viscosity and the extensional viscosity were measured at a measurement temperature of 230 ° C. using a twin capillary rheometer (manufactured by ROSAND).

(8) The releasability from the mold at the time of injection molding was evaluated by visually observing the surface of the molded resin mold and checking for the presence or absence of mold release (cloud).
The 50-side resin mold was observed, and “no” was indicated when no release defect was observed, and “exist” was indicated when even one release defect was found.

(9) The stringing at the time of injection molding was evaluated by the length of the resin thread with a thin sprue end obtained at the time of resin mold molding.
The length of the resin yarn was measured for five sprues, and the case where the average value was 10 mm to 30 mm was marked with ◯, and the case where it exceeded 30 mm was marked with x.

(10) The transfer rate of the resin mold is determined using the scanning atomic force microscope (NanoScope IIIa manufactured by Digital Instruments Co., Ltd.), and the values of the land height (Hs) of the Ni stamper and the groove depth (Hd) of the resin mold. It was calculated by applying the following equation.
Transfer rate (%) = Hd / Hs × 100
The transfer rate of the resin mold needs to be 97 to 103%.

(11) The branching index represents the intrinsic viscosity [η] Bra of the branched alicyclic structure-containing thermoplastic resin, and the intrinsic viscosity [η] of the linear alicyclic structure-containing thermoplastic resin hydrogenated product having the same weight average molecular weight. It was calculated as the value divided by Lin.
Intrinsic viscosity [η] is obtained by measuring the viscosity at four points of concentration adjustment with a multi-point method using a Udderohde viscometer at 60 ° C for a sample dissolved in cyclohexane, and extrapolating the relationship between each measurement point to zero concentration. Asked.

Production Example 1
After adding 250 parts of dehydrated cyclohexane to a reactor at room temperature and in a nitrogen atmosphere, 0.84 part of 1-hexene, 0.06 part of dibutyl ether and 0.11 part of triisobutylaluminum were mixed, and the mixture was then heated to 45 ° C. 85 parts of tricyclo [4.3.12,5] dec-3-ene (hereinafter sometimes abbreviated as “DCP”), 8-ethyl-tetracyclo [4.4.0.12,5. 17,10] dodec-3-ene (hereinafter may be abbreviated as “ETD”) and 15 parts of a 0.7% toluene solution of tungsten hexachloride were continuously added over 2 hours for polymerization. The polymerization conversion rate was 100%.
The obtained polymerization reaction liquid was transferred to a pressure resistant hydrogenation reactor, 5 parts of a diatomaceous earth-supported nickel catalyst (Nissan Gardler G-96D, nickel support rate 58%) and 100 parts of cyclohexane were added, The reaction was carried out at a hydrogen pressure of 4.4 MPa for 8 hours. This reaction solution was filtered under pressure using Radiolite # 500 as a filter bed at a pressure of 0.25 MPa (funda filter manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd.) to remove the hydrogenation catalyst, and the colorless and transparent norbornene-based ring-opening polymer hydrogen The compound was obtained.
The hydride of this norbornene ring-opening polymer had a weight average molecular weight (Mw) of 30,000, a molecular weight distribution (Mw / Mn) of 2.7, a hydrogenation rate of 99.5%, and a branching index of 1.00. It was.
Subsequently, 0.50 parts of antioxidant: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) with respect to 99.50 parts of the norbornene-based ring-opening polymer hydride Propionate] (Irganox 1010 manufactured by Ciba Geigy) was added to the obtained solution and dissolved. Next, it is sequentially filtered through a Zeta Plus filter 30H (pore size 0.5 to 1 μm) manufactured by Cuneo Filter, and further filtered through another metal fiber filter (pore size 0.4 μm, manufactured by Nichidai Co., Ltd.). Minutes removed.
Next, using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.), the solvent was removed from the solution cyclohexane and other volatile components at a temperature of 270 ° C. and a pressure of 1 kPa or less, and directly connected to a concentrator. The resin composition (A) of the ring-opening copolymer hydrogenated product was obtained by extruding into a strand shape from a die in a molten state, pelletizing after cooling.
This resin composition (A) had a glass transition temperature of 105 ° C. and an MFR of 13.8 g / 10 min. Table 1 shows the shear viscosity and the extensional viscosity of the resin composition (A).

Production Example 2
0.50 parts of antioxidant: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] with respect to 99.47 parts of the norbornene-based ring-opening polymer hydride (Irganox 1010 manufactured by Ciba Geigy Co., Ltd.) and 0.03 part of a hydroxyl group-containing partial ester compound (pentaerythritol distearate (Unistar H476D manufactured by NOF Co., Ltd.)) as a release agent was added in the same manner as in Production Example 1. A resin composition (B) was obtained.
This resin composition (B) had a glass transition point of 104 ° C. and an MFR of 14.3 g / 10 min. The shear viscosity and elongational viscosity of the resin composition (B) are shown in Table 1.

Production Example 3
A resin composition (C) was obtained in the same manner as in Production Example 2, except that 1-hexene was changed to 0.6 part.
The hydride of norbornene-based ring-opening polymer had a weight average molecular weight (Mw) of 40000, a molecular weight distribution (Mw / Mn) of 3.0, a hydrogenation rate of 99.5%, and a branching index of 1.00.
The glass transition point of the resin composition (C) was 104 ° C., and the MFR was 5 g / 10 minutes. Table 1 shows the shear viscosity and elongational viscosity of the resin composition (C).

Production Example 4
A resin composition (D) was obtained in the same manner as in Production Example 2, except that 0.18 part of vinyl norbornene was added for polymerization.
The weight average molecular weight (Mw) of the norbornene ring-opening polymer hydride was 3.4300, the molecular weight distribution (Mw / Mn) was 3.3, the hydrogenation rate was 99.5%, and the branching index was 0.65. .
The glass transition point of the resin composition (D) was 103 ° C., and the MFR was 13 g / 10 minutes. Table 1 shows the shear viscosity and the extensional viscosity of the resin composition (D).

Production Example 5
Except for adding 0.10 parts of a hydroxyl group-containing partial ester compound: pentaerythritol distearate (Unistar H476D manufactured by NOF Corporation) as a mold release agent to 99.40 parts of the norbornene ring-opening polymer hydride. Resin composition (E) was obtained in the same manner as in Production Example 4.
The glass transition point of the resin composition (E) was 101 ° C., and the MFR was 15 g / 10 minutes. Table 1 shows the shear viscosity and the extension viscosity of the resin composition (E).

Production Example 6
Hydroxyl group-containing partial ester compound: 0.03 part hydroxyl group-containing fatty acid ester compound: 12-hydroxystearic acid triglyceride (Kao wax manufactured by Kao Corporation) as a release agent instead of pentaerythritol distearate (Nistar H476D manufactured by NOF Corporation) A resin composition (F) was obtained in the same manner as in Production Example 4 except that 85P) was added.
The glass transition point of the resin composition (F) was 103 ° C., and the MFR was 13.2 g / 10 minutes. Table 1 shows the shear viscosity and the extensional viscosity of the resin composition (F).

Production Example 7
A resin composition (F) was obtained in the same manner as in Production Example 4 except that the vinyl norbornene was changed to 0.08 part.
The weight average molecular weight (Mw) of the norbornene ring-opening polymer hydride was 3.2000, the molecular weight distribution (Mw / Mn) was 3.00, the hydrogenation rate was 99.5%, and the branching index was 0.94. .
The glass transition point of the resin composition (G) was 104 ° C., and the MFR was 13 g / 10 minutes. Table 1 shows the shear viscosity and the extensional viscosity of the resin composition (G).

Production Example 8
A resin composition (H) was obtained in the same manner as in Production Example 4 except that vinyl norbornene was changed to NBdimer.
The hydride of norbornene-based ring-opening polymer had a weight average molecular weight (Mw) of 35300, a molecular weight distribution (Mw / Mn) of 3.3, a hydrogenation rate of 99.5%, and a branching index of 0.61.
The glass transition point of the resin composition (H) was 104 ° C., and the MFR was 13 g / 10 min. Table 1 shows the shear viscosity and the extensional viscosity of the resin composition (H).

Production Example 9
0.59 parts of antioxidant: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4) with respect to 99.37 parts of the borned norbornene ring-opening polymer obtained in Production Example 2 -Hydroxyphenyl) propionate] (Irganox 1010 manufactured by Ciba Geigy Co., Ltd.), 0.03 part of a hydroxyl group-containing partial ester compound as a release agent: pentaerythritol distearate (Unistar H476D manufactured by NOF Corporation) and ultra high molecular polyethylene powder ( 0.10 parts of Mitsui Chemicals Mipelon XM220, viscosity average molecular weight 2 million) was added, and twin screw kneader (TEM-35B manufactured by Toshiba Machine Co., Ltd., screw diameter 37 mm, L / D = 32, screw rotation speed 150 rpm, resin) Kneaded at a temperature of 240 ° C. and a feed rate of 20 kg / hour) and extruded to obtain a resin composition (I).
The glass transition point of the resin composition (I) was 104 ° C., and the MFR was 12 g / 10 minutes. Table 1 shows the shear viscosity and elongational viscosity of the resin composition (I).

Production Example 10
0.29 parts of a hydroxyl group-containing partial ester compound as a release agent: pentaerythritol distearate (Unistar H476D manufactured by NOF Corporation) with respect to 99.28 parts of the norbornene ring-opening polymer hydride obtained in Production Example 4. ) Was added in the same manner as in Production Example 4 to obtain a resin composition (J).
The glass transition point of the resin composition (J) was 101 ° C., and the MFR was 17 g / 10 minutes. The shear viscosity and elongational viscosity of the resin composition (J) are shown in Table 1.

Production Example 11
Instead of the hydroxyl group-containing partial ester compound, 0.03 parts of a fatty acid ester compound not containing a hydroxyl group: stearic acid triglyceride (Rikemaru VT manufactured by Riken Vitamin Co., Ltd.) was added in the same manner as in Production Example 4. A resin composition (K) was obtained.
The glass transition point of the resin composition (K) was 104 ° C., and the MFR was 13 g / 10 minutes. Table 1 shows the shear viscosity and the extensional viscosity of the resin composition (K).

Production Example 12
A resin composition (L) was obtained in the same manner as in Production Example 4 except that vinyl norbornene was changed to 0.30 part.
The weight average molecular weight (Mw) of the norbornene ring-opening polymer hydride was 3.8000, the molecular weight distribution (Mw / Mn) was 3.5, the hydrogenation rate was 99.5%, and the branching index was 0.46. .
The glass transition point of the resin composition (L) was 104 ° C., and the MFR was 25 g / 10 min. Table 1 shows the shear viscosity and elongational viscosity of the resin composition (L).

Production Example 13
Except for adding 0.30 part of ultra high molecular weight polyethylene powder (Miperon XM220 manufactured by Mitsui Chemicals, Inc.) to 99.17 parts of hydride of norbornene-based ring-opening polymer obtained in Production Example 2, Production Example 9 and Similarly, a resin composition (M) was obtained.
The glass transition point of the resin composition (M) was 104 ° C., and the MFR was 6 g / 10 minutes. Table 1 shows the shear viscosity and the extension viscosity of the resin composition (M).

Production Example 14
Except for adding 0.01 part of ultra high molecular weight polyethylene powder (Miperon XM220 manufactured by Mitsui Chemicals) to 99.46 parts of the norbornene-based ring-opening polymer hydride obtained in Production Example 2, Production Example 9 and Similarly, a resin composition (N) was obtained.
The glass transition point of the resin composition (N) was 103 ° C., and the MFR was 13 g / 10 min. Table 1 shows the shear viscosity and the extensional viscosity of the resin composition (N).

Production Example 15
120 kg of tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (hereinafter sometimes referred to as TCD) was added to a reaction vessel charged with 258 liters of cyclohexane at room temperature under a nitrogen stream and stirred for 5 minutes. Further, triisobutylaluminum was added so that the concentration in the system was 1.0 ml / liter. Subsequently, ethylene was circulated at normal pressure while stirring to create an ethylene atmosphere in the system. The internal temperature of the autoclave was kept at 70 ° C. and pressurized with ethylene so that the internal pressure was 6 kg / cm ^{2 as a} gauge pressure. After stirring for 10 minutes, 0.4 liters of toluene solution containing isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride and methylalumoxane prepared in advance was added to the system, and the copolymerization reaction of ethylene and NB was started. I let you. The catalyst concentration at this time was 0.018 mmol / liter for isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride and 8.0 mmol / liter for methylalumoxane with respect to the entire system.

During the polymerization, ethylene was continuously supplied into the system, the temperature was maintained at 70 ° C., and the internal pressure was maintained at 6 kg / cm ² as a gauge pressure. After 60 minutes, isopropyl alcohol was added to stop the polymerization reaction. After depressurization, the polymer solution was taken out, and then contacted with an aqueous solution in which 5 liters of concentrated hydrochloric acid was added to 1 m ^{3 of} water at a ratio of 1: 1 with vigorous stirring to transfer the catalyst residue to the aqueous phase. After leaving this contact liquid mixture, the aqueous phase was separated and removed, and further washed with water twice to purify and separate the polymerization liquid phase.
The obtained norbornene-based addition polymer had a weight average molecular weight (Mw) of 41,000, a molecular weight distribution (Mw / Mn) of 3.5, and the repeating unit amount derived from TCD in the polymer was 25 mol%.

Next, the purified and separated polymer solution was brought into contact with 3 times the amount of acetone under strong stirring to precipitate the copolymer, and then the solid part (copolymer) was collected by filtration and sufficiently washed with acetone. Further, in order to extract unreacted monomers present in the polymer, this solid part was put into acetone so as to be 40 kg / m ^3, and then an extraction operation was performed at 60 ° C. for 2 hours. After the extraction treatment, the solid part was collected by filtration, and dried under nitrogen flow at 130 ° C. and 350 mmHg for 12 hours to obtain a norbornene-based addition polymer (O). The branching index of the norbornene addition polymer (G) was 1.00.
Subsequently, 0.50 parts of antioxidant: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate with respect to 99.50 parts of norbornene-based addition polymer (O) ] (Irganox 1010 manufactured by Ciba Geigy) was added to the obtained solution and dissolved. Next, it is sequentially filtered through a Zeta Plus filter 30H (pore size 0.5 to 1 μm) manufactured by Cuneo Filter, and further filtered through another metal fiber filter (pore size 0.4 μm, manufactured by Nichidai Co., Ltd.). Minutes removed.
Next, using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.), the solvent was removed from the solution cyclohexane and other volatile components at a temperature of 270 ° C. and a pressure of 1 kPa or less, and directly connected to a concentrator. The resin composition (O) was obtained by extruding into a strand form from a die in a molten state, cooling and pelletizing.
The glass transition temperature of the resin composition (O) was 115 ° C., and the MFR was 13.8 g / 10 min. The shear viscosity and elongational viscosity of the resin composition (O) are shown in Table 1.

Production Example 16
0.50 parts of antioxidant: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (99.47 parts of norbornene-based addition polymer (G)) ( Resin in the same manner as in Production Example 15 except that Irganox 1010 manufactured by Ciba Geigy Co., Ltd. and 0.03 part of a hydroxyl group-containing partial ester compound: pentaerythritol distearate (Unistar H476D manufactured by NOF Corporation) were added as a release agent. A composition (P) was obtained.
The glass transition point of the resin composition (P) was 114 ° C., and the MFR was 15.2 g / 10 minutes. Table 1 shows the shear viscosity and the extensional viscosity of the resin composition (P).

Production Example 17
A resin composition (Q) was obtained in the same manner as in Production Example 15 except that the polymerization ratio of ethylene and NBdimer to TCD was changed as shown in Table 1.
The norbornene-based addition polymer has a weight average molecular weight (Mw) of 43,000, a molecular weight distribution (Mw / Mn) of 3.5, a TCD-derived repeating unit amount in the polymer of 25 mol%, and a vinyl norbornene-derived polymer in the polymer. The repeating unit amount was 0.18 mol%, and the branching index was 0.6.
The glass transition point of the resin composition (Q) was 103 ° C., and the MFR was 10 g / 10 minutes. Table 1 shows the shear viscosity and elongational viscosity of the resin composition (Q).

Example 1
Production of Resin Mold The resin composition (D) obtained in Production Example 4 was injection-molded to obtain a disk-shaped resin mold having an inner diameter of 15 mm, an outer diameter of 120 mm, and a thickness of 0.6 mm.

  The plasticizing apparatus used for injection molding is a mold having a cavity depth of 0.580 mm, to which a Ni stamper for DVD + R having a concentric uneven pattern with a width of 0.16 μm, an arrangement pitch of 0.32 μm, and a depth of 160 nm is attached. It was an injection molding machine (SD40ER manufactured by Sumitomo Heavy Industries, Ltd.).

The resin temperature (barrel set maximum temperature) was 350 ° C., the mold fixing side was 91 ° C., and the mold movable side was 69 ° C. The maximum compression force of the mold is 35 tons, the initial opening width of the mold (initial mold opening amount) is set to 0.4 mm by the mold opening amount control, and the maximum compression force is 0.12 seconds after the start of injection. Closed the mold. The amount of filled resin was 6.4 g, and the maximum injection speed was 130 mm / s.
The obtained resin mold (D) was evaluated for releasability, stringing and transfer rate. The results are shown in Table 2.

Example 2
The resin mold (E) obtained in Production Example 5 was subjected to injection molding in the same manner as in Example 1 to evaluate the mold release property, stringing and transfer rate of the resin mold. The results are shown in Table 2.

Example 3
The resin mold (F) obtained in Production Example 6 was subjected to injection molding in the same manner as in Example 1 to evaluate the releasability, stringing and transfer rate of the resin mold obtained. The results are shown in Table 2.

Example 4
The resin mold (G) obtained in Production Example 7 was subjected to injection molding in the same manner as in Example 1 to evaluate the mold release property, stringing and transfer rate of the resin mold. The results are shown in Table 2.

Example 5
A resin mold obtained by injection molding the resin composition (H) obtained in Production Example 8 in the same manner as in Example 1 was evaluated for releasability, stringing and transfer rate. The results are shown in Table 2.

Example 6
The resin mold (I) obtained in Production Example 9 was subjected to injection molding in the same manner as in Example 1 to evaluate the mold release property, stringing and transfer rate of the resin mold. The results are shown in Table 2.

Example 7
The resin mold (Q) obtained in Production Example 17 was subjected to injection molding in the same manner as in Example 1 to evaluate the releasability, stringing and transfer rate of the resin mold obtained. The results are shown in Table 2.

Comparative Example 1
The resin mold (A) obtained in Production Example 1 was subjected to injection molding in the same manner as in Example 1 to evaluate the releasability, stringing and transfer rate of the resin mold obtained. The results are shown in Table 2.

Comparative Example 2
The resin mold (B) obtained in Production Example 2 was subjected to injection molding in the same manner as in Example 1 to evaluate the release properties, stringing, and transfer rate of the resin mold. The results are shown in Table 1.

Comparative Example 3
The resin mold (C) obtained in Production Example 3 was subjected to injection molding in the same manner as in Example 1 to evaluate the releasability, stringing and transfer rate of the resin mold obtained. The results are shown in Table 2.

Comparative Example 4
The resin mold (J) obtained in Production Example 10 was subjected to injection molding in the same manner as in Example 1 to evaluate the mold release property, stringing, and transfer rate of the resin mold. The results are shown in Table 2.

Comparative Example 5
The resin mold (K) obtained in Production Example 11 was subjected to injection molding in the same manner as in Example 1 to evaluate the releasability, stringing and transfer rate of the resin mold. The results are shown in Table 2.

Comparative Example 6
The resin mold (L) obtained in Production Example 12 was subjected to injection molding in the same manner as in Example 1 to evaluate the release properties, stringing, and transfer rate of the resin mold. The results are shown in Table 2.

Comparative Example 7
The resin mold (M) obtained in Production Example 13 was subjected to injection molding in the same manner as in Example 1 to evaluate the releasability, stringing and transfer rate of the resin mold obtained. The results are shown in Table 2.

Comparative Example 8
The resin mold (N) obtained in Production Example 14 was subjected to injection molding in the same manner as in Example 1 to evaluate the mold release property, stringing and transfer rate of the resin mold. The results are shown in Table 2.

Comparative Example 9
The resin mold (O) obtained in Production Example 15 was subjected to injection molding in the same manner as in Example 1 to evaluate the mold release property, stringing and transfer rate of the resin mold. The results are shown in Table 2.

Comparative Example 10
The resin mold (P) obtained in Production Example 16 was subjected to injection molding in the same manner as in Example 1 to evaluate the releasability, stringing and transfer rate of the resin mold obtained. The results are shown in Table 2.

The resin compositions of Examples 1 to 7 had good releasability and stringiness, and the resin mold made of the resin composition had good transferability.
The resin composition of Comparative Example 1 that did not contain a hydroxyl group-containing ester compound caused poor mold release.
The resin composition of Comparative Example 2 having an excessively low extensional viscosity caused stringing.
The transfer rate of the resin mold made of the resin composition of Comparative Example 3 having a too high shear viscosity was low.
The resin composition of Comparative Example 4 in which the content of the hydroxyl group-containing ester compound was too large caused stringing.
The resin composition of Comparative Example 5 that did not contain a hydroxyl group-containing ester compound caused poor mold release.
The resin composition of Comparative Example 6 in which the shear viscosity and the extension viscosity were too low caused stringing, and the uneven pattern of the resin mold made of the resin composition was deformed, resulting in transfer failure.
The transfer rate of the resin mold made of the resin composition of Comparative Example 7 having too high shear viscosity was low.
The uneven pattern of the resin mold made of the resin composition of Comparative Example 9 containing no hydroxyl group-containing ester compound was deformed, resulting in transfer failure.
The resin composition of Comparative Example 10 having a too low extensional viscosity caused stringing, and the uneven pattern of the resin mold made of the resin composition was deformed, resulting in transfer failure.

Claims (8)

A resin composition containing an alicyclic structure-containing thermoplastic resin and a hydroxyl group-containing ester compound, wherein the hydroxyl group-containing ester compound content is 0.02 to 0.20 parts by mass with respect to 100 parts by mass of the resin composition. A resin composition having a shear viscosity of 20 to 50 Pa · s at 230 ° C. and a shear rate of 10,000 / s, and an extension viscosity of 6 to 20 kPa · s at 230 ° C. and an extension rate of 100 / s. The resin composition according to claim 1, wherein the alicyclic structure-containing thermoplastic resin has a branching index in the range of 0.5 to 0.98. The resin composition according to claim 1, comprising 0.01 to 1.0 part by mass of polyethylene having a viscosity average molecular weight of 1,500,000 to 3,000,000 with respect to 100 parts by mass of the resin composition. The resin composition according to any one of claims 1 to 3, wherein the alicyclic structure-containing thermoplastic resin is a hydride of a norbornene-based ring-opening polymer. The resin composition according to any one of claims 1 to 3, wherein the alicyclic structure-containing thermoplastic resin is a norbornene-based addition polymer. A resin mold comprising the resin composition according to claim 1. A curable resin is applied on the substrate, the resin mold described in claim 6 is overlaid on the obtained curable resin layer, and the resin mold is peeled and removed after the curable resin layer is cured. Manufacturing method of a molded object. A method for producing a molded body, comprising filling a curable resin in an internal space formed by a resin mold according to claim 6, curing the curable resin, and then peeling and removing the resin mold.