JP5778884B2 - Resin composition, pentaerythritol derivative composition and method for producing the same - Google Patents

Description

  The present invention relates to a resin composition comprising a polymer having an alicyclic structure in at least a part of repeating structural units and a pentaerythritol derivative composition.

  Since the cyclic polyolefin resin is excellent in transparency and can withstand use under high temperature conditions, it is widely used as various optical components. However, when the molded product obtained from the cyclic polyolefin resin is used under high temperature and high humidity, the resin may be whitened.

  As a solution to such a problem, Patent Document 1 describes that an ester of glycerin and a fatty acid is blended. Patent Document 2 describes blending pentaerythritol distearate.

  However, when a resin composition in which these additives are blended is used for an optical component that requires higher optical performance, the initial optical performance may not be sufficient. In addition, optical performance degradation at high temperature and high humidity is only judged by haze and appearance. Even when the initial characteristics are satisfied, the spectral light transmittance decreases on the short wavelength side after the high temperature and high humidity test, and slight aberrations occur. Changes could affect the performance of optical instruments.

JP 2003-238774 A JP-A-9-19494

  An object of the present invention is to provide a resin composition capable of obtaining a transparent thermoplastic molded article excellent in optical performance and further suppressed in degradation of optical performance at high temperature and high humidity, and a pentaerythritol derivative composition added to the resin composition It is in providing a thing and its manufacturing method.

  In order to solve the above problems, the present invention has been studied, and as a result, the amount of the pentaerythritol derivative composition added to the polymer having an alicyclic structure in at least a part of the repeating structural units, and the structure and composition of the pentaerythritol derivative composition The inventors have found that there is an optimum range for the ratio, and have reached the present invention.

（式中、ｘ，ｙは共重合比を示し、０／１００≦ｙ／ｘ≦９５／５を満たす実数である。）で表される、エチレンとテトラシクロ［４．４．０．１ ^2,5 ．１ ^7,10 ］-３-ドデセンとの共重合体またはその水素添加物、または８−エチルテトラシクロ［４．４．０．１ ^２，５ ．１ ^７，１０ ］−ドデカ−３−エンの開環重合体の水素添加物である重合体１００質量部に対し、
ペンタエリスリトール、ペンタエリスリトールの脂肪酸モノエステル、ペンタエリスリトールの脂肪酸ジエステル、ペンタエリスリトールの脂肪酸トリエステル、およびペンタエリスリトールの脂肪酸テトラエステルを含むペンタエリスリトール誘導体組成物を１．０質量部以上３．０質量部以下含み、
前記脂肪酸モノエステル、前記脂肪酸ジエステル、前記脂肪酸トリエステル、および前記脂肪酸テトラエステルを構成する脂肪酸が、ステアリン酸又はパルミチン酸であり、
前記ペンタエリスリトール誘導体組成物の組成が、式（ａ）および（ｂ）；
０．２％ ≦ ［Ａ₀］ ≦ ２％ （ａ）
６０％ ≦ Ａ_１＋Ａ_２ ≦ ８０％ （ｂ）
（但し、式（ａ）中、［Ａ_０］は、ガスクロマトグラフィー法において定量された、前記ペンタエリスリトールの、前記ペンタエリスリトール誘導体組成物中の含有質量％を示す。なお、式（ａ）において、前記ペンタエリスリトール、前記脂肪酸モノエステル、前記脂肪酸ジエステル、前記脂肪酸トリエステル、および前記脂肪酸テトラエステルの合計質量を１００質量％とする。
また、式（ｂ）中、Ａ_１は、前記脂肪酸モノエステルのゲル浸透クロマトグラフ（ＧＰＣ）法における、下記条件で測定されたピーク面積％を示し、Ａ_２は、前記脂肪酸ジエステルのＧＰＣ法における、下記条件で測定されたピーク面積％を示す。なお、式（ｂ）において、前記ペンタエリスリトール、前記脂肪酸モノエステル、前記脂肪酸ジエステル、前記脂肪酸トリエステル、および前記脂肪酸テトラエステルの各々のピークの合計面積をピーク面積１００％とする。）
を満たすことを特徴とする樹脂組成物。
測定機器：ＨＬＣ−８２２０ＧＰＣ（東ソー社製）
カラム：Ｇ２０００ＨＸＬ＋Ｇ１０００ＨＸＬ
溶媒：ＴＨＦ
流量：１．０ｍＬ/ｍｉｎ
カラム温度：４０℃
サンプル濃度：０．３％
注入量：１００μＬ
検出感度：０．１００ｍＶ／分
検出器：ＲＩ
標準物質：ポリスチレン（東ソー社製、Ｍｗ＝５２６、２６３０、１０２００）
That is, the present invention is shown below.
[1] The following general formula:

(Wherein, x, y represent a copolymerization ratio and 0/100 is a real number satisfying ≦ y / x ≦ 95/5 .) Represented by ethylene and tetracyclo [4.4.0.1 ^{2, 5} . Copolymer with 1 ^7,10 ] -3-dodecene or a hydrogenated product thereof, or 8-ethyltetracyclo [4.4.0.1 ^2,5 . To dodeca-3-Ru hydrogenated product der en ring-opening polymer polymer 100 parts by weight, - 1 ^7,10]
Pentaerythritol, fatty acid monoester of pentaerythritol, fatty acid diester of pentaerythritol, fatty acid triester of pentaerythritol, and pentaerythritol derivative composition containing fatty acid tetraester of pentaerythritol are 1.0 part by weight or more and 3.0 parts by weight or less. Including
The fatty acid constituting the fatty acid monoester, the fatty acid diester, the fatty acid triester, and the fatty acid tetraester is stearic acid or palmitic acid,
The pentaerythritol derivative composition has the formulas (a) and (b);
0.2% ≦ [A ₀ ] ≦ 2% (a)
60% ≦ A ₁ + A ₂ ≦ 80% (b)
(Wherein (a), [A _0] is quantified in gas chromatography, of the pentaerythritol shows content by mass% in the pentaerythritol derivative composition. In Expression (a) The total mass of the pentaerythritol, the fatty acid monoester, the fatty acid diester, the fatty acid triester, and the fatty acid tetraester is 100% by mass.
In the formula (b), _{A 1} is in a gel permeation chromatograph (GPC) method of the fatty acid monoester, a peak area% measured under the following conditions, _{A 2} is in the GPC method of said fatty acid diester The peak area% measured under the following conditions is shown. In the formula (b), the total area of the respective peaks of the pentaerythritol, the fatty acid monoester, the fatty acid diester, the fatty acid triester, and the fatty acid tetraester is 100% peak area. )
The resin composition characterized by satisfy | filling.
Measuring instrument: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: G2000HXL + G1000HXL
Solvent: THF
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Sample concentration: 0.3%
Injection volume: 100 μL
Detection sensitivity: 0.100 mV / min
Detector: RI
Standard material: polystyrene (Made by Tosoh Corporation, Mw = 526, 2630, 10200)

[2] The resin composition according to [1], wherein the formula (a) is represented as follows:
0.2% ≦ [A ₀ ] ≦ 1% (a)
(In formula (a), [A ₀ ] is as defined above.)

[ 3 ] Pentaerythritol, fatty acid monoester of pentaerythritol, fatty acid diester of pentaerythritol, fatty acid triester of pentaerythritol, and fatty acid tetraester of pentaerythritol, and the fatty acid constituting these esters is stearic acid or palmitic acid A pentaerythritol derivative composition,
The composition of the derivative composition satisfies the formulas (a) and (b), and ethylene and tetracyclo [4.4.0.1 ^2,5 . Copolymer with 1 ^7,10 ] -3-dodecene or a hydrogenated product thereof, or 8-ethyltetracyclo [4.4.0.1 ^2,5 . A pentaerythritol derivative composition, which is used as an additive for a polymer selected from hydrogenated ring-opening polymers of ^{17, 10} ] -dodec-3-ene .
0.2% ≦ [A ₀ ] ≦ 2% (a)
60% ≦ A ₁ + A ₂ ≦ 80% (b)
(Wherein (a), [A _0] is quantified in gas chromatography, of the pentaerythritol shows content by mass% in the pentaerythritol derivative composition. In Expression (a) The total mass of the pentaerythritol, the fatty acid monoester, the fatty acid diester, the fatty acid triester, and the fatty acid tetraester is 100% by mass.
In the formula (b), _{A 1} is in a gel permeation chromatograph (GPC) method of the fatty acid monoester, a peak area% measured under the following conditions, _{A 2} is in the GPC method of said fatty acid diester The peak area% measured under the following conditions is shown. In the formula (b), the total area of the respective peaks of the pentaerythritol, the fatty acid monoester, the fatty acid diester, the fatty acid triester, and the fatty acid tetraester is 100% peak area. )
Measuring instrument: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: G2000HXL + G1000HXL
Solvent: THF
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Sample concentration: 0.3%
Injection volume: 100 μL
Detection sensitivity: 0.100 mV / min
Detector: RI
Standard material: polystyrene (Made by Tosoh Corporation, Mw = 526, 2630, 10200)

[ 4 ] The pentaerythritol derivative composition according to [ 3 ], wherein the formula (a) is represented as follows:
0.2% ≦ [A ₀ ] ≦ 1% (a)
(In formula (a), [A ₀ ] is as defined above.)

[ 5 ] pentaerythritol is esterified by reacting a fatty acid having 12 to 22 carbon atoms in an amount of 1.0 to 1.7 mol with respect to 1 mol of pentaerythritol;
Filtering the esterified product obtained in the step, and the method for producing a pentaerythritol derivative composition according to [ 3 ] or [ 4 ].

[ 6 ] In the above step of esterifying pentaerythritol,
The method for producing a pentaerythritol derivative composition according to [ 5 ], wherein pentaerythritol having a sodium content of 100 ppm or less is used.

  The resin composition of the present invention is optimal as a raw material for forming transparent parts, and can provide a transparent thermoplastic molded article that is excellent in optical performance and further suppressed in deterioration of optical performance at high temperature and high humidity. Furthermore, by using the pentaerythritol derivative composition of the present invention as an additive for a polymer having an alicyclic structure in at least a part of the repeating structural units, the resulting resin composition can obtain the above effects. .

(Polymer having an alicyclic structure in at least a part of the repeating structural unit)
A polymer having an alicyclic structure in at least a part of the repeating structural unit of the present invention (hereinafter, also simply referred to as “polymer having an alicyclic structure”) has an alicyclic structure in at least a part of the repeating unit of the polymer. Any polymer having a group structure may be used, and specifically, a polymer having one or more structures represented by the general formula (2) is preferably included.

In formula (2), x and y represent copolymerization ratios and are real numbers satisfying 0/100 ≦ y / x ≦ 95/5. x and y are on a molar basis.
n represents the number of substitutions of the substituent Q, and is a real number of 0 ≦ n ≦ 2, preferably 0.
R ^a is a 2 + n-valent group selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms.
R ^b is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 28 carbon atoms.
R ^c is a tetravalent group selected from the group consisting of hydrocarbon groups having 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms.
Q is a halogen atom, a halogenated alkyl group, an alkoxy group or —COOR ^d . R ^d is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Preferably, it is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.
Each of R ^a , R ^b , R ^c and Q may be one kind, or may have two or more kinds in any ratio.

In the general formula (2), R ^a is preferably one or more divalent groups selected from hydrocarbon groups having 2 to 12 carbon atoms, and more preferably n = 0. In this case, it is a divalent group represented by the general formula (3), and most preferably a divalent group in which p is 0 or 1 in the following general formula (3). The structure of ^Ra may be used alone or in combination of two or more.

Here, in Formula (3), p is an integer of 0-2.
In the general formula (2), examples of R ^b include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a 2-methylpropyl group. Preferably a hydrogen atom and / or a methyl group, and most preferably a hydrogen atom.

In the general formula (2), the following general formula in the case of n = 0

Examples of the divalent group represented by the formulas include groups represented by the following general formulas (4) to (6).

In formula (4) to formula (6), R ^a is as described above.
Further, the type of polymerization is not limited at all in the present invention, and various known polymerization types such as addition polymerization and ring-opening polymerization can be applied. Examples of the addition polymerization include a random copolymer, a block copolymer, and alternating copolymerization. In the present invention, it is preferable to use a random copolymer from the viewpoint of suppressing deterioration of optical performance.

  When the structure of the resin used as the main component is as described above, it is excellent in optical properties such as transparency, refractive index and birefringence, and a highly accurate optical component can be obtained.

(Example of a polymer having an alicyclic structure in at least a part of the repeating structural unit)
The polymers represented by the general formula (2) are roughly divided into the following four types of polymers (i) to (iv).
(I) Copolymer of ethylene or α-olefin and cyclic olefin (ii) Ring-opening polymer or hydrogenated product thereof (iii) Vinyl alicyclic hydrocarbon polymer (iv) Other polymer explain.

((I) Copolymer of ethylene or α-olefin and cyclic olefin)
(I) A copolymer of ethylene or α-olefin and a cyclic olefin is a cyclic olefin copolymer represented by the general formula (7). For example, it consists of a structural unit (A) derived from a linear or branched α-olefin having 3 to 30 carbon atoms and a structural unit (B) derived from a cyclic olefin.

In formula (7), R ^a is a divalent group selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms.
R ^b is a hydrogen atom or a monovalent group selected from the group consisting of hydrocarbon groups having 1 to 28, preferably 1 to 10, more preferably 1 to 5 carbon atoms.
Each of R ^a and R ^b may be one kind, or may have two or more kinds in any ratio.
x and y represent copolymerization ratios and are real numbers satisfying 5/95 ≦ y / x ≦ 95/5. Preferably 50/50 ≦ y / x ≦ 95/5, and more preferably 55/45 ≦ y / x ≦ 80/20. x and y are on a molar basis.

(Constitutional unit derived from ethylene or α-olefin (A))
The structural unit (A) derived from ethylene or an α-olefin is a structural unit derived from the following ethylene or a linear or branched α-olefin having 3 to 30 carbon atoms.

  Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1 -Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Of these, ethylene is preferred. Two or more of these structural units derived from ethylene or α-olefin may be contained as long as the effects of the present invention are not impaired.

(Constitutional unit derived from cyclic olefin (B))
The structural unit (B) derived from the cyclic olefin is composed of at least one selected from the group consisting of structural units derived from the cyclic olefin represented by the following general formula (8), general formula (9), and general formula (10). .
The cyclic olefin represented by the general formula (8) has the following structure.

In formula (8), u is 0 or 1, v is 0 or a positive integer, and w is 0 or 1. When w is 1, the ring represented by w is a 6-membered ring, and when w is 0, this ring is a 5-membered ring. R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 may be the same as or different from each other, and are a hydrogen atom, a halogen atom, or a hydrocarbon group.

  The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Moreover, as a hydrocarbon group, a C1-C20 alkyl group, a C1-C20 halogenated alkyl group, a C3-C15 cycloalkyl group, or an aromatic hydrocarbon group is mentioned normally. .

  More specifically, examples of the alkyl group include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, octadecyl and the like. Examples of the halogenated alkyl group include groups in which one or more halogen atoms have been substituted on the alkyl group having 1 to 20 carbon atoms. Examples of the cycloalkyl group include cyclohexyl, and examples of the aromatic hydrocarbon group include phenyl and naphthyl.

Further, in the general formula (8), R ⁷⁵ and R ⁷⁶ , R ⁷⁷ and R ⁷⁸ , R ⁷⁵ and R ⁷⁷ , R ⁷⁶ and R ⁷⁸ , R ⁷⁵ and R ⁷⁸ , or R ⁷⁶ and R ⁷⁷ may be bonded to each other, that is, may be combined with each other to form a monocyclic or polycyclic group. Furthermore, the monocyclic or polycyclic ring thus formed may have a double bond. Since a copolymer having a high glass transition temperature (Tg) can be obtained with a smaller content of polycyclic rings than monocyclic rings, polycyclic rings are preferred from the viewpoint of heat resistance. Furthermore, there is an advantage that it can be produced with a small amount of cyclic olefin. Specific examples of the monocyclic or polycyclic group formed here include the following.

In the above examples, the carbon atom numbered 1 or 2 represents the carbon atom to which R ⁷⁵ (R ⁷⁶ ) or R ⁷⁷ (R ⁷⁸ ) is bonded in the general formula (8).

R ⁷⁵ and R ⁷⁶ or R ⁷⁷ and R ⁷⁸ may form an alkylidene group. This alkylidene group usually has 2 to 20 carbon atoms. Specific examples of the alkylidene group include ethylidene, propylidene, isopropylidene and the like.

  The cyclic olefin represented by the general formula (9) has the following structure.

In the formula (9), x and d are 0 or a positive integer of 1 or more, and y and z are 0, 1 or 2. R ^{81 to} R ⁹⁹ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an alkoxy group, and R ⁸⁹ and R ⁹⁰ are bonded to each other. The carbon atom bonded to R ⁹³ or the carbon atom bonded to R ⁹¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. When y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring.
As a halogen atom, the same thing as the halogen atom in the said Formula (8) can be illustrated.

  Examples of the aliphatic hydrocarbon group include an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms. More specifically, examples of the alkyl group include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, octadecyl and the like. Examples of the cycloalkyl group include cyclohexyl.

  Examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group, and specific examples include phenyl, tolyl, naphthyl, benzyl, and phenylethyl.

Examples of the alkoxy group include methoxy, ethoxy, propoxy and the like. Here, the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded are directly or an alkylene group having 1 to 3 carbon atoms. It may be connected via. That is, when the two carbon atoms are bonded via an alkylene group, R ⁸⁹ and R ⁹³ or R ⁹⁰ and R ⁹¹ are combined with each other to form a methylene group (—CH ₂ -), ethylene group _(-CH 2 CH ₂ -) or propylene group _{(-CH 2 CH 2 CH 2 -} ) to form one alkylene group of the.

Furthermore, when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Specifically, when y = z = 0, the following aromatic rings formed by R ⁹⁵ and R ⁹² are exemplified. Since a copolymer having a high glass transition temperature (Tg) can be obtained with a smaller content of polycyclic rings than monocyclic rings, polycyclic rings are preferred from the viewpoint of heat resistance. Furthermore, there is an advantage that it can be produced with a small amount of cyclic olefin.

l is the same as d in the general formula (9).
The cyclic olefin represented by the general formula (10) has the following structure.

In the formula (10), R ¹⁰⁰ and R ¹⁰¹ may be the same or different from each other, and are a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18. Preferred examples of the hydrocarbon group having 1 to 5 carbon atoms include an alkyl group, a halogenated alkyl group, and a cycloalkyl group. These specific examples are clear from the specific examples of R ^{61 to} R ^{78 in} the above formula (8).

  As the structural unit (B) derived from the cyclic olefin represented by the general formula (8), (9) or (10) as described above, specifically, a bicyclo-2-heptene derivative (bicyclohept-2-ene derivative) ), Tricyclo-3-decene derivatives, tricyclo-3-undecene derivatives, tetracyclo-3-dodecene derivatives, pentacyclo-4-pentadecene derivatives, pentacyclopentadecadiene derivatives, pentacyclo-3-pentadecene derivatives, pentacyclo-4-hexadecene derivatives , Pentacyclo-3-hexadecene derivatives, hexacyclo-4-heptadecene derivatives, heptacyclo-5-eicosene derivatives, heptacyclo-4-eicosene derivatives, heptacyclo-5-heneicosene derivatives, octacyclo-5-docosene derivatives, nonacyclo-5-penta Cene derivatives, nonacyclo-6-hexacocene derivatives, cyclopentadiene-acenaphthylene adduct derivatives, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene derivatives, 1,4-methano-1,4,4a, 5 , 10,10a-hexahydroanthracene derivatives, cycloalkylene derivatives having 3 to 20 carbon atoms, and the like.

Further, among the structural units (B) derived from the cyclic olefin represented by the above general formula (8), (9) or (10), tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene derivative, hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . ^09,14 ] -4-heptadecene derivatives and derivatives of compounds represented by the following structure are exemplified as preferred embodiments.

  5-Phenyl-bicyclo [2.2.1] hept-2-ene

5-Methyl-5-phenyl-bicyclo [2.2.1] hept-2-ene

  5-Tolyl-bicyclo [2.2.1] hept-2-ene

  5- (Ethylphenyl) -bicyclo [2.2.1] hept-2-ene

  5- (Isopropylphenyl) -bicyclo [2.2.1] hept-2-ene

  5- (α-Naphthyl) -bicyclo [2.2.1] hept-2-ene

  5- (Biphenyl) -bicyclo [2.2.1] hept-2-ene

  5,6- (Diphenyl) -bicyclo [2.2.1] hept-2-ene

  1,4-methano-1,4,4a, 9a-tetrahydrofluorene

  1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene

  Cyclopentadiene-acenaphthylene adduct

  Cyclopentadiene-benzyne adduct

  Benzonorbornadiene derivatives

Particularly preferably, the cyclic olefin is tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, cyclopentadiene-benzyne adduct and cyclopentadiene-acenaphthylene adduct, Most preferably, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene.

  The cyclic olefin represented by the general formula (8) or (9) as described above can be produced by subjecting cyclopentadiene and an olefin having a corresponding structure to Diels-Alder reaction. Two or more kinds of the structural units (B) derived from the cyclic olefin represented by the general formula (8), (9) or (10) may be contained. Moreover, what superposed | polymerized using the said monomer can be modified | denatured as needed, and the structure of the structural unit derived from a monomer can be changed in that case. For example, a benzene ring or the like in a monomer-derived structural unit can be converted into a cyclohexyl ring depending on conditions by hydrogenation treatment.

In the present invention, “(i) a copolymer of ethylene or an α-olefin and a cyclic olefin” includes ethylene and tetracyclo [4.4.0.1 ^2,5 . It is preferable that it is a copolymer consisting of 1 ^7,10 ] -3-dodecene.

  In addition, the type of copolymerization is not limited at all in the present invention, and various known copolymerization types such as random copolymer, block copolymer, alternating copolymerization and the like can be applied, but random copolymer is preferable. .

((Ii) Ring-opening polymer or hydrogenated product thereof)
(Ii) The ring-opening polymer or a hydrogenated product thereof is a cyclic olefin polymer containing a structural unit represented by the general formula (5) among the structures given as preferred examples in the general formula (2). .

  The cyclic olefin polymer may have a polar group. Examples of the polar group include a hydroxyl group, a carboxyl group, an alkoxy group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyl group, an amino group, and an ester group.

  The cyclic olefin polymer is usually obtained by polymerizing a cyclic olefin, specifically by ring-opening polymerization of an alicyclic olefin. In addition, the cyclic olefin polymer having a polar group is obtained, for example, by introducing a compound having a polar group into the cyclic olefin polymer by a modification reaction, or using a monomer containing a polar group as a copolymerization component. Obtained by copolymerization.

Specifically, as the alicyclic olefin used to obtain the cyclic olefin polymer,
Bicyclo [2.2.1] -hept-2-ene (common name: norbornene), 5-methyl-bicyclo [2.2.1] -hept-2-ene, 5,5-dimethyl-bicyclo [2. 2.1] -Hept-2-ene, 5-ethyl-bicyclo [2.2.1] -hept-2-ene, 5-butyl-bicyclo [2.2.1] -hept-2-ene, 5 -Hexyl-bicyclo [2.2.1] -hept-2-ene, 5-octyl-bicyclo [2.2.1] -hept-2-ene, 5-octadecyl-bicyclo [2.2.1]- Hept-2-ene, 5-ethylidene-bicyclo [2.2.1] -hept-2-ene, 5-methylidene-bicyclo [2.2.1] -hept-2-ene, 5-vinyl-bicyclo [ 2.2.1] -Hept-2-ene, 5-propenyl-bicyclo [2.2.1] -Hept-2-ene, 5-methoxy-carbinyl-bicyclo [2.2.1] -hept-2-ene, 5-cyano-bicyclo [2.2.1] -hept-2-ene, 5-methyl -5-methoxycarbonyl-bicyclo [2.2.1] -hept-2-ene, 5-ethoxycarbonyl-bicyclo [2.2.1] -hept-2-ene, bicyclo [2.2.1]- Hept-5-enyl-2-methylpropionate, bicyclo [2.2.1] -hept-5-enyl-2-methyloctanoate, bicyclo [2.2.1] -hept-2-ene-5 , 6-dicarboxylic anhydride, 5-hydroxymethylbicyclo [2.2.1] -hept-2-ene, 5,6-di (hydroxymethyl) -bicyclo [2.2.1] -hept-2-ene Ene, 5-hydroxy-i-propylbicycle [2.2.1] -Hept-2-ene, 5,6-dicarboxy-bicyclo [2.2.1] -hept-2-ene, bicyclo [2.2.1] -hept-2-ene -5,6-dicarboxylic acid imide, 5-cyclopentyl-bicyclo [2.2.1] -hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] -hept-2-ene, 5-cyclo Hexenyl-bicyclo [2.2.1] -hept-2-ene, 5-phenyl-bicyclo [2.2.1] -hept-2-ene, tricyclo [4.3.0.1 ^2,5 ] deca -3,7-diene (common name: dicyclopentadiene), tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, tricyclo [4.4.0.1 ^2,5 ] undeca-3 , 7-diene, tricyclo [4.4.0.1 ^2,5] undec -3,8 Diene, tricyclo [4.4.0.1 ^2,5] undec-3-ene, tetracyclo ^{[7.4.0.1 10,13.} 0 ^2,7] - trideca -2,4,6-11- tetraene (alias: 1,4-methano -1,4,4a, 9a- tetrahydrofluorene), tetracyclo ^{[8.4.0.1 11, 14} . 0 ^3,8 ] -tetradeca-3,5,7,12-11-tetraene (also known as 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene), tetracyclo [4.4 .0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene (common name: tetracyclododecene), 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-carboxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-cyclohexenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-phenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^{9, 13]} - pentadeca-3,10-diene, pentacyclo [7.4.0.1 ^3,6. 1 ^10,13 . Norbornene monomers such as 0 ^2,7 ] -pentadeca-4,11-diene;
Cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H -Monocyclic cycloalkenes such as indene, cycloheptene;
Vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane;
And cycloaliphatic conjugated diene monomers such as cyclopentadiene and cyclohexadiene. The alicyclic olefins can be used alone or in combination of two or more.

A copolymerizable monomer can be copolymerized as necessary. Specific examples thereof include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl- 1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1- Ethylene or α-olefin having 2 to 20 carbon atoms such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene;
Cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H -Cycloolefins such as indene;
Non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene; and the like. These monomers can be used alone or in combination of two or more.

  The polymerization method of the alicyclic olefin is not particularly limited and can be performed according to a known method. These ring-opening polymers are preferably used after hydrogenation from the viewpoints of heat resistance, stability, and optical properties. A known method can be used as the hydrogenation method.

((Iii) vinyl alicyclic hydrocarbon polymer)
(Iii) A vinyl alicyclic hydrocarbon polymer is obtained by using a vinyl aromatic hydrocarbon compound as a monomer and a hydrogenated product of a (co) polymer or a vinyl alicyclic hydrocarbon compound as a monomer. (Co) polymers produced. Examples of vinyl compounds include vinyl aromatic compounds and vinyl alicyclic hydrocarbon compounds.

  Examples of vinyl aromatic compounds include styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-isopropylstyrene, α-t-butylstyrene, 2-methylstyrene, 3-methylstyrene, and 4-methylstyrene. Styrene such as 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, monochlorostyrene, dichlorostyrene, monofluorostyrene, 4-phenylstyrene And the like.

As vinyl alicyclic hydrocarbon compounds, vinylcyclohexanes such as vinylcyclohexane and 3-methylisopropenylcyclohexane;
4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-vinylcyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-vinylcyclohexene, 2-methyl-4-isopropenylcyclohexene, etc. Examples thereof include vinylcyclohexenes.

In the present invention, other monomers copolymerizable with the aforementioned monomers may be copolymerized. Examples of copolymerizable monomers include α-olefin monomers such as ethylene, propylene, isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, and 4-methyl-1-pentene;
Cyclopentadiene monomers such as cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 5-methylcyclopentadiene, 5,5-dimethylcyclopentadiene, dicyclopentadiene;
Monocyclic olefin monomers such as cyclobutene, cyclopentene and cyclohexene;
Conjugated diene monomers such as butadiene, isoprene, 1,3-pentadiene, furan, thiophene, 1,3-cyclohexadiene;
Nitrile monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile;
(Meth) acrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate;
Unsaturated fatty acid monomers such as acrylic acid, methacrylic acid and maleic anhydride;
Phenylmaleimide;
Methyl vinyl ether;
And heterocyclic ring-containing vinyl compound monomers such as N-vinylcarbazole and N-vinyl-2-pyrrolidone.

  The monomer mixture used for the polymerization is usually 50% by mass or more, preferably a vinyl aromatic compound and / or a vinyl alicyclic hydrocarbon compound from the viewpoint of heat resistance, low birefringence, mechanical strength, and the like. Is preferably 70 to 100% by mass, more preferably 80 to 100% by mass. The monomer mixture may contain both a vinyl aromatic compound and a vinyl alicyclic hydrocarbon compound.

  The method for polymerizing the vinyl aromatic hydrocarbon compound or the vinyl alicyclic hydrocarbon compound is not particularly limited and can be performed according to a known method. The (co) polymer obtained from the vinyl aromatic hydrocarbon compound is preferably used as a hydrogenated product from the viewpoints of heat resistance, stability and optical properties. A known method can be used as the hydrogenation method.

  The hydrogenated product of the (co) polymer obtained from the vinyl aromatic hydrocarbon compound may have a phenyl group hydrogenation rate of preferably 95% or more, more preferably 99% or more. By the hydrogenation treatment, the phenyl group in the resin structure is hydrogenated to become a cyclohexyl group. The molded body containing this resin has improved light transmittance on the short wavelength side and reduced birefringence and optical anisotropy. At the same time, the unreacted monomer and impurities are subjected to a hydrogenation treatment, so that resistance to heat and light is improved. By treating the hydrogenation rate so as to be in the above range, these effects are particularly excellent.

((Iv) other polymers)
Examples of the other polymer (iv) include a monocyclic cycloalkene polymer, an alicyclic conjugated diene monomer polymer, and an aromatic olefin polymer. Even a structure not included in iii) can be arbitrarily selected within the range of the general formula (2). Examples include (i) to (iii) those obtained by copolymerizing each other or a known copolymerizable monomer.

  In addition, the type of copolymerization is not limited at all in the present invention, and various known copolymerization types such as random copolymer, block copolymer, alternating copolymerization and the like can be applied, but random copolymer is preferable. .

Among the four types of polymers roughly classified in (i) to (iv) above, those that are preferable in terms of optical properties are (i) copolymers of ethylene or α-olefin and cycloolefin, and the most preferable among them. Is ethylene tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene copolymer.

(Other structures that can be used as part of the main chain)
In addition, the polymer having an alicyclic structure used in the present invention is not limited to the good physical properties of the product obtained by the molding method of the present invention. You may have the repeating structural unit induced | guided | derived. The copolymerization ratio is not limited, but is preferably 20 mol% or less, more preferably 0 to 10 mol%. If the copolymerization amount is 20 mol% or less, high-accuracy optical without impairing optical properties. Parts can be obtained. Moreover, the kind of copolymerization is not limited.

(Molecular weight of a polymer having an alicyclic structure in at least a part of the repeating structural unit)
The molecular weight of the polymer having an alicyclic structure used in the present invention is not limited. However, when the intrinsic viscosity [η] is used as an alternative index of the molecular weight, it is preferably measured in decalin at a temperature of 135 ° C. The intrinsic viscosity [η] is 0.03 to 10 dl / g, more preferably 0.05 to 5 dl / g, and most preferably 0.10 to 2 dl / g. When the intrinsic viscosity [η] is in the above range, good moldability can be obtained and the mechanical strength of the molded product is not impaired.

(Glass transition temperature of a polymer having an alicyclic structure in at least a part of the repeating structural unit)
The glass transition temperature (Tg) of the polymer having an alicyclic structure in at least a part of the repeating structural units used in the present invention is preferably 50 to 240 ° C. More preferably, it is 50-160 degreeC. Most preferably, it is 100-150 degreeC. When the glass transition temperature (Tg) is in the above range, sufficient heat resistance can be obtained and good moldability can be obtained when the molded product is used as an optical component.

  The measuring device of the glass transition temperature is not limited. For example, the glass transition temperature of a thermoplastic amorphous resin can be measured using a differential scanning calorimeter (DSC). For example, the method etc. which measure with a temperature increase rate of 10 degree-C / min using SEIKO electronic industry Co., Ltd. DSC-20 are mentioned.

(Example of a method for producing a polymer having an alicyclic structure in at least a part of repeating structural units)
Although the manufacturing method of the polymer which has such an alicyclic structure is not limited, Each can be manufactured as follows.

  (I) Copolymers of ethylene or α-olefins and cyclic olefins include, for example, JP-A-60-168708, JP-A-612012016, JP-A-61-115912, JP-A-6-115912. Appropriate conditions are selected according to methods such as 61-115916, JP-A 61-271308, JP-A 61-272216, JP-A 62-252406, JP 62-252407, etc. Can be manufactured. (Ii) A ring-opening polymer or a hydrogenated product thereof is prepared by a method such as JP-A-60-26024, JP-A-9-268250, JP-A-63-145324, or JP-A-2001-72839. Thus, it can be manufactured by appropriately selecting conditions. (Iii) The vinyl alicyclic hydrocarbon-based polymer is selected by appropriately selecting conditions according to methods such as International Publication No. 01/092412 pamphlet, Japanese Patent Application Laid-Open No. 2003-276047, Japanese Patent Application Laid-Open No. 2004-83813, etc. Can be manufactured.

(Hydrogenation)
Further, in the production process of the polymer having an alicyclic structure, at least once, the polymer or a system containing the polymer and a monomer as a raw material is contacted with a hydrogenation catalyst and hydrogen, and the polymer And / or hydrogenating at least a part of unsaturated bonds of the monomer can improve the optical performance such as heat resistance and transparency of the polymer. The hydrogenation so-called hydrogenation can be performed by a conventionally known method.

(Residual monomer)
It is preferable that the process for producing a polymer having an alicyclic structure or the process for producing a resin composition includes an unreacted monomer reducing process. Examples of the reduction step may include hydrogen addition reaction to double bonds by melt devolatilization, polymer crystallization, phase separation process, and hydrogenation process. By reducing the residual monomer, there are the effects of improving the thermal stability of the resin, improving the light transmittance and diffraction efficiency by reducing the appearance defect during molding, and reducing the gas generated during molding. The residual amount of residual monomer is preferably 5000 ppm or less, more preferably 1000 ppm, and most preferably 500 ppm or less.

(Pentaerythritol derivative composition)
The pentaerythritol derivative composition of the present invention has the general formula (1);

(In the formula, R represents an alkyl group having 11 to 21 carbon atoms, and n represents a real number of 0 to 4.)
It is represented by

The composition of the pentaerythritol derivative composition represented by the general formula (1) is represented by the formulas (a) and (b);
0.2% ≦ [A ₀ ] ≦ 2% (a)
60% ≦ A ₁ + A ₂ ≦ 100% (b)
(In the formula (a), [A ₀ ] is represented by the general formula (1) of the compound having a structure where n = 0 in the general formula (1) quantified by the gas chromatography method. In the formula (a), the total mass of all compounds having a structure where n = 0 to 4 in the general formula (1) is 100 mass%.
In formula (b), A ₁ represents the peak area% in the GPC method of a compound having a structure where n = 1 in general formula (1), and A ₂ represents n = 2 in general formula (1). The peak area% in the GPC method of the compound which has a structure which is is shown. In the formula (b), the sum of the peak areas of the compounds having the structure of n = 1 to 4 in the general formula (1) is defined as 100% peak area. )
Meet. The pentaerythritol derivative composition of the present invention is used as an additive for a polymer having an alicyclic structure in at least a part of repeating structural units, has excellent optical performance, and further suppresses deterioration of optical performance at high temperature and high humidity. A transparent thermoplastic molded product can be obtained.

  The pentaerythritol derivative composition is usually a mixture of compounds having a structure where n = 0, 1, 2, 3, 4 in the general formula (1). The pentaerythritol derivative composition of the present invention may contain other additives.

  In the general formula (1), from the viewpoint of the above effect, R is preferably an alkyl group having 15 to 17 carbon atoms.

(Pentaerythritol in pentaerythritol derivative composition)
The pentaerythritol derivative composition represented by the general formula (1) used in the resin composition of the present invention has a composition represented by the formula (a);
0.2% ≦ [A ₀ ] ≦ 2% (a)
(In the formula (a), [A ₀ ] is a compound (pentaerythritol) having a structure in which n = 0 in the general formula (1) quantified by a gas chromatography method. In the formula (a), the total mass of all compounds having a structure where n = 0 to 4 in the general formula (1) is 100 mass. %)
Meet.

The content of pentaerythritol represented by the formula (a) is the formula (a ′);
0.3% ≦ [A ₀ ] ≦ 1% (a ′)
(However, in the formula (a ′), [A ₀ ] is the same as the formula (a).)
It is preferable to satisfy.

  In order to satisfy the above formula (a) or formula (a ′), pentaerythritol can be appropriately removed from the pentaerythritol derivative composition by a filtration step.

  If the content of pentaerythritol is 0.2% or more, the molded product obtained by molding the resin composition has sufficient heat and heat resistance, and even when used as a high-precision optical component under high temperature and high humidity, the spectral beam Deterioration of optical performance such as change in transmittance and change in aberration is suppressed.

  In addition, when the content of pentaerythritol is 2% or less, clogging of the filter is suppressed even when the resin composition is melt-filtered using a polymer filter attached to an extruder, and productivity is improved. Furthermore, since the phase separation of pentaerythritol can be suppressed in a molded product obtained by molding the obtained resin composition, a molded product having excellent transparency and homogeneity can be obtained.

  In other words, when the content of pentaerythritol satisfies the above formula, changes in optical performance such as changes in spectral light transmittance and aberrations under high temperature and high humidity are suppressed, and productivity of the resin composition and molding obtained Excellent transparency and homogeneity of objects.

(Measurement method of pentaerythritol content)
The content of pentaerythritol is quantified by gas chromatography by preparing a calibration curve using pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.).

Specifically, for example, the following measurement conditions can be exemplified.
Measuring instrument: 6890N (Agilent Technologies)
Column: DB-1HT (manufactured by J & W)
Carrier gas: He (constant flow mode)
Detector: FID

(Monoester and diester in pentaerythritol derivative composition)

  The pentaerythritol derivative composition used in the resin composition of the present invention includes, as essential components, a monoester of pentaerythritol and a fatty acid (hereinafter simply referred to as a monoester) in which n = 1 in the general formula (1) and And / or a diester of pentaerythritol and a fatty acid in which n = 2 in the general formula (1) (hereinafter simply referred to as a diester).

The monoester and diester content is determined by formula (b);
60% ≦ A ₁ + A ₂ ≦ 100% (b)
(In the formula (b), A ₁ represents the peak area% in the GPC method of the compound having a structure where n = 1 in the general formula (1), and A ₂ is n = 2 in the general formula (1). The peak area% in the GPC method of a compound having a certain structure is shown, where, in formula (b), the sum of the peak areas of the compounds having the structure where n = 1 to 4 in formula (1) is the peak area. 100%)
Meet.

The content of the monoester and diester represented by the formula (b) is the formula (b ′);
65% ≦ A ₁ + A ₂ ≦ 100% (b ′)
(However, in the formula, A ₁ and A ₂ are the same as above.)
It is preferable that it exists in the range.

  If the content of monoester and diester is not less than this lower limit, the resulting resin composition has sufficient heat and heat resistance. The content of monoester and diester is preferably 90% or less, and most preferably 80% or less in consideration of filterability during production.

  That is, when the content of monoester and diester satisfies the above formula, the resin composition is excellent in heat-and-moisture resistance, and changes in optical performance such as changes in spectral light transmittance and aberrations of the molded product under high temperature and high humidity. Is suppressed.

  In order to realize this composition ratio, it is possible to adjust the charge ratio and reaction conditions during the esterification reaction of pentaerythritol and a fatty acid having 12 to 22 carbon atoms when producing this pentaerythritol derivative composition.

(Quantification method of monoester and diester)
The amount ratio of monoester and diester in the pentaerythritol derivative composition of the present invention can be calculated from an analysis chart using gel permeation chromatograph (GPC) under the following conditions.

Although the measuring instrument is not limited, for example, it can be measured using the following apparatus and conditions.
HLC-8220 GPC (manufactured by Tosoh Corporation), column: G2000HXL + G1000HXL (manufactured by Tosoh Corporation), solvent: THF, sample concentration: 0.3%. Detector: RI

(Method for producing pentaerythritol derivative composition)
The method for producing a pentaerythritol derivative composition used in the present invention includes the following steps.
Step (a): Pentaerythritol is esterified by reacting a fatty acid having 12 to 22 carbon atoms in an amount of 1.0 to 1.7 mol with respect to 1 mol of pentaerythritol.
Step (b): The esterified product of pentaerythritol obtained in step (a) is filtered.

  First, in step (a), a predetermined amount of pentaerythritol and a predetermined amount of fatty acid having 12 to 22 carbon atoms are subjected to a dehydration reaction at 220 to 240 ° C. under nitrogen blowing to esterify pentaerythritol. Examples of the fatty acid having 12 to 22 carbon atoms include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid and the like. Palmitic acid, from the viewpoint of whitening resistance and compatibility with the resin, Stearic acid is preferred. The esterification reaction is performed at a temperature in the dehydration reaction system of 220 to 240 ° C. under nitrogen blowing. Depressurization during the dehydration reaction is not preferred because fatty acid distills out of the system and the charge ratio changes.

The charged molar ratio of the fatty acid is usually 1.0 to 1.7 mol, preferably 1.3 to 1.7 mol, relative to 1.0 mol of pentaerythritol.
By reacting at the above molar ratio and preferably at 220 to 240 ° C., more preferably at 230 to 240 ° C., the monoester and diester contents can satisfy the above formula (b).

  In step (a), the sodium content in the raw material pentaerythritol is preferably 100 ppm or less, more preferably 90 ppm or less. Since sodium derived from pentaerythritol production raw material affects the coloration during the esterification reaction, it is preferable to use pentaerythritol with the sodium content reduced to the above range.

Next, in step (b), the esterified product of pentaerythritol obtained in step (a) is filtered.
For filtration, the esterified pentaerythritol obtained is preferably adjusted to a temperature of 70 to 90 ° C., more preferably 70 to 80 ° C., and while maintaining the temperature, radiolite (manufactured by Showa Chemical Industry Co., Ltd.) Etc., and preferably under reduced pressure filtration of 60 kPa or less, more preferably 40 kPa or less, or preferably pressure filtration of 100 to 600 kPa, more preferably 200 to 510 kPa. Thereby, the pentaerythritol containing mass% in a pentaerythritol derivative composition can satisfy | fill said Formula (a).

(Processing method for pentaerythritol derivative composition)
As described above, the method for producing a pentaerythritol derivative composition includes an esterification reaction step of pentaerythritol and a fatty acid. Therefore, coloring may occur during the esterification reaction. Further, the ester obtained by the reaction may undergo transesterification in the molten state to cause a composition change, and coloring may occur.

  In that case, a pentaerythritol derivative composition with little coloring can be obtained by suppressing coloring after the reaction during the esterification reaction or by decolorizing the reaction product. Therefore, it is also preferable to perform the following treatment for suppressing coloring.

  Specifically, it is very effective to treat the pentaerythritol derivative composition with hydrogen peroxide. The amount of hydrogen peroxide added is preferably 0.01 parts by mass or more and 0.50 parts by mass or less with respect to 100 parts by mass of the pentaerythritol derivative composition.

  If the addition amount of hydrogen peroxide is 0.01 parts by mass or more, the decolorization effect of the reaction product (pentaerythritol derivative composition) is sufficient. If it is 0.50 parts by mass or less, the transesterification reaction is unlikely to occur in the hydrogen peroxide treatment step, so that the composition change of the pentaerythritol derivative composition is suppressed. It is also economically preferable.

  That is, from the viewpoint of suppressing the decoloring effect of the pentaerythritol derivative composition and the composition change of the pentaerythritol derivative composition, the amount of hydrogen peroxide added is preferably within the above range.

  As the hydrogen peroxide treatment, for example, a pentaerythritol derivative composition is melted at 70 to 85 ° C. while blowing nitrogen, an arbitrary amount of 35% hydrogen peroxide is added, and stirring is continued for 0.5 to 1 hour, and then vacuum is applied. A method of performing dehydration at a degree of 50 to 100 mmHg can be mentioned.

  Moreover, it is also preferable to perform the process including the step of melting the pentaerythritol derivative composition at a temperature of 80 ° C. or less and the step of spray cooling the obtained melt.

  The step of melting the pentaerythritol derivative composition is preferably performed under nitrogen blowing while controlling the melting temperature to 80 ° C. or lower, preferably 70 to 80 ° C. When the melting temperature is 80 ° C. or lower, composition change due to transesterification in the molten state and ester coloring can be suppressed. Further, it is preferable that the melting temperature is 70 ° C. or higher because the ester viscosity is in a range suitable for liquid feeding.

  In the step of spray cooling the melt, the opening of the filter of the spray cooling equipment is usually 75 to 250 microns, preferably 100 to 200 microns. With this size, the pentaerythritol derivative composition can be mass-produced. If it is 75 microns or more, clogging of pentaerythritol hardly occurs, and if it is 250 microns or less, it is preferable because pentaerythritol is not clogged in the melt feed pump and liquid leakage does not occur.

  When a pentaerythritol derivative composition obtained by performing such a method or process for suppressing coloration is added to the polymer of the present invention, a resin composition having better light transmittance can be obtained.

(Resin composition)
In the resin composition of the present invention, the pentaerythritol derivative composition represented by the general formula (1) is added to 1.100 parts by mass of a polymer having an alicyclic structure in at least a part of the repeating structural units. The resin composition is contained in an amount of 0 to 3.0 parts by mass, preferably 1.2 to 2.7 parts by mass.

  When the added amount of the pentaerythritol derivative composition is 1.0 part by mass or more, the molded product obtained by molding the resin composition has sufficient moisture and heat resistance, and used as a high-precision optical component under high temperature and high humidity. However, it does not cause changes in optical performance such as changes in spectral light transmittance and aberrations.

  Further, when the amount of the pentaerythritol derivative composition added is 3.0 parts by mass or less, the solubility of the pentaerythritol derivative composition in the resin composition becomes sufficient, and at the same time, it is possible to reduce mold contamination during injection molding, Since the pentaerythritol derivative composition can suppress phase separation in the molded product, a molded product excellent in transparency and homogeneity can be obtained.

  That is, the resin composition of the present invention having the above-described composition ratio is excellent in the moisture and heat resistance of the resulting molded product, and is excellent in reducing mold stains during injection molding and in the transparency and homogeneity of the molded product.

  The resin composition of the present invention is optimal as a raw material for forming transparent parts, and in particular, it is possible to obtain a transparent thermoplastic molded article excellent in whitening resistance at high temperature and high humidity.

  More specifically, the resin composition of the present invention has low water absorption, birefringence, optical distortion, coloring, white turbidity, haze, heat resistance, refractive index, light transmittance, spectral light transmittance, and high temperature. A transparent thermoplastic molded article having excellent whitening resistance at high humidity can be obtained, and the moldability is also excellent.

(Additives that can be added as optional components to the resin composition)
As the resin composition, in addition to the polymer having an alicyclic structure in at least a part of the repeating structural unit, the pentaerythritol derivative composition represented by the general formula (1), the resin composition of the present invention. As long as it does not impair the good physical properties, known additives can be used as optional components.
Examples of additives that can be added include known antioxidants, secondary antioxidants, lubricants, mold release agents, antifogging agents, weathering stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, and metal deactivators. Is exemplified.

(Antioxidant that can be added as an optional component to the resin composition)
Among these, it is preferable to add an antioxidant so that the good optical properties of the resin composition of the present invention are not impaired during molding. As the antioxidant, a phenol-based stabilizer is preferably used.

The phenol-based stabilizer is a stabilizer having a phenol skeleton in the structure. Usually, the structure contains a characteristic group such as a group consisting of 3,5-dimethyl-4-hydroxyphenyl group, 2,4-dimethyl-3-hydroxyphenyl group, 3-methyl-2-hydroxyphenyl group, or a derivative thereof. .

Specific examples include, for example, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-tert-amyl-6- Acrylate-based phenol compounds described in JP-A Nos. 63-179953 and 1-168643 such as (1- (3,5-di-tert-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate;
2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (6-tert-butyl-m-cresol), 4,4′-thiobis (3 -Methyl-6-tert-butylphenol), bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, 3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy- 5- 3-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis (methylene-3- (3 ′, 5 '-Di-tert-butyl-4'-hydroxyphenylpropionate) methane [ie, pentaerythrimethyl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenylpropionate)), tri Alkyl-substituted phenolic compounds such as ethylene glycol bis (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate) and tocophenol;
6- (4-hydroxy-3,5-di-tert-butylanilino) -2,4-bisoctylthio-1,3,5-triazine, 6- (4-hydroxy-3,5-dimethylanilino)- 2,4-bisoctylthio-1,3,5-triazine, 6- (4-hydroxy-3-methyl-5-tert-butylanilino) -2,4-bisoctylthio-1,3,5-triazine, And triazine group-containing phenolic compounds such as 2-octylthio-4,6-bis- (3,5-di-tert-butyl-4-oxyanilino) -1,3,5-triazine; Among these, tetrakis (methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenylpropionate) methane is preferable because of excellent heat resistance and stability.

  The addition amount of the antioxidant is not particularly limited, but is preferably 0.05 to 1.2 parts by mass with respect to 100 parts by mass of the polymer having an alicyclic structure in at least a part of the repeating structural units. As the most preferred embodiment, the amount added when tetrakis (methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenylpropionate) methane is used is at least a part of the repeating structural unit. The amount is 0.1 to 0.5 parts by mass based on 100 parts by mass of the polymer having an alicyclic structure.

  If it is 0.05 parts by mass or more, the antioxidant effect is sufficient, and when molding the resin composition of the present invention, it is possible to reduce changes in hue and deterioration of optical performance during molding suspension or continuous molding. Moreover, if it is 1.2 parts by mass or less, the solubility of the phenolic stabilizer in the resin composition will be sufficient, and it is possible to reduce mold contamination during injection molding, and at the same time, the phenolic stabilizer is phase-separated in the molded product. Therefore, a molded product having excellent transparency and homogeneity can be obtained.

(Production method of resin composition)
The manufacturing method of the resin composition of this invention is not specifically limited, It can manufacture by a well-known method. Specifically, a polymer having an alicyclic structure and a hindered amine compound, a phosphorus stabilizer and a hydrophilic stabilizer depending on the purpose, and other stabilizers within the range not impairing the object of the present invention. After adding and mixing, flash drying, or mixing each component using a Henschel mixer, ribbon blender, melt blender, homomixer, etc., and then pelletizing using an extruder, pellet resin composition It can be obtained as a product. Furthermore, it can be obtained as a molded product by an injection molding method, an extrusion molding method, a blow molding method, a vacuum molding method, a slush molding method or the like according to the shape of the target molded product.

(Total light transmittance and spectral light transmittance)
When using the resin composition of this invention for an optical use, since it is essential to permeate | transmit light, it is preferable that light transmittance is favorable. The light transmittance is defined by the spectral light transmittance or the total light transmittance depending on the application.

  When it is assumed that all light rays are used or in a plurality of wavelength regions, the total light transmittance is required to be good, and the total light transmittance in a state where the antireflection film is not provided on the surface is 85% or more, preferably Is 88-93%. If the total light transmittance is 85% or more, a necessary amount of light can be secured. As a method for measuring the total light transmittance, a known method can be applied, and a measuring device is not limited. For example, in accordance with ASTM D1003, a thermoplastic and amorphous resin is formed into a sheet having a thickness of 3 mm, and a haze meter is used. And a method for measuring the total light transmittance of a sheet obtained by molding the resin composition of the present invention.

  Further, in the case of an optical system utilized only in a specific wavelength range, for example, a laser optical system, even if the total light transmittance is not high, it can be used if the spectral light transmittance in the wavelength range is good. In this case, the spectral light transmittance in a state where the antireflection film is not provided on the surface at the used wavelength is preferably 85% or more, more preferably 86 to 93%. If the spectral light transmittance is 85% or more, a necessary amount of light can be secured. Moreover, a well-known method can be applied as a measuring method and apparatus, and specifically, a spectrophotometer can be exemplified.

Hereinafter, the present invention will be described more specifically based on examples. First, a synthesis example of the pentaerythritol derivative composition used in the examples is shown.
(Measurement method of pentaerythritol amount)
Measuring method Measuring instrument: 6890N (Agilent Technologies)
Column: DB-1HT (manufactured by J & W)
(30m × 250μm × 0.1μm)
Carrier gas: He (constant flow mode)
Split ratio: 50: 1
Detector: FID
Inlet temperature: 330 ° C
Detector temperature: 330 ° C
Measurement temperature conditions: 100 ° C. → Temperature rise at 10 ° C./min→Hold at 380 ° C. for 27 minutes Detection sensitivity: Uptake speed, 20 Hz
Minimum peak width, 0.01 min
Injection volume: 1 μl (split method)

Preparation of calibration curve sample (1) About 0.5 mg, 1.0 mg, and 2.0 mg of pentaerythritol (Wako Pure Chemicals: Reagent) are weighed accurately in a 10 cc screw tube. (Amount collected: Record up to the last digit)
(2) After step (1), 1 cc of the TMS agent is placed in the screw tube and the lid is closed. (TMS agent: TMSI-H: manufactured by GL Sciences: Reagents)
(3) After the step (2), the screw tube is lightly shaken in a 80 ° C. warm bath to allow the reaction to proceed. (About 10 minutes)
(4) After step (3), 5 cc of ion exchange water is put into the screw tube to eliminate the activity of TMS.
(5) After step (4), add 1.00 cc of hexane into the screw tube, shake well, and then leave the screw tube to stand. (Hall pipette used)
(6) After step (5), water / hexane is separated in the screw tube, so the hexane layer is collected and used as a gas chromatograph sample.
(7) Measure the sample obtained in step (6) under the above conditions and create a calibration curve

Preparation of measurement sample (a) About 20 mg of a 10 cc screw tube is weighed out of the pentaerythritol derivative composition. (Amount collected: Record up to the last digit)
(B) After step (a), 1 cc of the TMS agent is placed in the screw tube, and the lid is closed. (TMS agent: TMSI-H: manufactured by GL Sciences: Reagents :)
(C) After step (b), lightly shake the screw tube in a warm bath at 80 ° C. to allow the reaction to proceed. (About 10 minutes)
(D) After the step (c), 5 cc of ion-exchanged water is put into the screw tube to eliminate the activity of TMS.
(E) After step (d), 1.00 cc of hexane is placed in the screw tube, shaken well, and then allowed to stand. (Hall pipette used)
(F) Since water / hexane is separated after step (e), the hexane layer is collected and used as a gas chromatograph sample.
(G) Measurement is performed using the sample obtained in step (f), and the amount of pentaerythritol in the pentaerythritol derivative composition is determined from the calibration curve.

(Quantification method of monoester and diester)
The GPC method was performed under the following conditions.
Measuring instrument: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: G2000HXL + G1000HXL
Solvent: THF
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Sample concentration: 0.3%
Injection volume: 100 μL
Detection sensitivity: 0.100 mV / min Detector: RI
Standard material: polystyrene (Made by Tosoh Corporation, Mw = 526, 2630, 10200)
GPC measurement was performed under the above conditions, and the distribution of the degree of esterification was determined by the area ratio of the chart.

(Synthesis Example 1)
In a 500 ml glass four-necked flask, 122.4 g (0.9 mol) of pentaerythritol (manufactured by Guangei Chemical Co., Ltd.) and 248.4 g of stearic acid (Lunac S-40 manufactured by Kao Corp.) 9 mol) was weighed, and the dehydration esterification reaction was carried out at 235 ° C. until the acid value was 2.0 or less while blowing nitrogen. Thereafter, the inside of the reaction system is cooled to 70 to 80 ° C., and the pressure is filtered under reduced pressure (30.1 kPa) using a filter aid (Radiolite # 700) while maintaining the temperature. Composition of the pentaerythritol derivative of Synthesis Example 1 I got a thing.
Table 1 shows the ester composition and the amount of pentaerythritol of the pentaerythritol derivative composition.

(Synthesis Examples 2-1 and 2-2)
In a 500 ml glass four-necked flask, 81.6 g (0.6 mol) of pentaerythritol (manufactured by Guangei Chemical Co., Ltd.) and 215.3 g of stearic acid (Lunac S-40 manufactured by Kao Corporation) 78 mol) was weighed and subjected to esterification under the same reaction conditions as in Synthesis Example 1 to obtain the pentaerythritol derivative composition of Synthesis Example 2-1. Thereafter, filtration under reduced pressure was performed in the same manner as in Synthesis Example 1 to obtain the pentaerythritol derivative composition of Synthesis Example 2-2.
Table 1 shows the ester composition and the amount of pentaerythritol of these pentaerythritol derivative compositions.

(Synthesis Examples 3-1 and 3-2)
In a 500 ml glass four-necked flask, 81.6 g (0.6 mol) of pentaerythritol (manufactured by Koei Chemical Co., Ltd.) and 248.4 g of stearic acid (Lunac S-40 manufactured by Kao Corporation) (0. 9 mol) was weighed and subjected to esterification under the same reaction conditions as in Synthesis Example 1 to obtain a pentaerythritol derivative composition of Synthesis Example 3-1. Thereafter, filtration under reduced pressure was performed in the same manner as in Synthesis Example 1 to obtain the pentaerythritol derivative composition of Synthesis Example 3-2.
Table 1 shows the ester composition and the amount of pentaerythritol of the pentaerythritol derivative composition.

(Synthesis Example 4)
In a 500 ml glass four-necked flask, 68.0 g (0.5 mol) of pentaerythritol (manufactured by Guangei Chemical Co., Ltd.) and 234.6 g of stearic acid (Lunac S-40 manufactured by Kao Corp.) 85 mol) was weighed and subjected to an esterification reaction under the same reaction conditions as in Synthesis Example 1. Thereafter, filtration under reduced pressure was performed in the same manner as in Synthesis Example 1 to obtain a pentaerythritol derivative composition of Synthesis Example 4.
Table 1 shows the ester composition and the amount of pentaerythritol of the pentaerythritol derivative composition.

(Synthesis Example 5)
In a 500 ml glass four-necked flask, 68.0 g (0.5 mol) of pentaerythritol (manufactured by Guangei Chemical Co., Ltd.) and 276.0 g of stearic acid (Lunac S-40 manufactured by Kao Corporation) (1. 0 mol) was weighed and the esterification reaction was carried out under the same reaction conditions as in Synthesis Example 1. Thereafter, filtration under reduced pressure was performed in the same manner as in Synthesis Example 1 to obtain a pentaerythritol derivative composition of Synthesis Example 5.
Table 1 shows the ester composition and the amount of pentaerythritol of the pentaerythritol derivative composition.

(Synthesis Example 6)
In a 500 ml glass four-necked flask, 68.0 g (0.5 mol) of pentaerythritol (manufactured by Guangei Chemical Co., Ltd.) and 234.6 g of stearic acid (Lunac S-40 manufactured by Kao Corp.) 85 mol) was weighed and subjected to an esterification reaction under the same reaction conditions as in Synthesis Example 1. Then, it was left to stand at 60 ° C. for one day and under reduced pressure filtration in the same manner as in Synthesis Example 1 to obtain a pentaerythritol derivative composition of Synthesis Example 6.
Table 1 shows the ester composition and the amount of pentaerythritol of the pentaerythritol derivative composition.

(Synthesis Example 7)
In a 500 ml glass four-necked flask, 81.6 g (0.6 mol) of pentaerythritol (manufactured by Koei Chemical Co., Ltd.) and 248.4 g of stearic acid (Lunac S-40 manufactured by Kao Corporation) (0. 9 mol) was weighed and the esterification reaction was carried out under the same reaction conditions as in Synthesis Example 1. Thereafter, filtration under reduced pressure was performed in the same manner as in Synthesis Example 1 to obtain a pentaerythritol derivative composition of Synthesis Example 7. The resulting pentaerythritol derivative composition had a monoester area% of 26%, a diester area% of 42%, and a pentaerythritol mass% of 0.4%. The b value measured by the following method was 3.8.

  Thereafter, the pentaerythritol derivative composition was treated with hydrogen peroxide by the following method to determine the composition and b value. The monoester area% of the pentaerythritol derivative composition was 26%, the area% of the diester was 42%, The mass% of pentaerythritol was 0.4%, and the b value was 2.5. Table 1 shows the ester composition and the amount of pentaerythritol of the pentaerythritol derivative composition.

b Value Measurement Method After dissolving 70 parts by mass of pentaerythritol derivative composition, 27 parts by mass of isopropanol, and 3 parts by mass of ion-exchanged water uniformly in a hot water bath at 50 to 60 ° C., immediately, Spectro Color Meter manufactured by Tokyo Denshoku Industries Co., Ltd. Used and measured by transmission method.

Hydrogen peroxide treatment method The pentaerythritol derivative composition is melted at 70 to 85 ° C. under nitrogen blowing, and then 35% excess is added so that hydrogen peroxide is 0.1 part by mass with respect to 100 parts by mass of the pentaerythritol derivative composition. Hydrogen oxide water was added and stirring was continued for 1 hour, followed by dehydration at a vacuum degree of 5 to 10 mmHg to obtain a pentaerythritol derivative composition.

(Synthesis Example 8-1)
In a 500 ml glass four-necked flask, 81.6 g (0.6 mol) of pentaerythritol having a sodium content of 75 ppm (industrial product manufactured by Guangei Chemical Co., Ltd.) and stearic acid (Lunac S-40 manufactured by Kao Corp.) 248 .4 g (0.9 mol) was weighed and subjected to an esterification reaction under the same reaction conditions as in Synthesis Example 1. Thereafter, filtration under reduced pressure was performed in the same manner as in Synthesis Example 1 to obtain the pentaerythritol derivative composition of Synthesis Example 8-1. Table 1 shows the ester composition and the amount of pentaerythritol of the pentaerythritol derivative composition. The b value was 3.8.

(Synthesis Example 8-2)
Synthesis Example 8-2 was performed in the same manner as in Synthesis Example 8-1, except that pentaerythritol having a sodium content of 200 ppm was used. Table 1 shows the ester composition and the amount of pentaerythritol of the resulting pentaerythritol derivative composition. The b value was 5.5.

(Synthesis Example 9)
After obtaining the pentaerythritol derivative composition of Synthesis Example 8-1, while maintaining the reaction system at 72 to 78 ° C., the supply pressure to the spray cooler is 19 kg / cm ² and the nozzle inlet pressure is 25 kg / cm ² , pentaerythritol. The derivative composition was supplied and spray cooling was performed at a cold air temperature of 11 to 13 ° C. Table 1 shows the ester composition and the amount of pentaerythritol of the resulting pentaerythritol derivative composition. The b value was 3.8.

(Example of resin production)
<Production Example 1: Resin A (ethylene-cycloolefin copolymer)>
A cyclic olefin random copolymer flash-dried was obtained in the same manner as described in the examples of JP-A-3-220211. That is, a cyclic olefin random copolymer was obtained by the following method.

VO (OC ₂ H ₅ ) Cl ₂ was diluted with cyclohexane to prepare a vanadium catalyst having a vanadium concentration of 6.7 mmol / L-cyclohexane. Ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 Cl _1.5 ) was diluted with cyclohexane to prepare an organoaluminum compound catalyst having an aluminum concentration of 107 mmol / L-hexane.

Cyclic olefin-based random copolymer was continuously converted into ethylene and tetracyclo [4,4,0,1 ^2,5 , 1 ⁷ as a cyclic olefin using a stirring type polymerizer (inner diameter: 500 mm, reaction volume: 100 L). ^{, 10} ] -3-dodecene (hereinafter sometimes simply referred to as “tetracyclododecene”). In carrying out this copolymerization reaction, the vanadium catalyst prepared by the above method is polymerized in an amount such that the vanadium catalyst concentration relative to cyclohexane in the polymerization vessel used as the polymerization solvent is 0.6 mmol / L. Supplied in. In addition, the vanadium catalyst is diluted with cyclohexane in advance so that the vanadium catalyst concentration immediately before being supplied to the polymerization vessel is less than twice the concentration of the catalyst in the polymerization vessel, and then supplied to the polymerization vessel. did.

Ethylaluminum sesquichloride, which is an organoaluminum compound, was fed into the polymerization vessel in such an amount that Al / V = 8.0. The above-mentioned copolymerization reaction was continuously carried out at a polymerization temperature of 11 ° C. and a polymerization pressure of 0.18 MPa (1.8 kg / cm ² G).

The cyclic olefin-based random copolymer solution extracted from the polymerization vessel is fed into a pipe, premixed, and a NaOH solution having a concentration of 25% by weight as boiler water and a pH regulator is added to the mixed solution. The polymerization reaction was stopped, and the catalyst residue remaining in the copolymer was removed (decalcified) from the mixed solution. As a stabilizer, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] is added to the polymer as a stabilizer in this decalcified mixed solution so that the amount of the polymer added is 100 parts by mass. It was added as a 0.3 weight parts against once before entering the flash drying step, and mixed for 1 hour using a stirring tank having an effective volume of 1.0 m ^3.

A double tube heater (outer tube diameter 2B, inner tube diameter 3 / 4B, length 21 m) using 2.0 MPa (20 kg / cm ² G) water vapor as a heating source is added to the mixed weight in the mixed solution. A mixed solution having a coalescence concentration of 5% by weight was supplied in an amount of 150 kg / H, and the mixed solution was heated to 180 ° C.

Using a double tube flash dryer (outer tube diameter 2B, inner tube diameter 3 / 4B, length 27m) and flash hopper (volume 200L) together with the polymerization solvent from the mixed solution that has undergone the heating process as described above Most of the unreacted tetracyclododecene was removed. As a heating source of the double tube flash dryer, 2.5 MPa (25 kg / cm ² G) of water vapor was used. Thus, Resin A was obtained. Resin A had an intrinsic viscosity of 0.50 dl / g and TMA of 143 ° C. The measurement conditions are as follows.

Intrinsic viscosity [η]: The intrinsic viscosity was measured at 135 ° C. using an Atlantic viscometer.
Softening point [TMA]: Measured by thermal deformation behavior of 1.0 mm thick sheet using Thermomechanical Analyzer manufactured by DuPont. That is, a quartz needle was placed on the sheet, a load of 50 g was applied, the temperature was raised at 5 ° C./min, and the temperature at which the needle entered 0.1 mm was defined as TMA.

Weight average molecular weight (Mw), molecular weight distribution (MWD)
Using GPC Alliance 2000 (Waters)
Column: TSKgel GMH6-HT × 2 + TSKgel GMH6-HTL × 2 (total 30 cm × 4, Tosoh Corporation)
Detector: Differential refractometer Measurement solvent: o-dichlorobenzene Measurement flow rate: 1 mL / mi
nMeasurement temperature: 140 ° C
Sample injection volume: 500 μL
Standard sample: monodisperse polystyrene x 16 (manufactured by Tosoh Corporation)
Was analyzed.

Glass transition temperature (Tg)
Using DSC-20 manufactured by SEIKO Electronics Co., Ltd. in nitrogen at 10 ° C./min. After raising the temperature to 250 ° C. under the temperature raising conditions, the sample was once quenched and then measured at a temperature raising rate of 10 ° C./min.
Melt flow index (MFR)
Measured at 260 ° C and a load of 2.16 kg according to ASTM D1238.

<Production Example 2: Resin B (hydrogenated ethylene-cycloolefin copolymer)>
Resin A obtained in Production Example 1 was dissolved in cyclohexane to prepare a concentration of 15% by weight. To 300 g of the solution, 1.3 g of Raney nickel catalyst (nickel content 40 wt%) was added and reacted at a hydrogen partial pressure of 3 MPa and a temperature of 100 ° C. for 4 hours. After filtering the catalyst, the reaction solution was added to acetone to precipitate a polymer, and a resin B was obtained by filtration and drying. Resin B had a hydrogenation rate of almost 100%, an intrinsic viscosity of 0.5 dl / g, and TMA of 143 ° C.

<Production Example 3: Resin C (cyclic olefin ring-opening polymer hydrogenated product)>
Into a reactor having a heat exchange facility using 200 liters of an aqueous medium substituted with nitrogen, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene (hereinafter abbreviated as ETCD) 1,000 parts by mass and cyclohexane 24,000 parts by mass, tri-i-butylaluminum [iBu ₃ Al] 68 parts by mass as a polymerization catalyst Then, 26 parts by mass of isobutyl alcohol and 14 parts by mass of acetone as a reaction preparation agent and 188 parts by mass of 1-hexene diluted with 2,000 parts by mass of cyclohexane as a molecular weight modifier were added. The error of 1-hexene addition was 1%. After the temperature of the reaction solution at this stage was 40 ° C., the temperature of the aqueous medium was set to 25 ° C., and a mixed solution of 18 parts by mass of tungsten hexachloride and 15,200 parts by mass of cyclohexane was added. The increase in reaction heat from the start of the reaction was confirmed to be 4.3 ° C., and the mixture was stirred at that temperature for 5 minutes. Next, while controlling the temperature of the aqueous medium and maintaining the reaction system at 45 ° C., a mixed solution of 19,000 parts by mass of ETCD, 26 parts by mass of tungsten hexachloride, and 22,000 parts by mass of cyclohexane was put into the system. It was dripped continuously over 2 hours. After completion of the dropwise addition, the ring-opening polymerization was terminated by stirring for 30 minutes at 45 ° C. In the obtained ring-opening polymer, a component having a weight average molecular weight (Mw) of 14,100, a molecular weight distribution (MWD) of 2.15, and a molecular weight of 300,000 or more was not detected. Moreover, since the peak of the unreacted monomer was not detected by gas chromatography analysis of the reaction solution, it was confirmed that the reaction rate was 100%.

This polymerization reaction liquid was transferred to an autoclave, and 34,000 parts by mass of cyclohexane was added. To this was added 500 parts by mass of a diatomaceous earth-supported nickel catalyst as a hydrogenation catalyst, the inside of the reactor was replaced with hydrogen, the pressure was increased at about 10 kg / cm ² , and the temperature was increased to 160 ° C. with stirring. When the temperature was stabilized, the hydrogen pressure was maintained at 40 kg / cm ² , and the reaction was carried out for 8 hours while replenishing hydrogen consumed in the reaction process. After completion of the hydrogenation reaction, the hydrogenation catalyst was filtered off, and an antioxidant, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl), was added to the hydrogenated polymer solution. ) Propionate] was added in an amount of 0.2 parts by mass to 100 parts by mass of the hydrogenated polymer, and then the solvent was removed at 280 ° C. under reduced pressure drying. Next, the molten resin was pelletized by an extruder under a nitrogen atmosphere to obtain Resin C. Resin C has an Mw of 32,000, a hydrogenation rate of 99% or more, and a melt flow rate (MFR) at 280 ° C. of 50 g / 10 min. , Tg was 140 ° C.

<Production Example 4: Resin D (hydrogenated product of styrene-isoprene polymer)>
76.8 parts by mass of styrene and 3.2 parts by mass of isoprene were added to a stainless steel pressure-resistant container purged with nitrogen, and mixed and stirred to prepare a mixed monomer. Next, 320 mass parts of dehydrated cyclohexane, 4 mass parts of mixed monomer and 0.1 mass part of dibutyl ether were charged into a stainless steel autoclave equipped with a nitrogen-substituted electromagnetic stirring apparatus, and n-butyllithium was stirred while stirring at 50 ° C. Polymerization was started by adding 0.454 parts by mass of a hexane solution (concentration 15%), and polymerization was performed. After 0.5 hours had elapsed from the start of the polymerization (the polymerization conversion rate at this point was about 96%), 76 parts by mass of the mixed monomer was continuously added over 1 hour. After 0.5 hours from the end of the addition of the mixed monomer (the polymerization conversion rate at this point was about 95%), 0.1 part by mass of isopropyl alcohol was added to stop the reaction, and styrene-isoprene random copolymer was added. A polymerization reaction solution in which the polymer was dissolved was obtained.

  Next, 3 parts by mass of a stabilized nickel hydrogenation catalyst E22U (manufactured by JGC Chemical Co., Ltd .; 60% nickel-supported silica-alumina carrier) is added to and mixed with 400 parts by mass of the above polymerization reaction solution to obtain a mixed solution, which is heated by heating. A stainless steel autoclave equipped with an apparatus and an electromagnetic stirrer was charged. Hydrogen gas was supplied to the autoclave and a hydrogenation reaction was performed for 6 hours while maintaining the temperature inside the autoclave at 160 ° C. and 4.5 MPa while stirring. After completion of the hydrogenation reaction, the solution was filtered under pressure at a pressure of 0.25 MPa using a pressure filter equipped with Radiolite # 800 as a filter bed (Hunda filter, manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd.). Obtained.

  To the obtained colorless and transparent solution, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10 with respect to 100 parts by mass of the polymer solid content. -Tetrakis-t-butyldibenzo [d, f] [1.3.2] dioxaphosphin (light transmittance at 400 nm by a quartz cell having a light path length of 10 mm in a 5% by weight solution of chloroform is 99.8%) 1 part by mass and main chain hydride of styrene-isoprene-styrene block copolymer (SEPS, styrene / isoprene weight ratio = 30/70, melt flow rate of about 70 g / min (230 ° C., 2.16 kgf)) 0.2 A part by mass was added and dissolved.

  This solution was filtered through a metal fiber filter (pore size: 0.5 μm, manufactured by Nichidai). The filtrate was then filtered through a zeta plus filter 3OS (pore size 0.5-1 μm, manufactured by Cuno), and further filtered through a metal fiber filter (pore size 0.2 μm, manufactured by Nichidai) to remove foreign matters. The obtained filtrate (polymer concentration = 20%) was heated to 250 ° C. and continuously supplied to a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.) at a pressure of 3 MPa. The pressure in the concentration drier was adjusted to 60 kPa, and the temperature of the polymer solution in the drier was adjusted to 260 ° C. for concentration. Next, the concentrated solution was further supplied to the same type of concentration dryer at a pressure of 1.5 MPa while maintaining the temperature at 260 ° C. The pressure in the second stage concentration dryer was adjusted to 1.5 kPa, and the temperature of the polymer was adjusted to 270 ° C. to remove the solvent. The polymer from which the solvent was removed was extruded to obtain resin D pellets. Resin D had an Mw of 83,000, an Mw / Mn of 1.2, a hydrogenation rate of approximately 100%, and a Tg of 125 ° C.

(Evaluation methods in Examples and Comparative Examples)
Measurement methods in Examples and Comparative Examples are as follows.
In the measurement, it has an optical surface of 45 mmφ × 3 mm (thickness) injection-molded by an injection molding machine (IS-50EP manufactured by Toshiba Machine Co., Ltd.) set at a cylinder temperature of 260 ° C. and a mold temperature of 125 ° C. A test piece was used.

Optical quality: The ZYGO interferometer PTI250 type was used, and the RMS value of the transmitted wavefront at the center 10 mmφ of the test piece was recorded. An RMS value of 0.05λ or less was accepted.
◇ Haze: Measured based on ASTM D1003. The haze was determined to be 1.0% or less.

◇ Environmental test: After the above measurement, the test piece was left in an atmosphere of a temperature of 80 ° C. and a relative humidity of 90% for 48 hours. The optical quality and haze were measured again.
(Evaluation of optical quality (RMS value) after environmental test)
A case where the RMS value was 0.05λ or less was determined to be acceptable.
(Evaluation of haze after environmental test)
The case where the haze was 1.0% or less was determined to be acceptable.
◇ 370 nm, 450 nm spectral light transmittance: Using a UV-2450 type ultraviolet / visible spectrophotometer manufactured by Shimadzu Corporation, 370 nm, 450 nm spectral light transmittance before and after the environmental test was measured.

(Examples and comparative examples)
Resins A to D obtained in Production Examples and Synthesis Examples or commercially available additives were directly charged into an extruder in a molten state to obtain a resin composition. The seeds / mixing mass ratios of the used resin and synthesis examples or commercially available additives are as shown in Table-2 and Table-3. In addition, the mixing mass ratio in a table | surface was shown with the addition amount (mass part) of the additive with respect to 100 mass parts of resin.

Specifically, the same direction of rotation, screw diameter 120 mmφ, vent holes at positions L / D = 10 and L / D = 20 from the resin charging portion, and additive charging holes at the position L / D = 24 A synthesis example in which a cyclic olefin random copolymer obtained in the production example was charged from a resin charging portion and heated and melted at 80 ° C. using a certain twin screw extruder of L / D = 45.5 or commercially available The additive was charged from the additive charging hole, and a resin composition was obtained with a screw rotation speed of 250 rpm, a motor power of 50 to 60 kw, and a vent pressure set to 3 Torr.
The evaluation result of the obtained resin composition is shown according to Table-2 and Table-3.

Claims (6)

The following general formula:

(Wherein, x, y represent a copolymerization ratio and 0/100 is a real number satisfying ≦ y / x ≦ 95/5 .) Represented by ethylene and tetracyclo [4.4.0.1 ^{2, 5} . Copolymer with 1 ^7,10 ] -3-dodecene or a hydrogenated product thereof, or 8-ethyltetracyclo [4.4.0.1 ^2,5 . To dodeca-3-Ru hydrogenated product der en ring-opening polymer polymer 100 parts by weight, - 1 ^7,10]
Pentaerythritol, fatty acid monoester of pentaerythritol, fatty acid diester of pentaerythritol, fatty acid triester of pentaerythritol, and pentaerythritol derivative composition containing fatty acid tetraester of pentaerythritol are 1.0 part by weight or more and 3.0 parts by weight or less. Including
The fatty acid constituting the fatty acid monoester, the fatty acid diester, the fatty acid triester, and the fatty acid tetraester is stearic acid or palmitic acid,
The pentaerythritol derivative composition has the formulas (a) and (b);
0.2% ≦ [A ₀ ] ≦ 2% (a)
60% ≦ A ₁ + A ₂ ≦ 80% (b)
(Wherein (a), [A _0] is quantified in gas chromatography, of the pentaerythritol shows content by mass% in the pentaerythritol derivative composition. In Expression (a) The total mass of the pentaerythritol, the fatty acid monoester, the fatty acid diester, the fatty acid triester, and the fatty acid tetraester is 100% by mass.
In the formula (b), _{A 1} is in a gel permeation chromatograph (GPC) method of the fatty acid monoester, a peak area% measured under the following conditions, _{A 2} is in the GPC method of said fatty acid diester The peak area% measured under the following conditions is shown. In the formula (b), the total area of the respective peaks of the pentaerythritol, the fatty acid monoester, the fatty acid diester, the fatty acid triester, and the fatty acid tetraester is 100% peak area. )
The resin composition characterized by satisfy | filling.
Measuring instrument: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: G2000HXL + G1000HXL
Solvent: THF
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Sample concentration: 0.3%
Injection volume: 100 μL
Detection sensitivity: 0.100 mV / min
Detector: RI
Standard material: polystyrene (Made by Tosoh Corporation, Mw = 526, 2630, 10200) The said formula (a) is represented as follows, The resin composition of Claim 1 characterized by the above-mentioned;
0.2% ≦ [A ₀ ] ≦ 1% (a)
(In formula (a), [A ₀ ] is as defined above.) Pentaerythritol, fatty acid monoester of pentaerythritol, fatty acid diester of pentaerythritol, fatty acid triester of pentaerythritol, and fatty acid tetraester of pentaerythritol, and the fatty acid constituting these esters is stearic acid or palmitic acid, A pentaerythritol derivative composition comprising:
The composition of the derivative composition satisfies the formulas (a) and (b), and ethylene and tetracyclo [4.4.0.1 ^2,5 . Copolymer with 1 ^7,10 ] -3-dodecene or a hydrogenated product thereof, or 8-ethyltetracyclo [4.4.0.1 ^2,5 . A pentaerythritol derivative composition, which is used as an additive for a polymer selected from hydrogenated ring-opening polymers of ^{17, 10} ] -dodec-3-ene .
0.2% ≦ [A ₀ ] ≦ 2% (a)
60% ≦ A ₁ + A ₂ ≦ 80% (b)
(Wherein (a), [A _0] is quantified in gas chromatography, of the pentaerythritol shows content by mass% in the pentaerythritol derivative composition. In Expression (a) The total mass of the pentaerythritol, the fatty acid monoester, the fatty acid diester, the fatty acid triester, and the fatty acid tetraester is 100% by mass.
In the formula (b), _{A 1} is in a gel permeation chromatograph (GPC) method of the fatty acid monoester, a peak area% measured under the following conditions, _{A 2} is in the GPC method of said fatty acid diester The peak area% measured under the following conditions is shown. In the formula (b), the total area of the respective peaks of the pentaerythritol, the fatty acid monoester, the fatty acid diester, the fatty acid triester, and the fatty acid tetraester is 100% peak area. )
Measuring instrument: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: G2000HXL + G1000HXL
Solvent: THF
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Sample concentration: 0.3%
Injection volume: 100 μL
Detection sensitivity: 0.100 mV / min
Detector: RI
Standard material: polystyrene (Made by Tosoh Corporation, Mw = 526, 2630, 10200) The said formula (a) is represented as follows, The pentaerythritol derivative composition of Claim 3 characterized by the above-mentioned;
0.2% ≦ [A ₀ ] ≦ 1% (a)
(In formula (a), [A ₀ ] is as defined above.) A step of esterifying pentaerythritol by reacting stearic acid or palmitic acid in an amount of 1.0 mol to 1.7 mol with respect to 1 mol of pentaerythritol;
Method for producing a pentaerythritol derivative composition according to claim 3 or 4, characterized in that it comprises a step of filtering the resulting esterified product in the process. In the step of esterifying pentaerythritol,
The method for producing a pentaerythritol derivative composition according to claim 5 , wherein pentaerythritol having a sodium content of 100 ppm or less is used.