JP6517066B2 - Resin composition and use thereof - Google Patents

Description

  The present invention relates to a resin composition containing a polymer containing an alicyclic structure in at least a part of a repeating structural unit and its use.

  Polyolefin resins are widely used as molding materials in various fields, but have problems such as charging of the surface of the resulting molded body. The followings have been proposed to solve such problems.

  Patent Document 1 discloses using, as a polyolefin resin, an antistatic agent composed of a C11 to C28 polyhydric alcohol ester, a predetermined nitrogen-containing compound, and a predetermined aliphatic alcohol. As this polyhydric alcohol ester, diglycerin monooleate etc. are illustrated.

Patent Document 2 discloses a thermoplastic resin composition containing a predetermined amount of polyglycerin fatty acid ester. As this polyglycerin fatty acid ester, diglycerin monooleate etc. are illustrated. And in the Example, the result in which the devitrification resistance under high temperature and humidity was improved is described.
On the other hand, the following documents can be mentioned as what used cyclic polyolefin resin.

  Patent Document 3 includes a thermoplastic norbornene resin, a compound (a) having a structure in which an OH group of an alcohol is ester-bonded to an OH group-containing saturated fatty acid, and a saturated alcohol having 16 or more carbon atoms (b). Disclosed is a resin composition containing the same. As this compound (a), 12-hydroxystearic acid triglyceride is described.

Japanese Patent Application Laid-Open No. 61-28537 Japanese Patent Application Laid-Open No. 61-157558 JP-A-9-241484

In recent years, development of in-vehicle safety equipment such as an out-of-vehicle monitor has progressed, and the demand for in-vehicle camera lens components is increasing. Automotive parts are required to have high heat resistance. Cyclic polyolefin resins are widely used for optical components such as lenses because of their excellent optical properties and mechanical properties. However, at present, it has not been possible to obtain a cyclic polyolefin resin composition having high heat resistance required for in-vehicle lenses and moisture and heat resistance.
Patent Documents 1 and 2 do not describe a cyclic polyolefin resin containing an alicyclic structure, and it is further confirmed that when diglycerin monooleate or the like is used, properties required for optical applications can be obtained. Not.

An object of the present invention is to provide a resin composition which can obtain a molded article which is excellent in optical performance and in which deterioration of optical performance under high temperature and high humidity conditions is suppressed, and its use.
An object of the present invention is to provide an optical component such as an on-vehicle camera lens component made of a resin composition which is further excellent in optical performance, heat resistance and moisture and heat resistance.

（上記式（７）中、Ｒ ^ａ は、下記一般式（３）

（上記式（３）中、ｐは、０〜２の整数である。）で表される２価の基である。
Ｒ ^ｂ は、水素原子、または炭素原子数１〜１０の炭化水素基よりなる群から選ばれる１価の基である。Ｒ ^ａ およびＲ ^ｂ は、それぞれ１種であってもよく、２種以上を任意の割合で有していてもよい。
ｘ，ｙは共重合比を示し、５／９５≦ｙ／ｘ≦９５／５を満たす実数である。ｘ，ｙはモル基準である。）
で表される一種以上の構造を有する環状オレフィン系重合体であるポリマーと、
ジグリセリンと炭素数１２〜１８の飽和または不飽和脂肪酸との脂肪酸エステルと、
を、前記ポリマー１００重量％に対して、前記脂肪酸エステルを０．３〜１．０重量％の量で含む、樹脂組成物（ただし、帯電防止剤として、グリセリン脂肪酸エステルと、ポリグリセリン脂肪酸エステルと、高級アルコールのエチレンオキサイド付加体、芳香族ヒドロキシ化合物のエチレンオキサイド付加体、ヒドロキシル基を有する多価アルコール脂肪酸エステルのエチレンオキサイド付加体、またはヒドロキシル基を有する油脂のエチレンオキサイド付加体とを含む場合、
帯電防止剤として、グリセリン脂肪酸エステルと、ポリグリセリン脂肪酸エステルと、窒素原子にアルキル基が結合していてもよいジエタノールアミン脂肪酸エステルとを含む場合、
帯電防止剤として、グリセリン脂肪酸エステルと、ポリグリセリン脂肪酸エステルと、高級アルコールのエチレンオキサイド付加体、芳香族ヒドロキシ化合物のエチレンオキサイド付加体、ヒドロキシル基を有する多価アルコール脂肪酸エステルのエチレンオキサイド付加体、またはヒドロキシル基を有する油脂のエチレンオキサイド付加体と、窒素原子にアルキル基が結合していてもよいジエタノールアミン脂肪酸エステルとを含む場合、および
下記一般式（１）で表される化合物を含む場合を除く。

〔上記式（１）中、Ｑ^１は炭素数８〜２２の直鎖状または分岐状のアルキル基であって、Ｑ^２は芳香環を有する炭素数６〜１０の有機基であって、Ｍ^＋はナトリウムカチオン、カリウムカチオン、アンモニウム、ホスホニウムであって、ａは０または１である。〕）。
［２］ 前記脂肪酸エステルが、ジグリセリン不飽和脂肪酸エステルである［１］に記載の樹脂組成物。
［３］ 前記ポリマーが、テトラシクロ［４．４．０．１^２，５．１^７，１０］−３−ドデセンとエチレンとの共重合体である、［１］または［２］に記載の樹脂組成物。
［４］ さらにグリセリン脂肪酸エステルを含む、［１］〜［３］のいずれかに記載の樹脂組成物。
［５］ 前記一般式（７）で表される環状オレフィン系重合体のガラス転移点が、１３０〜１６０℃の範囲にある、［１］〜［４］のいずれかに記載の樹脂組成物。
［６］ ［１］〜［５］のいずれかに記載の樹脂組成物を硬化して得られる成形体。
［７］ ［６］に記載の成形体からなる光学部品。
［８］ ［７］に記載の光学部品からなるｆθレンズ。
［９］ ［７］に記載の光学部品からなる撮像レンズ。
［１０］ ［７］に記載の光学部品からなるプリズム。
［１１］ ［７］に記載の光学部品からなる導光板。
［１２］ ［７］に記載の光学部品からなる車載カメラレンズ部品。 The present invention is shown below.
[1] The following general formula ( 7 )

(In the above formula (7), R ^a is ^{a group} represented by the following general formula (3)

(In the above formula (3), p is an integer of 0 to 2) is a divalent group represented by the formula (3).
R ^b is a hydrogen atom or a monovalent group selected from the group consisting of a hydrocarbon group having 1 to 10 carbon atoms. Each of R ^a and R ^b may be one type, and may have two or more types in any ratio.
x and y each represent a copolymerization ratio and are real numbers satisfying 5/95 ≦ y / x ≦ 95/5. x and y are on a molar basis. )
A polymer which is a cyclic olefin polymer having one or more structures represented by
Fatty acid esters of diglycerin and saturated or unsaturated fatty acids having 12 to 18 carbon atoms ;
A resin composition containing the fatty acid ester in an amount of 0.3 to 1.0% by weight with respect to 100% by weight of the polymer (however , glycerin fatty acid ester and polyglycerin fatty acid ester as an antistatic agent) And ethylene oxide adduct of higher alcohol, ethylene oxide adduct of aromatic hydroxy compound, ethylene oxide adduct of polyhydric alcohol fatty acid ester having hydroxyl group, or ethylene oxide adduct of fat and oil having hydroxyl group,
In the case where the antistatic agent includes a glycerin fatty acid ester, a polyglycerin fatty acid ester, and a diethanolamine fatty acid ester in which an alkyl group may be bonded to a nitrogen atom,
As an antistatic agent, glycerin fatty acid ester, polyglycerin fatty acid ester, ethylene oxide adduct of higher alcohol, ethylene oxide adduct of aromatic hydroxy compound, ethylene oxide adduct of polyhydric alcohol fatty acid ester having hydroxyl group, or The case of containing an ethylene oxide adduct of fat and oil having a hydroxyl group, and a diethanolamine fatty acid ester in which an alkyl group may be bonded to a nitrogen atom, and a case where the compound represented by the following general formula (1) is included are excluded.

[In the above formula (1), Q ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, and Q ² is an organic group having 6 to 10 carbon atoms having an aromatic ring, and M ⁺ Is a sodium cation, potassium cation, ammonium, phosphonium, and a is 0 or 1. ]).
[2] The resin composition according to [ 1 ], wherein the fatty acid ester is a diglycerin unsaturated fatty acid ester.
[3] The polymer is tetracyclo [4.4.0.1 ^2,5 . The resin composition as described in [1] or [2] which is a copolymer of ^1,7,10 ] -3-dodecene and ethylene.
[4] The resin composition according to any one of [1] to [3] , further containing a glycerine fatty acid ester.
[5] The resin composition according to any one of [1] to [4] , wherein the glass transition point of the cyclic olefin polymer represented by the general formula (7) is in the range of 130 to 160 ° C.
The molded object obtained by hardening | curing the resin composition in any one of [6] [1]-[ 5 ].
The optical component which consists of a molded object as described in [7] [ 6 ].
[8] An fθ lens comprising the optical component according to [ 7 ].
The imaging lens which consists of an optical component as described in [9] [ 7 ].
[10] A prism comprising the optical component according to [ 7 ].
The light-guide plate which consists of an optical component as described in [11] [ 7 ].
[12] An on-vehicle camera lens component comprising the optical component according to [ 7 ].

  The resin composition of the present invention is excellent in high-temperature moldability and is most suitable as a molding material for transparent parts. According to the resin composition of the present invention, it is possible to obtain a transparent thermoplastic molded article which is excellent in optical performance and in which deterioration of the optical performance under high temperature and high humidity conditions is suppressed. That is, according to the resin composition of this invention, optical components, such as a vehicle-mounted camera lens component which was excellent in the balance of these characteristics, can be provided.

Hereinafter, the resin composition of the present invention will be described by way of embodiments.
The resin composition of the present embodiment contains a polymer containing an alicyclic structure in at least a part of the repeating structural unit, and a fatty acid ester of a fatty acid and a polyhydric alcohol having one or more ether groups.

[Polymer containing an alicyclic structure in at least a part of the repeating structural unit]
A polymer containing an alicyclic structure in at least a part of the repeating structural unit (hereinafter, also simply referred to as "a polymer containing an alicyclic structure") contains an alicyclic structure in at least a part of the repeating unit of the polymer In particular, it is preferable to include a polymer having one or more types of structures represented by General Formula (2).

In Formula (2), x and y show a copolymerization ratio and are real numbers which satisfy | fill 0/100 <= y / x <= 95/5. x and y are on a molar basis.
n represents the number of substitution 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, preferably 2 to 12 carbon atoms.
R ^b is a hydrogen atom or a monovalent group selected from the group consisting of 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, 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 hydrogen atom or a monovalent group selected from the group consisting of a hydrocarbon group having 1 to 10 carbon atoms. Preferably, they are 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 type, or two or more types may be included in an arbitrary ratio.

In the above 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 the case, it is a divalent group represented by General Formula (3), and most preferably a divalent group in which p is 0 or 1 in General Formula (3) below. The structure of R ^a may be used alone or in combination of two or more.

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

  Moreover, in the said General formula (2), the following general formula in the case of n = 0

As a bivalent group represented by these, the group represented by following General formula (4)-(6) etc. is mentioned.

In formulas (4) to (6), R ^a is as described above.
Further, the type of polymerization is not limited at all in this embodiment, and various known polymerization types such as addition polymerization and ring opening polymerization can be applied. As addition polymerization, random copolymer, block copolymer, alternating copolymerization, etc. can be mentioned. In the present embodiment, 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 possible to obtain an optical component having excellent optical properties such as transparency, refractive index and birefringence, and high precision.

(An example of a polymer containing an alicyclic structure in at least a part of a repeating structural unit)
The polymers represented by the general formula (2) can be roughly classified into the following four polymers (i) to (iv).
(I) Copolymer of ethylene or α-olefin and cyclic olefin (ii) Ring-opened polymer or hydrogenated product thereof (iii) Vinyl alicyclic hydrocarbon based polymer (iv) Other polymers explain.

((I) Copolymer of ethylene or α-olefin and cyclic olefin)
(I) The copolymer of ethylene or α-olefin and cyclic olefin is a cyclic olefin-based copolymer represented by the general formula (7). For example, it comprises ethylene or 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 the 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 a hydrocarbon group 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 type, or two or more types may be included in an arbitrary ratio.

  x and y each represent a copolymerization ratio and are real numbers satisfying 5/95 ≦ y / x ≦ 95/5. Preferably, 50/50 ≦ y / x ≦ 95/5, more preferably 55/45 ≦ y / x ≦ 80/20, and particularly preferably 60/40 ≦ y / x ≦ 70/30. x and y are on a molar basis. Within this range, the glass transition temperature is high, which is preferable in that heat resistance suitable for optical parts such as in-vehicle camera lens parts can be obtained.

(Constituent 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 ethylene or a linear or branched α-olefin having 3 to 30 carbon atoms as described below.

  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 types 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.

(Constituent unit derived from cyclic olefin (B))
The structural unit (B) derived from cyclic olefin is at least one selected from the group consisting of structural units derived from cyclic olefins 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 using w is a 6-membered ring, and when w is 0, the ring is a 5-membered ring. R ^{61 to} R ⁷⁸ and R ^a1 and R ^{b1, which} may be the same or different, 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. As a halogenated alkyl group, the group which the one or several halogen atom substituted by the said C1-C20 alkyl group is mentioned. Further, examples of the cycloalkyl group include cyclohexyl and the like, and examples of the aromatic hydrocarbon group include phenyl and naphthyl.

Furthermore, in the above 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, in combination 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 polycycles than single rings, polycycles are preferable from the viewpoint of heat resistance. Furthermore, there is an advantage that it can be produced with a small amount of charged cyclic olefin. Specific examples of the monocyclic or polycyclic group formed herein include the following.

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

An alkylidene group may be formed by R ⁷⁵ and R ⁷⁶ , or R ⁷⁷ and R ⁷⁸ . The 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 Formula (9), x and d are 0 or 1 or more positive integers, 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 And the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded 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 said Formula (8) can be illustrated.

  As an aliphatic hydrocarbon group, a C1-C20 alkyl group or a C3-C15 cycloalkyl group is mentioned. More specifically, examples of the alkyl group include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, octadecyl and the like. The cycloalkyl group includes cyclohexyl and the like.

  The aromatic hydrocarbon group includes an aryl group, an aralkyl group and the like, and specific examples include phenyl, tolyl, naphthyl, benzyl and phenylethyl.

The alkoxy group includes 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 May be linked via That is, when the above two carbon atoms are linked via an alkylene group, R ⁸⁹ and R ⁹³ or R ⁹⁰ and R ⁹¹ cooperate 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, the following aromatic rings formed by R ⁹⁵ and R ⁹² when y = z = 0 are mentioned. Since a copolymer having a high glass transition temperature (Tg) can be obtained with a smaller content of polycycles than single rings, polycycles are preferable from the viewpoint of heat resistance. Furthermore, there is an advantage that it can be produced with a small amount of charged 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 formula (10), R ¹⁰⁰ and R ^{101, which} may be the same or different, are a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18. As a C1-C5 hydrocarbon group, Preferably an alkyl group, a halogenated alkyl group, or a cycloalkyl group can be mentioned. These specific examples are clear from the specific examples of R ^{61 to} R ⁷⁸ of the above formula (8).

  As the structural unit (B) derived from a 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 derivative, hexacyclo-4-heptadecene derivative, heptacyclo-5-eicosene derivative, heptacyclo-4-eicosene derivative, heptacyclo-5-heneicosene derivative, octacyclo-5-docose derivative, nonacyclo-5-penta Sen derivative, nonacyclo-6-hexacocene derivative, derivative of cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene derivative, 1,4-methano-1,4,4a, 5 10, 10a-hexahydroanthracene derivatives, cycloalkylene derivatives having 3 to 20 carbon atoms, and the like.

Further, among structural units (B) derived from cyclic olefins represented by the above general formula (8), (9) or (10), tetracyclo [4.4.0.1 ^2,5 . 17 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 structures 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 derivative

Also 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 Diels-Alder reaction of cyclopentadiene with an olefin having a corresponding structure. Two or more types of structural units (B) derived from cyclic olefins represented by these general formulas (8), (9) or (10) may be contained. Moreover, what was polymerized using the said monomer can be denatured as needed, and the structure of the structural unit derived from a monomer can be changed in that case. For example, by hydrogenation treatment, a benzene ring or the like in a structural unit derived from a monomer can be made into a cyclohexyl ring depending on conditions.

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

  Also, the type of copolymerization is not limited at all in this embodiment, and various known types of copolymerization such as random copolymer, block copolymer, alternating copolymerization, etc. can be applied, but preferably random copolymer is there.

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

  The cyclic olefin polymer may have a polar group. As a polar group, a hydroxyl group, a carboxyl group, an alkoxy group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyl group, an amino group, an ester group etc. are mentioned.

  The cyclic olefin polymers are usually obtained by polymerizing cyclic olefins, specifically by ring-opening polymerization of alicyclic olefins. Further, the cyclic olefin polymer having a polar group may be prepared, for example, by introducing a compound having a polar group into the cyclic olefin polymer by a modification reaction, or using a monomer having a polar group as a copolymerization component. It is obtained by copolymerizing.

Specific examples of alicyclic olefins used to obtain cyclic olefin polymers include 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 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-bi Chloro [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-methyl octanate, bicyclo [2.2.1] -hept-2-ene-5,6-dicarboxylic anhydride, 5-hydroxymethylbicyclo [2.2.1] -hept- 2-ene, 5,6-di (hydroxymethyl)- Cyclo [2.2.1] -hept-2-ene, 5-hydroxy-i-propylbicyclo [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-dicarboximide, 5-cyclopentyl-bicyclo [2.2.1] -hept-2-ene 5-cyclohexyl-bicyclo [2.2.1] -hept-2-ene, 5-cyclohexenyl-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 ] c Ndeca-3,7-diene, tricyclo [4.4.0.1 ^2,5 ] undeca-3,8-diene, tricyclo [4.4.0.1 ^2,5 ] undec-3-ene, tetracyclo [4. 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 (alias: 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene), tetracyclo [4.4 .0.1 ^2,5 . ^{17 10} ] -dodec-3-ene (common name: tetracyclododecene), 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 17 ¹⁰ ] -dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 17 ¹⁰ ] -dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 17 ¹⁰ ] -dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 17 ¹⁰ ] -dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 17 ¹⁰ ] -dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] - dodeca-3-ene, 8-methoxycarbonyloxy - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] - dodeca-3-ene, 8-methyl-8-methoxycarbonyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] - dodeca-3-ene, 8-hydroxymethyl - tetracyclo [4.4.0.1 ^{2, 5.} 17 ¹⁰ ] -dodec-3-ene, 8-carboxy-tetracyclo [4.4.0.1 ^2,5 . 17 ¹⁰ ] -dodec-3-ene, 8-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . 17 ¹⁰ ] -dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] - dodeca-3-ene, 8-cyclohexenyl - tetracyclo [4.4.0.1 ^{2, 5.} 17 ¹⁰ ] -dodec-3-ene, 8-phenyl-tetracyclo [4.4.0.1 ^2,5 . ^{17 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-based 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 and cycloheptene;
Vinyl alicyclic hydrocarbon-based monomers such as vinylcyclohexene and vinylcyclohexane;
Alicyclic conjugated diene-based monomers such as cyclopentadiene and cyclohexadiene; and the like. The alicyclic olefins can be used alone or in combination of two or more.

In addition, the copolymerizable monomer can be copolymerized as needed. 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 having 2 to 20 carbon atoms, such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, or α-olefins;
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. From the viewpoint of heat resistance, stability and optical properties, these ring-opening polymers are preferably hydrogenated before use. The hydrogenation method can use a well-known method.

((Iii) Vinyl alicyclic hydrocarbon-based polymer)
(Iii) Vinyl alicyclic hydrocarbon polymers are obtained from vinyl aromatic hydrocarbon compounds as monomers (co) polymer hydrogenated products or vinyl alicyclic hydrocarbon compounds as monomers (Co) polymers. As a vinyl compound, a vinyl aromatic compound, a vinyl alicyclic hydrocarbon compound, etc. can be mentioned.

  As a vinyl aromatic compound, styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-isopropylstyrene, α-t-butylstyrene, 2-methylstyrene, 3-methylstyrene, 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.

Examples of vinyl alicyclic hydrocarbon compounds include 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 and the like Vinylcyclohexenes and the like can be mentioned.

In the present embodiment, 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-based monomers such as cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 5-methylcyclopentadiene, 5,5-dimethylcyclopentadiene, dicyclopentadiene and the like;
Monocyclic olefin monomers such as cyclobutene, cyclopentene and cyclohexene;
Conjugated diene-based monomers such as butadiene, isoprene, 1,3-pentadiene, furan, thiophene and 1,3-cyclohexadiene;
Nitrile monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like;
(Meth) acrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, etc .;
Unsaturated fatty acid monomers such as acrylic acid, methacrylic acid and maleic anhydride;
Phenyl maleimide;
Methyl vinyl ether;
Heterocycle-containing vinyl compound monomers such as N-vinylcarbazole, N-vinyl-2-pyrrolidone and the like can be mentioned.

  From the viewpoint of heat resistance, low birefringence, mechanical strength, etc., the mixture of the above-mentioned monomers used for polymerization is usually at least 50% by mass of a vinyl aromatic hydrocarbon compound and / or a vinyl alicyclic hydrocarbon compound. Those containing preferably 70 to 100% by mass, more preferably 80 to 100% by mass are preferable. The monomer mixture may contain both a vinyl aromatic hydrocarbon compound and a vinyl alicyclic hydrocarbon compound.

  The polymerization method of 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 substance from the viewpoint of heat resistance, stability, and optical physical properties. The hydrogenation method can use a well-known method.

  The hydrogenation product of the (co) polymer obtained from the vinyl aromatic hydrocarbon compound may have a hydrogenation rate of phenyl group of preferably 95% or more, more preferably 99% or more. By hydrogenation treatment, the phenyl group in the resin structure is hydrogenated to form a cyclohexyl group. The molded product containing this resin improves the light transmittance on the short wavelength side, and reduces birefringence and optical anisotropy. At the same time, the unreacted monomers and impurities are subjected to hydrogenation treatment to improve the resistance to heat and light. These effects are particularly excellent when the hydrogenation rate is in the above range.

((Iv) Other polymers)
(Iv) Other polymers include, for example, polymers of monocyclic cycloalkenes, polymers of alicyclic conjugated diene-based monomers, aromatic olefin polymers, etc. Even a structure not included in iii) can be arbitrarily selected within the range of the general formula (2). For example, those obtained by copolymerizing the above (i) to (iii) with each other or known copolymerizable monomers can be mentioned.

  Also, the type of copolymerization is not limited at all in this embodiment, and various known types of copolymerization such as random copolymer, block copolymer, alternating copolymerization, etc. can be applied, but preferably random copolymer is there.

Among the four polymers roughly classified in the above (i) to (iv), preferred in terms of optical properties are (i) copolymers of ethylene or α-olefin and cycloolefin, and among them, the most preferred one 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 containing an alicyclic structure used in the present embodiment is, if necessary, another copolymerizable monomer as long as the good physical properties of the product obtained by the molding method of the present embodiment are not impaired. It may have a repeating structural unit derived from The copolymerization ratio is not limited, but is preferably 20 mol% or less, more preferably 0 to 10 mol%, and if the copolymerization amount is 20 mol% or less, high-precision optical without impairing the optical properties. You can get parts. Also, the type of copolymerization is not limited.

(Molecular weight of polymer containing alicyclic structure in at least part of repeating structural units)
The molecular weight of the polymer containing an alicyclic structure used in the present embodiment is not limited, but when limiting viscosity [η] is used as an alternative index of molecular weight, it is preferably measured in decalin at a temperature of 135 ° C. The intrinsic viscosity [.eta.] Is preferably 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 body is not impaired.

(Glass transition temperature of polymer containing alicyclic structure in at least part of repeating structural unit)
The glass transition temperature (Tg) of the polymer containing an alicyclic structure in at least a part of the repeating structural unit used in the present embodiment is preferably 100 to 180 ° C. More preferably, it is 120-160 ° C. Most preferably, it is 130 to 160 ° C. When the molded article is used as an optical component such as an on-vehicle camera lens component as the glass transition temperature (Tg) is in the above range, sufficient heat resistance can be obtained, and good moldability can be obtained. .
The higher the amount of alicyclic structural units, the higher the glass transition temperature can generally be. Ethylene and tetracyclo [4.4.0.1 ^2,5 . A copolymer comprising the ^{compound (7,10} ) -3-dodecene, wherein the copolymerization ratio is 55/45 ≦ y / x ≦ 80/20, particularly preferably 60/40 ≦ y / x ≦ 70. The glass transition temperature can be made into the said range as it is / 30.

  The measuring apparatus etc. of glass transition temperature are not limited. For example, a differential scanning calorimeter (DSC) can be used to measure the glass transition temperature of the thermoplastic amorphous resin. For example, a method of measuring at a temperature rising rate of 10 ° C./min using a DSC-20 manufactured by SEIKO Electronic Industry Co., Ltd. can be mentioned.

(An example of a method for producing a polymer containing an alicyclic structure in at least a part of a repeating structural unit)
Although the manufacturing method of the polymer containing such an alicyclic structure is not limited, each can be manufactured as follows.

(I) Copolymers of ethylene or α-olefin and a cyclic olefin are disclosed, for example, in JP-A 60-168708, JP-A 61-120816, JP-A 61-115912, JP-A The conditions are appropriately selected according to the methods of JP-A-61-215916, JP-A-61-271308, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407, etc. Can be manufactured by
(Ii) The ring-opened polymer or the hydrogenated product thereof can be produced by methods such as JP-A-60-26024, JP-A-9-268250, JP-A-63-145324, JP-A-2001-72839, etc. It can manufacture by selecting conditions suitably according to. (Iii) The vinyl alicyclic hydrocarbon-based polymer can be prepared by appropriately selecting the conditions according to the method disclosed in WO 01/092412, JP 2003-276047, JP 2004-83813, etc. It can be manufactured.

(Hydrogenation)
Furthermore, in the step of producing a polymer containing an alicyclic structure, the polymer or the system comprising the polymer and a raw material monomer is brought into contact with a hydrogenation catalyst and hydrogen at least once to obtain the polymer and the polymer By hydrogenating at least a part of the unsaturated bond possessed by the monomer, the optical performance such as heat resistance and transparency of the polymer can be improved. In addition, the said hydrogenation so-called hydrogenation can be performed by a conventionally well-known method.

(Residual monomer)
It is preferable that the step of producing a polymer containing an alicyclic structure or the step of producing a resin composition include a step of reducing unreacted monomers. As the reduction step, melt devolatization, polymer crystallization, phase separation process, hydrogenation reaction to double bond by hydrogenation process can be exemplified. By reducing the residual monomer, it is possible to improve the thermal stability of the resin, to improve the light transmittance and the diffraction efficiency by reducing the appearance defect during molding, and to reduce the generated gas at the molding operation. The residual amount of residual monomer is preferably 5000 ppm or less, more preferably 1000 ppm or less, and most preferably 500 ppm or less.

[Fatty acid ester]
The fatty acid ester is an ester of a fatty acid and a polyhydric alcohol having one or more ether groups. In addition, the ether group of polyhydric alcohol does not contain the ether group in ester group.
Examples of polyhydric alcohols having one or more ether groups include diglycerin, triglycerin, tetraglycerin and sorbitan.
In this embodiment, the fatty acid ester can include diglycerin fatty acid ester. The diglycerin fatty acid ester is obtained by esterifying at least one of four hydroxy groups contained in diglycerin with a fatty acid.

As fatty acids, saturated fatty acids such as butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and the like;
Monounsaturated fatty acids such as crotonic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, gadeuric acid, eicosenic acid;
Diunsaturated fatty acids such as linoleic acid, eicosadienoic acid, docosadienoic acid;
Triunsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, eicosatrienoic acid;
Examples thereof include tetraunsaturated fatty acids such as stearidonic acid, arachidonic acid, and eicosatetraenoic acid.

As diglycerin fatty acid esters, diglycerin monocaprylate, diglycerin dicaprylate, diglycerin monocaprate, diglycerin monocaprate, diglycerin dicaprate, diglycerin monolaurate, diglycerin dilaurate, diglycerin monomyristate, diglycerin dimyristate , Diglycerin saturated fatty acid esters such as diglycerin monopalmitate, diglycerin dipalmitate, diglycerin monostearate, diglycerin distearate, diglycerin monobehenate, diglycerin dibehenate;
And diglycerin unsaturated fatty acid esters such as diglycerin monooleate and diglycerin diolate; and the like, and one or more selected from these may be used in combination.
In this embodiment, the diglycerin fatty acid ester is preferably an ester of diglycerin and a saturated or unsaturated fatty acid having 12 to 18 carbon atoms selected from the above.

  In addition, it is preferable to contain a diglycerin unsaturated fatty acid ester as a main component from a viewpoint of the effect of this invention, and it is more preferable to also contain the diglycerin monooleate as a main component among them. Since the diglycerin skeleton has hydrophilicity and the fatty acid improves the compatibility with the resin, the transparency is maintained and the heat and moisture resistance is excellent.

The resin composition can comprise at least one diglycerin fatty acid ester. Preferred embodiments of the at least one diglycerin fatty acid ester include monoesters alone or a combination of monoesters and diesters.
In this embodiment, the monoester alone or the total of the monoester and the diester is 0.3 to 1.0% by weight, preferably 0.4 to 0.9% by weight, based on 100% by weight of the polymer. Preferably, it can be contained in an amount of 0.5 to 0.8% by weight.

  The glass transition temperature (Tg) of the polymer containing an alicyclic structure in at least a part of the repeating structural unit used in the present embodiment is in the above range, and the diglycerin fatty acid ester is contained in the above range The composition has good heat and humidity resistance while maintaining sufficient heat resistance. That is, the Tg of the composition is high, and the decrease in transparency due to the moist heat resistance test is small. Such a molded article made of the resin composition of the present invention can be suitably used as an on-vehicle optical component, in particular, an on-vehicle camera lens component.

<Resin composition>
The resin composition (resin composition for optical material) of the present embodiment is a fatty acid ester of a polymer having an alicyclic structure in at least a part of the repeating structural unit, and a polyhydric alcohol having one or more fatty acids and one or more ether groups. And.
Since the fatty acid ester contains a structural unit derived from a fatty acid, it is possible to obtain a molded body excellent in compatibility with the polymer (olefin resin) and excellent in transparency. Furthermore, the diglycerin fatty acid ester has a hydrophilic functional group such as a hydroxyl group, an ether group or a carbonyl group. Therefore, even when molding is performed under high temperature and high humidity conditions, it is presumed that the water absorbed in the resin composition is dispersed, and the aggregation of water causing deterioration of the optical performance is suppressed. Therefore, it is considered that in a molded article excellent in transparency, deterioration of optical performance under high temperature and high humidity conditions can be prevented.
The composition of the present embodiment can further contain a glycerin fatty acid ester.

The fatty acid ester of a fatty acid and a polyhydric alcohol having one or more ether groups is 0.4 to 1.2% by weight, preferably 0.4 to 1.% by weight with respect to 100% by weight of the polymer having an alicyclic structure. It can be included in an amount of 0% by weight, more preferably 0.45 to 1.0% by weight. In the above-mentioned range, it is possible to obtain an optical component excellent in optical properties such as transparency, refractive index and birefringence, and having high accuracy. In addition, mold stains are suppressed, and heat and humidity resistance and antistatic properties are excellent.
In addition, when molding the resin composition under an air atmosphere and high temperature conditions, if the amount of the stabilizer (the above-mentioned fatty acid ester) to be added is small as in the above range, the resin composition due to oxidative degradation of the stabilizer Since the coloration of the object can be suppressed, the heat aging resistance is also excellent.

  Such a resin composition of the present embodiment is optimal as a molding material for transparent parts, and in particular, it is excellent in optical performance such as haze and light transmittance, and deterioration of optical performance under high temperature and high humidity conditions is suppressed. Furthermore, it is possible to obtain a transparent thermoplastic molded article having excellent antistatic properties. In addition, since mold stain resistance is improved, the production stability is also excellent. That is, according to the resin composition of the present embodiment, an optical component having an excellent balance of these characteristics can be obtained.

(Additives that can be added to the resin composition as optional components)
In the resin composition, in addition to the polymer having an alicyclic structure in at least a part of the above-mentioned repeating structural unit and diglycerin fatty acid ester, within the range which does not impair the good physical properties of the resin composition of the present embodiment. Known additives can be used as optional components.
Additives that can be added include known antioxidants, secondary antioxidants, lubricants, mold release agents, antifogging agents, weathering stabilizers, light stabilizers, ultraviolet light absorbers, antistatic agents, metal deactivators Is illustrated.

(Antioxidant)
Among these, it is preferable to add an antioxidant so that the favorable optical physical properties of the resin composition of the present embodiment are not impaired at the time of molding. As an antioxidant, a phenol type stabilizer is used suitably.

  Phenolic stabilizers are stabilizers having a phenolic backbone in their 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 .

As a specific example, 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-63-179953 and JP-A-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'-hydroxyphenyl propionate) methane [ie, pentaerythrymethyl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl propionate)), tri] Alkyl substituted phenolic compounds such as ethylene glycol bis (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate), tocophenol and the like;
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, Triazine group-containing phenolic compounds such as 2-octylthio-4,6-bis- (3,5-di-tert-butyl-4-oxyanilino) -1,3,5-triazine; and the like. Among these, tetrakis (methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenylpropionate) methane is preferable because it is excellent in heat resistance and stability.

  Although the addition amount of the antioxidant is not particularly limited, it 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 unit. In the case of using tetrakis (methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl propionate) methane as the most preferred embodiment, the addition amount is at least a part of the repeating structural unit. The amount is 0.1 to 0.5 parts by mass with respect to 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 embodiment, it is possible to reduce the hue change and the deterioration of the optical performance at the time of molding cessation and continuous molding. . When the amount is 1.2 parts by mass or less, the solubility of the phenolic stabilizer in the resin composition is sufficient, and mold stains during injection molding can be reduced, and at the same time, the phenolic stabilizer phase-separates in the molded body As a result, it is possible to obtain a molded body excellent in transparency and homogeneity.

(Production method of resin composition and molded body)
The manufacturing method of the resin composition of this embodiment is not specifically limited, It can manufacture by a well-known method. Specifically, a polymer having an alicyclic structure, a diglycerin fatty acid ester, optionally a diglycerin, a phosphorus-based stabilizer and a hydrophilic stabilizer according to the purpose, and a range not impairing the purpose of the present invention Add the above-mentioned other stabilizers and mix them, and then flash-dry or mix the components using a Henschel mixer, ribbon blender, melt blender, homomixer etc. and pelletize using an extruder. Can be obtained as a pellet-like resin composition. Furthermore, a molded product can be obtained 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 a target molded product.

(Total light transmittance and spectral light transmittance)
When the resin composition of the present embodiment is used for optical applications, it is essential that the resulting molded body transmits light, and therefore, it is preferable that the light transmittance is good. The light transmittance is defined by the spectral light transmittance or the total light transmittance depending on the application.

  In the case where use in all light rays or a plurality of wavelength regions is assumed, it is necessary that the total light ray transmissivity be good, and the total light ray transmissivity in the state where the antireflective film is not provided on the surface is 85% or more, preferably Is 88 to 93%. If the total light transmittance is 85% or more, the necessary amount of light can be secured. The method of measuring the total light transmittance can be a known method, and the measuring device is not limited. For example, in accordance with ASTM D1003, a thermoplastic, amorphous resin is molded into a 3 mm thick sheet, and a haze meter is used. The method etc. which measure the total light transmittance of the sheet | seat obtained by shape | molding the resin composition of this embodiment using it, etc. are mentioned.

  In the case of an optical system used 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 anti-reflection film is not provided on the surface at a used wavelength is preferably 85% or more, more preferably 86 to 93%. If the spectral light transmittance is 85% or more, the necessary amount of light can be secured. In addition, as the measurement method and apparatus, known methods can be applied, and a spectrophotometer can be specifically exemplified.

(Antistatic property)
The absolute value of the surface potential of the molded product of the present embodiment is preferably 5 kV or less, more preferably 4 kV or less, and more preferably 3 kV or less.
(Heat resistant aging resistance)
In this embodiment, discoloration and yellowing of the molded body are represented by ΔYI. 50 or less is preferable, 45 or less is further more preferable, and 40 or less is more preferable for (DELTA) YI.

[Use]
The molded object obtained from the resin composition of this embodiment can be used as an optical component.
Examples of optical components include sensor lenses, pickup lenses, projector lenses, prisms, fθ lenses, imaging lenses, light guide plates, etc. From the viewpoint of the effect of the present invention, fθ lenses, imaging lenses, sensor lenses, prisms or It can be suitably used for a light plate.
In particular, molded articles obtained from the resin composition of the present invention have a surprising effect that they have a glass transition temperature in the range of 130 to 160 ° C., and have high heat resistance while satisfying moisture heat resistance and aging resistance. . Therefore, the molded object obtained from a resin composition can be used especially suitably for vehicle-mounted optical components. Examples of the on-vehicle optical component include a view camera lens, a sensing camera lens, a light focusing lens for a head-up display, and a light diffusion lens for a head-up display.

  Hereinafter, the present invention will be more specifically described based on examples.

Example 1
(Preparation of catalyst)
Diluted VO a _{(OC 2} H 5) Cl ₂ with cyclohexane, vanadium concentration was prepared vanadium catalyst is 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 milmol / L-hexane.

(polymerization)
Using a stirring type polymerizer (inner diameter 500 mm, reaction volume 100 L), ethylene and tetracyclo [4.4.0.1 ^2,5 . The copolymerization reaction was carried out with 1 ^{7, 10} ] -3-dodecene.
When carrying out this copolymerization reaction, the vanadium catalyst prepared by the above method is added in such an amount that the vanadium catalyst concentration relative to cyclohexane in the polymerization vessel used as the polymerization solvent is 0.6 mmol / L. Supplied inside.
In addition, ethylaluminum sesquichloride, which is an organoaluminum compound, was supplied into the polymerization vessel in an amount such that Al / V = 18.0. The copolymerization was carried out continuously at a polymerization temperature of 8 ° C. and a polymerization pressure of 1.8 kg / cm ² G.

(Deashing)
Ethylene tetracyclo [4.4.0.1 ^2,5 . The polymerization reaction is stopped by adding a 1, ^{7 10} !] 3-dodecene copolymer solution as a water and a pH adjuster, and a 25% by mass NaOH solution to this copolymer solution to stop the polymerization reaction, and Catalyst residues present in the copolymer solution were removed (deashed) from the copolymer solution (polymer solution A).
Ethylene-tetracyclo [4.4.0.1 ^2,5 . Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl) as a stabilizer for cyclohexane solution (polymer solution A, polymer concentration: 7.7% by mass) of a ^1,7,10 ! -3-dodecene copolymer -4-Hydroxyphenyl) propionate] is added in an amount of 0.4 parts by mass with respect to 100 parts by mass of the polymer, and then once the effective volume is 1.0 cm before entering the flash drying step. ^The mixture was mixed for 1 hour using a stirring vessel of ³ .

(Desolvation)
The concentration of the copolymer in the cyclohexane solution in a double tube heater (outer tube diameter 2B, inner tube diameter 3 / 4B, length 21 m) using steam of 20 kg / cm ² G as a heat source in the heating step The cyclohexane solution of the said copolymer made into 5 mass% was supplied in the quantity of 150 kg / H, and it heated at 180 degreeC.
The above heating is performed using a double tube flash dryer (outer tube diameter 2B, inner tube diameter 3/4 B, length 27 m) and a flash hopper (volume 200 L) using steam of 25 kg / cm ² G as a heat source Most of the unreacted monomers were removed together with the polymerization solvent, cyclohexane, from the cyclohexane solution of the copolymer obtained through the process to obtain a flash-dried, cyclic olefin random copolymer (Resin A) in a molten state. The glass transition temperature (Tg) of the resin A was 140 ° C.

(Extrusion)
After charging the above cyclic olefin random copolymer in a molten state from the resin charging portion of the extruder using a vented twin-screw kneading extruder, vacuum is applied via a trap for the purpose of removing volatiles from the vent portion. While suctioning with a pump, the melt stabilizer (Rikemar DO-100: manufactured by Riken Vitamin Co., Ltd.) described in Table 1 was added to the cylinder portion downstream of the vent portion 0.6 per 100% by weight of resin A. It was added in an amount of% by weight, and was kneaded and mixed on the downstream side of the vent part of the extruder. At this time, the extruder conditions were adjusted so that the difference between the maximum value and the minimum value of the extruder diverter resin temperature was within 3 ° C. Then, it was pelletized by an underwater pelletizer attached to the extruder outlet, and the obtained pellet was dried by hot air at a temperature of 100 ° C. for 4 hours. Furthermore, in order to suppress the mixing of iron atoms (Fe), a polymer production facility is a stainless steel pipe or a polymerization apparatus, and resin which is about 3 to 5 times the amount of resin calculated from the average residence time in the polymerization vessel A resin composition comprising a resin A was obtained by performing an operation of flowing for cleaning (purge) and thereafter collecting a sample.
In addition, the addition amount of the melting stabilizer in Table 2 is an addition amount (weight%) with respect to 100 weight% of polymers. Moreover, the melting stabilizer put the stabilizer of Table 1 in the container, and used what was heated at 85 degreeC for 10 hours. The same applies to other polymer production methods.

[Examples 2 and 3]
As described in Table 2, Kao Wax 85P (manufactured by Kao Corp.) or electro is used as a melting stabilizer using Rikemar DO-100 (manufactured by Riken Vitamin Co., Ltd.) or Poem DO-100V (manufactured by Riken Vitamin Co., Ltd.) A resin composition containing a resin A was prepared in the same manner as in Example 1 except that the composition of Table 2 was made using Stripper TS-5 (manufactured by Kao Corporation).

Example 4
Example 1 was repeated except that pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was not added as a stabilizer to polymer solution A of Example 1. Resin C was produced in the same manner. The glass transition temperature (Tg) of the resin C was 140 ° C. In the obtained resin C, 0.4 wt% of pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] as a stabilizer based on 100 wt% of the polymer And dry-blended for 20 minutes using a tumbler, then 100% by weight of resin C in a molten state, Rikemar L71-D (manufactured by Riken Vitamin Co., Ltd.), which is a melting stabilizer described in Table 1. The resin composition was charged directly into the extruder in an amount of 0.7% by weight based on the above to obtain a resin composition containing a resin C.
Specifically, cyclic olefin random obtained in the production example using a twin screw extruder of L / D = 30 having the same direction rotation, a screw diameter of 44 mm and a vent hole at the position of L / D = 24 from the resin charging portion The copolymer is charged from the resin charging part, charged from a commercially available stabilizer vent hole heated and melted at 80 to 120 ° C., and the screw rotation number 150 rpm, motor power 30 kW. The resin composition of Table 2 I got

[Examples 5 to 8, Comparative Examples 1 to 8]
A resin composition containing the resin C of Table 2 was produced in the same manner as in Example 4 except that the composition of Table 2 was used.

[Example 9]
A cyclic olefin random copolymer of a polymer in a molten state obtained in the same manner as in Example 1 except that the glass transition temperature (Tg) was adjusted to 148 ° C., was measured using a nickel / diatomaceous earth catalyst (N112 manufactured by JGC) The copolymer is hydrogenated by continuous hydrogenation under the conditions of a reaction temperature of 100 ° C., a reaction pressure of 1 MPa, and LHSV = 5 / hr, and pentaerythrityl-tetrakis [3- (3,5- (3-) as a stabilizer. The additive is added in an amount of 0.4 parts by mass with respect to 100 parts by mass of the polymer using di-t-butyl-4-hydroxyphenyl) propionate], and the resin is prepared in the same manner as in Example 1 I got B. The glass transition temperature (Tg) of the resin B was 148 ° C. Furthermore, in the same manner as in Example 1, except that a melt stabilizer (Rikemar DO-100: manufactured by Riken Vitamin Co., Ltd.) was added in an amount of 0.60% by weight based on 100% by weight of resin B, the resins of Table 2 A resin composition comprising B was produced.

[Example 10]
Furthermore, resin B in Table 2 was prepared in the same manner as in Example 9, except that a melting stabilizer (Kao wax 85P: manufactured by Kao Corporation) was added in an amount of 0.5% by weight based on 100% by weight of resin B. A resin composition comprising

[Example 11]
A cyclic olefin random copolymer (Resin D) was obtained in the same manner as in Example 1 except that the glass transition temperature (Tg) was adjusted to 151 ° C. The glass transition temperature (Tg) of the resin D was 151 ° C. Furthermore, resin D in Table 2 was prepared in the same manner as in Example 1 except that a melting stabilizer (Rikemar DO-100: manufactured by Riken Vitamin Co., Ltd.) was added in an amount of 0.70% by weight based on 100% by weight of resin D. A resin composition comprising

[Examples 12 to 14]
A resin composition containing the resin D of Table 2 was produced in the same manner as in Example 11 except that the composition of Table 2 was used.
The determination of the diglycerin fatty acid ester in the resin composition was performed by the following method.

(Method of determination)
Measuring method Measuring equipment: HP-5890 (Agilent Technologies)
Column: ZB-1 INFERNO 0.32 mmφ × 15 m
Temperature column 120 ° C → heat up at 9 ° C / min → hold at 390 ° C for 10 min
Detector temperature: 400 ° C
Carrier gas: He
Split ratio: 50: 1
Injection amount: 1 μm
Detector: FID

Preparation of Measurement Sample (1) 0.0130 g of an internal standard (n-butyl phthalate, special grade manufactured by Tokyo Kasei Kogyo Co., Ltd.) is weighed into a 50 mL measuring flask, made up with pyridine, and used as an internal standard solution.
(2) Precisely weigh 0.5 g of the resin composition sample in a 50 mL measuring flask, add 10 mL of cyclohexane, and dissolve with ultrasound.
(3) After step (2), while stirring the dissolved measuring flask, add dropwise acetone to white turbidity and then add acetone at once to reprecipitate the polymer, measure with acetone, stir for 1 minute with ultrasonic wave , Mix.
(4) After step (3), after standing, transfer 1 mL of the clear supernatant liquid into a vial and evaporate to dryness with nitrogen gas, and then 50 μL of internal standard solution and trimethylsilylating agent (BSTFA, Tokyo Kasei Co., Ltd. 200 μL is added, and a trimethylsilylation reaction is performed for 1 hour on a block heater heated to 90 ° C.
(5) After the step (4), after air cooling to room temperature, measurement is performed under the above conditions, and the ester composition ratio is determined from the area ratio of the chart.

  About the molded object obtained from the resin composition of Examples 1-14 and Comparative Examples 1-8, the physical property was measured with the following evaluation methods. The evaluation results are shown in Table-2.

(Evaluation method of molded body)
ヘ イ ズ Haze A test piece having an optical surface of 35 mm × 65 mm × 3 mm thickness was formed by injection molding at a cylinder temperature of 275 ° C. and a mold temperature of 120 ° C. using an injection molding machine (ROBOSHOT S2000i-30α manufactured by FANUC Co., Ltd.). The internal haze of a molded object used benzyl alcohol and was measured based on JISK-7105. The internal haze passed 1.0% or less.

試 験 Environmental test The test piece was left under an atmosphere of temperature 80 ° C and relative humidity 90% for 48 hours. Then, the haze was measured 3 hours after taking out. The change amount (hereinafter, ΔHaze) obtained by subtracting the haze before the environmental test from the haze after the environmental test was determined to be 1.0% or less.

Claims (12)

Following general formula ( 7 )

(In the above formula (7), R ^a is ^{a group} represented by the following general formula (3)

(In the above formula (3), p is an integer of 0 to 2) is a divalent group represented by the formula (3).
R ^b is a hydrogen atom or a monovalent group selected from the group consisting of a hydrocarbon group having 1 to 10 carbon atoms. Each of R ^a and R ^b may be one type, and may have two or more types in any ratio.
x and y each represent a copolymerization ratio and are real numbers satisfying 5/95 ≦ y / x ≦ 95/5. x and y are on a molar basis. )
A polymer which is a cyclic olefin polymer having one or more structures represented by
Fatty acid esters of diglycerin and saturated or unsaturated fatty acids having 12 to 18 carbon atoms ;
A resin composition containing the fatty acid ester in an amount of 0.3 to 1.0% by weight with respect to 100% by weight of the polymer (however , glycerin fatty acid ester and polyglycerin fatty acid ester as an antistatic agent) And ethylene oxide adduct of higher alcohol, ethylene oxide adduct of aromatic hydroxy compound, ethylene oxide adduct of polyhydric alcohol fatty acid ester having hydroxyl group, or ethylene oxide adduct of fat and oil having hydroxyl group,
In the case where the antistatic agent includes a glycerin fatty acid ester, a polyglycerin fatty acid ester, and a diethanolamine fatty acid ester in which an alkyl group may be bonded to a nitrogen atom,
As an antistatic agent, glycerin fatty acid ester, polyglycerin fatty acid ester, ethylene oxide adduct of higher alcohol, ethylene oxide adduct of aromatic hydroxy compound, ethylene oxide adduct of polyhydric alcohol fatty acid ester having hydroxyl group, or The case of containing an ethylene oxide adduct of fat and oil having a hydroxyl group, and a diethanolamine fatty acid ester in which an alkyl group may be bonded to a nitrogen atom, and a case where the compound represented by the following general formula (1) is included are excluded.

[In the above formula (1), Q ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, and Q ² is an organic group having 6 to 10 carbon atoms having an aromatic ring, and M ⁺ Is a sodium cation, potassium cation, ammonium, phosphonium, and a is 0 or 1. ]). The resin composition according to claim 1 , wherein the fatty acid ester is a diglycerin unsaturated fatty acid ester. The polymer is tetracyclo [4.4.0.1 ^2,5 . The resin composition according to claim 1 or 2 , which is a copolymer of ( ^17,10 ) -3-dodecene and ethylene. The resin composition according to any one of claims 1 to 3 , further comprising a glycerin fatty acid ester. The resin composition according to any one of claims 1 to 4 , wherein the glass transition point of the cyclic olefin polymer represented by the general formula (7) is in the range of 130 to 160 ° C. The molded object obtained by hardening | curing the resin composition in any one of Claims 1-5 . The optical component which consists of a molded object of Claim 6 . An fθ lens comprising the optical component according to claim 7 . An imaging lens comprising the optical component according to claim 7 . A prism comprising the optical component according to claim 7 . A light guide plate comprising the optical component according to claim 7 . An on-vehicle camera lens component comprising the optical component according to claim 7 .