KR102104540B1 - Cyclic olefin resin composition - Google Patents

Abstract

An object of the present invention is to provide a resin composition capable of producing a molded article having excellent heat resistance, light resistance, and moisture heat resistance.
The present invention is a resin composition containing a cyclic olefin-based resin, the compound (A) having a predetermined group, a compound (B) having a predetermined group, an ultraviolet absorber, a condensed phosphate ester, and a main chain. A block copolymer containing styrene, wherein the cyclic olefin resin has a load bending temperature at 1.8 MPa measured for a test piece not subjected to annealing by a method in accordance with ISO 75-1,2. 125 ° C or higher, and the content of the compound (A) and the compound (B) is the mass part of the compound (A) relative to 100 parts by mass of the cyclic olefin resin ≤ the mass of the cyclic olefin resin Provided is a resin composition that satisfies the mass part of compound (B).

Description

Cyclic olefin resin composition

The present invention relates to a cyclic olefin resin composition.

The cyclic olefin-based resin is a resin having a skeleton of a cyclic olefin in the main chain, and is a resin having many characteristics such as high transparency, high heat distortion temperature, low birefringence, and hydrolysis resistance. For this reason, cyclic olefin resins are used in various fields requiring such characteristics.

In particular, from the viewpoint of exhibiting high heat resistance, high transparency, and low birefringence, cyclic olefin resins are used as raw materials for optical devices such as lenses, light guide plates, and diffraction gratings. For example, Patent Document 1 discloses that a cyclic olefin-based resin containing a specific repeating unit in a predetermined ratio can be used as a raw material such as an optical lens.

[Patent Document 1] Japanese Patent Application Publication No. 2013-18962

However, there is a need to develop a composition containing a cyclic olefin-based resin capable of obtaining a molded article that has good heat resistance, light resistance, and moisture heat resistance at a higher balance and does not easily generate yellowing or cracks.

This invention was made | formed in order to solve the said subject, The objective is to provide the resin composition which can manufacture a molded article excellent in heat resistance, light resistance, and moisture heat resistance.

The present inventors have repeatedly studied in order to solve the above problems. As a result, it was found that the above problems can be solved according to a composition containing a specific component together with a cyclic olefin-based resin having a predetermined load bending temperature, and the present invention has been completed. More specifically, the present invention provides the following.

(1) cyclic olefin resin,

Compound (A) having a 3,5-di-tert-butyl-4-hydroxyphenyl group,

A compound (B) having a 2,2,6,6-tetramethyl-4-piperidyl group or 1,2,2,6,6-pentamethyl-4-piperidyl group, and

UV absorbers,

Condensed phosphate ester,

As a resin composition containing a block copolymer containing styrene in the main chain,

The cyclic olefin-based resin is a method according to ISO 75-1,2, and the load bending temperature at 1.8 MPa measured for a test piece without annealing is 125 ° C or higher,

The content of the compound (A) and the compound (B) is the mass part of the compound (A) with respect to 100 parts by mass of the cyclic olefin-based resin ≤ the mass of the compound (B) with respect to 100 parts by mass of the cyclic olefin-based resin A resin composition that satisfies parts by mass.

(2) The content of the ultraviolet absorber and the compound (B) is the mass of the compound (B) relative to 100 parts by mass of the ultraviolet absorber relative to 100 parts by mass of the cyclic olefin resin. The resin composition according to (1), which satisfies the wealth.

(3) The resin composition according to (1) or (2), wherein the cyclic olefin-based resin contains an additional copolymer of norbornene and ethylene.

(4) (1) to (3), wherein the compound (A) contains pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] The resin composition according to any one of the preceding.

(5) The compound (B) is C12 To C21 fatty acid and C18 unsaturated fatty acid 2,2,6,6-tetramethyl-4-piperidyl ester, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly [{6-morpholino-1,3,5-triazine-2,4-diyl} {(1,2,2,6,6-pentamethyl-4-piperidyl) imino} hexamethylene { (1,2,2,6,6-pentamethyl-4-piperidyl) imino}], and poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4 -Piperidyl) imino}], and the resin composition according to any one of (1) to (4), including at least one selected from the group consisting of compounds represented by the following formula (1).

(6) The ultraviolet absorber is 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylmethyl) phenol, 2,2'-methylenebis [6- ( 2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2- [4,6-bis (2,4-dimethylphenyl) -1,3, 5-triazine-2-yl] -5- (octyloxy) phenol, bis {2- [4- (4,6-diphenyl-1,3,5-triazin-2-yl) -3-hydr Hydroxyphenoxy] ethyl} dodecanedioate, and at least one selected from the group consisting of tetra-ethyl-2,2- (1,4-phenylene-dimethylidene) -bismalonate, (1) The resin composition according to any one of (5) to (5).

(7) The resin composition according to any one of (1) to (6), wherein the condensed phosphoric acid ester contains 1,3-phenylenebis (di-2,6-xylenylphosphate).

(8) The block copolymer has a styrene content of 45% by mass or more and 70% by mass or less, and at the same time, includes (1) to (7) a hydride of a block copolymer of styrene with butadiene and / or isoprene. ) The resin composition according to any one of the above.

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can manufacture a molded article excellent in heat resistance, light resistance, and moisture heat resistance is provided.

Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments.

<Resin composition>

The resin composition of the present invention is a method according to ISO 75-1,2, and a cyclic olefin resin having a load bending temperature at 1.8 MPa measured at 125 MPa or higher measured at a test specimen without annealing is 3,5. -Compound (A) having di-tert-butyl-4-hydroxyphenyl group and 2,2,6,6-tetramethyl-4-piperidyl group or 1,2,2,6,6-pentamethyl- It is a resin composition containing the compound (B) having a 4-piperidyl group, a UV absorber, a condensed phosphoric acid ester, and a block copolymer containing styrene in the main chain. Hereinafter, the configuration of the resin composition of the present invention will be described.

(Cyclic olefin resin)

The cyclic olefin-based resin in the present invention is a method according to ISO 75-1,2, and the load bending temperature at 1.8 MPa measured for a test piece not subjected to annealing (hereinafter referred to as "cyclic olefin-based resin") Load bending temperature ”) is not particularly limited as long as it is at least 125 ° C and is a polymer or copolymer containing a structural unit derived from a cyclic olefin in the main chain. When the load bending temperature of the cyclic olefin resin contained in the resin composition is 125 ° C or higher, sufficient heat resistance and moisture heat resistance can be provided to the molded article obtained from the resin composition. The lower limit of the load bending temperature of the cyclic olefin resin is preferably 125 ° C or higher from the viewpoint of easy suppression of yellowing of the molded article obtained from the resin composition. The upper limit of the load bending temperature of the cyclic olefin-based resin is preferably 170 ° C or lower, and more preferably 165 ° C or lower. The load bending temperature in the case where two or more types of cyclic olefin resins are used in combination in the present invention means a load bending temperature of a resin mixture in which all cyclic olefin resins are mixed.

The cyclic olefin-based resin having the above-mentioned load bending temperature, for example, adjusts the proportion of monomers (for example, norbornene or ethylene, etc.) constituting the cyclic olefin-based resin, or has a different glass transition point. It can be produced by blending an olefin-based resin or the like.

Examples of the polymer or copolymer containing a structural unit derived from a cyclic olefin in the main chain include, for example, an additive polymer of a cyclic olefin or a hydrogenated product thereof, an additional copolymer of a cyclic olefin and an α-olefin, or a hydrogenated product thereof. You can. The cyclic olefin resin may be used alone or in combination of two or more.

In addition, examples of the cyclic olefin-based resin include those in which the unsaturated compound having a polar group is grafted and / or copolymerized in the polymer or the copolymer containing a structural unit derived from a cyclic olefin in the main chain.

Examples of the polar group include a carboxyl group, an acid anhydride group, an epoxy group, an amide group, an ester group and a hydroxyl group, and examples of the unsaturated compound having a polar group include (meth) acrylic acid, maleic acid and maleic anhydride. , Itaconic anhydride, glycidyl (meth) acrylate, alkyl (meth) acrylate (1-10 carbon atoms), alkyl maleate (1-10 carbon atoms), (meth) acrylamide, (meth) acrylic acid-2 -Hydroxyethyl and the like.

Moreover, a commercially available resin can also be used as said copolymer used as cyclic olefin resin in this invention. Examples of commercially available cyclic olefin resins include, for example, TOPAS (registered trademark) (manufactured by TOPAS Advanced Polymers), Apel (registered trademark) (manufactured by Mitsui Chemicals), Zeonex (registered trademark) (manufactured by Japan Corporation), and Zeo. Noah (registered trademark) (manufactured by Japan Corporation), Aton (registered trademark) (manufactured by JSR), and the like.

Particularly preferred examples of the addition copolymer of the cyclic olefin and the α-olefin include [1] a structural unit derived from an α-olefin having 2 to 20 carbon atoms, and [2] the cyclic olefin represented by the following general formula (I). A copolymer containing the structural unit derived from it is mentioned.

(In the formula, R ¹ to R ¹² may be the same or different, respectively, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group,

R ⁹ and R ¹⁰ , R ¹¹ and R ¹² may be integrated to form a divalent hydrocarbon group,

R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may also form a ring with each other.

In addition, n represents 0 or a positive integer,

When n is 2 or more, R ⁵ to R ⁸ may be the same or different from each repeating unit.)

[[1] α-olefins with 2 to 20 carbon atoms]

The α-olefin having 2 to 20 carbon atoms is not particularly limited. For example, the same thing as Unexamined-Japanese-Patent No. 2007-302722 can be mentioned. In addition, these α-olefins may be used alone or in combination of two or more. Among these, ethylene alone is most preferred.

[[2] cyclic olefin represented by general formula (I)]

The cyclic olefin represented by general formula (I) is demonstrated. R ¹ to R ¹² in the general formula (I) may be the same or different, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. As a specific example of the cyclic olefin represented by general formula (I), the thing similar to JP 2007-302722 A can be mentioned.

These cyclic olefins may be used alone or in combination of two or more. Among these, it is preferable to use bicyclo [2.2.1] hepta-2-ene (common name: norbornene) alone.

[1] The polymerization method of the α-olefin having 2 to 20 carbon atoms and the cyclic olefin represented by [2] general formula (I) and the hydrogenation method of the obtained polymer are not particularly limited, and can be carried out according to a known method. You can.

Further, the polymerization catalyst used is not particularly limited, and a conventionally known catalyst such as a Ziegler-Natta-based, metathesis-based, or metallocene-based catalyst can be used to obtain a cyclic olefin-based resin by a known method. .

In addition, the hydrogenation method of the obtained cyclic olefin resin is not particularly limited, and a conventionally known method can be applied.

The cyclic olefin-based resin is necessary in a range not to impair the object of the present invention, other than the above-mentioned [1] α-olefin component having 2 to 20 carbon atoms and [2] the cyclic olefin component represented by the general formula (I). Accordingly, other copolymerizable unsaturated monomer components may be contained. The unsaturated monomer which may be optionally copolymerized is not particularly limited, and examples thereof include hydrocarbon-based monomers containing two or more carbon-carbon double bonds in one molecule. As a specific example of the hydrocarbon-based monomer containing two or more carbon-carbon double bonds in one molecule, the same ones as JP 2007-302722 A may be mentioned.

Among the above, as the cyclic olefin-based resin in the present invention, an addition copolymer of norbornene and ethylene is particularly preferred from the viewpoint of particularly easily exhibiting the effects of the present invention.

The lower limit of the glass transition point of the cyclic olefin resin is not particularly limited, but is preferably 130 ° C or higher, and more preferably 145 ° C or higher. When the glass transition point of the cyclic olefin-based resin is in this range, it is easy to impart heat resistance to the molded article obtained from the resin composition. Although the upper limit of the glass transition point of a cyclic olefin resin is not specifically limited, Preferably it is 190 degrees C or less, More preferably, it is 185 degrees C or less. When the glass transition point of the cyclic olefin resin is in this range, yellowing of the molded article obtained from the resin composition is easily suppressed.

As the glass transition point (Tg) of the cyclic olefin resin, a value measured under conditions of a heating rate of 20 ° C / min according to the DSC method (method described in ISO 11357-1, -2, -3) is adopted.

The lower limit of the cyclic olefin-based resin content is not particularly limited, but is preferably 65.0 mass% or more, more preferably 95.0 mass% or more in the resin composition. The upper limit of the cyclic olefin resin content is not particularly limited, but is preferably 98.0 mass% or less in the resin composition.

(Compound (A) and Compound (B))

Compound (A) having a 3,5-di-tert-butyl-4-hydroxyphenyl group (hereinafter also referred to as "compound (A)"), and 2,2,6,6-tetramethyl-4- The compound (B) having a piperidyl group or 1,2,2,6,6-pentamethyl-4-piperidyl group (hereinafter also referred to as "compound (B)") is cyclic with an ultraviolet absorber described later. By blending with the olefin-based resin-containing composition, the molded article obtained from the resin composition can be provided with a balance of heat resistance, light resistance, and moisture heat resistance.

In addition, as a result of examination by the present inventors, the contents of the compound (A) and the compound (B) satisfy the following relational expression 1, that is, the content of the compound (A) and the content of the compound (B) are the same, or the compound ( It has been found that by blending so that the content of the compound (B) is greater than the content of A), it is possible to impart particularly heat-resistant, light-resistant, and moisture-resistant heat to a molded article obtained from a resin composition.

Mass parts of compound (A) relative to 100 parts by mass of cyclic olefin resin ≤ Mass parts of compound (B) relative to 100 parts by mass of cyclic olefin resin ...

The content of the compound (A) and the compound (B) is not particularly limited as long as the relationship 1 is satisfied, but the content of the compound (B) is preferably 1 time or more, more preferably, the content of the compound (A) It may be 2 times or more, more preferably 3 times or more. In addition, the content of the compound (B) may be preferably 5 times or less, more preferably 3 times or less, based on the content of the compound (A).

Compound (A) may be hindered phenol (a compound containing a t-butyl group at the ortho positions on both sides with respect to a phenolic hydroxyl group). As a result of examination by the present inventor, instead of hindered phenol, one hindered phenol (a compound containing t-butyl group in one of the ortho positions on both sides with respect to the phenolic hydroxyl group) is also obtained from the resin composition. It has been found that the molded article cannot sufficiently provide heat resistance and light resistance.

The compound (A) is not particularly limited as long as it is a compound having a 3,5-di-tert-butyl-4-hydroxyphenyl group, but, for example, a monocyclic compound (for example, 2,6-di-t- Butyl-p-cresol, etc., polycyclic compounds (eg, 4,4'-methylenebis (2,6-di-t-butylphenol)) connected by a hydrocarbon group or a group containing a sulfur atom, 1,3, 5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, etc.), a compound having an ester group or an amide group (for example, n-octadecyl-3 -(4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, n-octadecyl-2- (4'-hydroxy-3', 5'-di-t-butyl Phenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate], 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di- t-pentylphenylacrylate, di-n-octadecyl-3,5-di-t-part Tyl-4-hydroxybenzylphosphonate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-dihydrocinnamamide), N, N'-ethylenebis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionamide], N, N'-tetramethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionamide], N, N'-hexamethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionamide], N, N'-bis [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, and the like). have. The compound (A) may be used alone or in combination of two or more.

Among the above, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] is particularly preferred from the viewpoint of easily exhibiting the effects of the present invention.

The compound (B) is not particularly limited as long as it is a compound having a 2,2,6,6-tetramethyl-4-piperidyl group or 1,2,2,6,6-pentamethyl-4-piperidyl group. Compound (B) may be used alone or in combination of two or more.

As a compound having a 2,2,6,6-tetramethyl-4-piperidyl group, 2,2,6,6-tetramethyl-4-piperidine stearin, fatty acid (C12-21 and C18 unsaturated) 2, 2,6,6-tetramethyl-4-piperidyl ester, poly [{6-morpholino-1,3,5-triazine-2,4-diyl} {(2,2,6,6- Tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (2,2 ', 6,6'- Tetramethyl-4-piperidyl) sebacate, dimethyl-1-succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [{6 -(1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) Imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], tetrakis (2,2,6,6-tetramethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, 1,1 '-(1,2-ethanediyl) bis (3, 3,5,5-tetramethylpiperazinone), (mix 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mix {2,2,6,6-tetramethyl-4- Piperidyl / β, β, β ', β'-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3 , 4-butanetetracarboxylate, poly [6-N-morpholinyl-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidine Dill) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imide], N, N'-bis (2,2,6,6-tetramethyl-4- Piperidyl) Condensate of hexamethylenediamine and 1,2-dibromoethane, [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- ( 2,2,6,6-tetramethyl-4-piperidyl) imino] propionamide, compounds represented by the following formula (1), and the like.

As a compound having 1,2,2,6,6-pentamethyl-4-piperidyl group, propanedioic acid [{4-methoxyphenyl} methylene] -bis (1,2,2,6,6- Pentamethyl-4-piperidyl) ester, bis- (1,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl ) -2-n-butylmalonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) {[3,5-bis (1,1-dimethylethyl) -4-hydro Hydroxyphenyl] methyl} butylmalonate, bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly [{6-morpholino-1,3,5 -Triazine-2,4-diyl} {(1,2,2,6,6-pentamethyl-4-piperidyl) imino} hexamethylene {(1,2,2,6,6-pentamethyl -4-piperidyl) imino}] (mix 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, Mix {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ', β'-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, N, N'-bis (3-aminoph Ropil) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5- And triazine condensates.

As the compound (B), fatty acids (C12-21 and C18 unsaturated) 2,2,6,6-tetramethyl-4-piperidyl ester, bis, especially from the viewpoint of easily exhibiting the effects of the present invention, among the above (2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly [{6-morpholino-1,3,5-triazine-2,4-diyl} {(1,2 , 2,6,6-pentamethyl-4-piperidyl) imino} hexamethylene {(1,2,2,6,6-pentamethyl-4-piperidyl) imino}], and poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-py Peridyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], and any one or more of the compounds represented by the following formula (1) is preferred. .

The content of the compounds (A) and (B) is not particularly limited as long as the relationship 1 is satisfied. In particular, from the viewpoint of easily exhibiting the effects of the present invention, the lower limit of the content of the compound (A) is preferably 0.01 parts by mass or more, and more preferably 0.10 parts by mass or more with respect to 100 parts by mass of the cyclic olefin resin. The upper limit of the content of the compound (A) is not particularly limited, but is 2.00 parts by mass or less with respect to 100 parts by mass of the cyclic olefin resin. The lower limit of the amount of the compound (B) is preferably 0.01 parts by mass or more, and more preferably 0.10 parts by mass or more with respect to 100 parts by mass of the cyclic olefin resin. The upper limit of the content of the compound (B) is not particularly limited, but is preferably 2.00 parts by mass or less with respect to 100 parts by mass of the cyclic olefin resin.

Moreover, the lower limit of the content of the compound (A) is preferably 0.01% by mass or more, and more preferably 0.10% by mass or more in the resin composition. Although the upper limit of the content of the compound (A) is not particularly limited, it is preferably 2.00% by mass or less in the resin composition. The lower limit of the amount of the compound (B) is preferably 0.01% by mass or more, and more preferably 0.10% by mass or more in the resin composition. Although the upper limit of the content of the compound (B) is not particularly limited, it is preferably 2.00% by mass or less in the resin composition.

(Ultraviolet absorbent)

The ultraviolet absorber is compounded with the cyclic olefin-based resin-containing composition together with the compounds (A) and (B), so that the molded article obtained from the resin composition can be provided with heat resistance, light resistance, and moisture heat resistance in a balance.

The type of the ultraviolet absorber is not particularly limited, but a benzotriazole-based ultraviolet absorber (2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylmethyl) phenol, 2, 2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], etc.), triazine-based ultraviolet absorbers (2- [4, 6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, bis {2- [4- (4,6-diphenyl-1) , 3,5-triazin-2-yl) -3-hydroxyphenoxy] ethyl} dodecanedioate, etc., other ultraviolet absorbers (tetra-ethyl-2,2- (1,4-phenylene-dimethyl) Liden) -bismalonate, etc.).

The ultraviolet absorbers can be used alone or in combination of two or more.

The content of the ultraviolet absorber is not particularly limited. From the viewpoint of easily increasing the heat resistance, light resistance, and moisture heat resistance in a balanced manner, the lower limit of the content of the ultraviolet absorber is preferably 0.01 parts by mass or more, and more preferably 0.10 parts by mass or more with respect to 100 parts by mass of the cyclic olefin resin. The upper limit of the content of the ultraviolet absorber is not particularly limited, but is 2.00 parts by mass or less with respect to 100 parts by mass of the cyclic olefin resin. Moreover, the lower limit of the content of the ultraviolet absorber is preferably 0.01% by mass or more, more preferably 0.10% by mass or more in the resin composition. The upper limit of the content of the ultraviolet absorber is preferably 2.00% by mass or less in the resin composition.

From the viewpoint of particularly easily increasing the heat resistance, light resistance, and moisture heat resistance in a balanced manner, the content of the ultraviolet absorber and the compound (B) is the same as the following relationship 2, that is, the content of the ultraviolet absorber and the content of the compound (B) are the same. Alternatively, it is preferable to blend so that the content of the compound (B) is higher than the content of the ultraviolet absorber.

Mass part of compound (B) relative to 100 parts by mass of the ultraviolet absorber relative to 100 parts by mass of the cyclic olefin resin.

The content of the ultraviolet absorber and the compound (B), the content of the compound (B) may be preferably 1 time or more, more preferably 2 times or more, and even more preferably 3 times or more with respect to the content of the ultraviolet absorber. . Further, the content of the compound (B) may be 5 times or less, more preferably 3 times or less, with respect to the content of the ultraviolet absorber.

(Condensed phosphate ester)

The condensed phosphate ester can impart good light resistance to the molded article obtained from the cyclic olefin-based resin-containing composition without inhibiting the action of the compound (A), compound (B), and ultraviolet absorber, and suppress yellowing of the molded article. can do.

As the condensed phosphoric acid ester, specifically, 1,3-phenylenebis (diphenylphosphate), 1,3-phenylenebis (di-4methylphenylphosphate), 1,3-phenylenebis (di-2,6) -Xylenylphosphate), 1,4-phenylenebis (diphenylphosphate), 1,4-phenylenebis (di-2,6-xylenylphosphate), 4,4'-biphenylenebis ( Diphenylphosphate), 4,4'-biphenylenebis (di-2,6-xylenylphosphate); Hydroquinone phosphates and biphenol phosphates corresponding to these phosphates; And condensed phosphate esters such as biphenol-A phosphates.

Among these, 1,3-phenylenebis (di-2,6-xylenyl phosphate) is particularly preferred from the viewpoint of easy light resistance.

The condensed phosphoric acid ester may be used alone or in combination of two or more.

The content of the condensed phosphoric acid ester is not particularly limited. From the viewpoint of easy to impart light resistance to the molded article obtained from the resin composition, the lower limit of the content of the condensed phosphoric acid ester is preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass or more with respect to 100 parts by mass of the cyclic olefin resin. . The upper limit of the content of the condensed phosphoric acid ester is not particularly limited, but is 1.00 parts by mass or less with respect to 100 parts by mass of the cyclic olefin resin. Moreover, the lower limit of the content of the condensed phosphate ester is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, in the resin composition. The upper limit of the content of the condensed phosphoric acid ester is preferably 1.00% by mass or less in the resin composition.

(Block copolymer containing styrene in the main chain)

The block copolymer containing styrene in the main chain (hereinafter also referred to as "block copolymer in the present invention") is cyclic without inhibiting the action of the compound (A), compound (B), and ultraviolet absorber. The molded article obtained from the olefin-based resin-containing composition can be provided with good heat and moisture resistance, and crack generation in a heat-resistant environment in the molded article can be suppressed.

The block copolymer in the present invention is not particularly limited as long as it contains styrene in the main chain, and those having an aromatic vinyl-based polymer block (hard segment) and a rubber block (soft segment), hydrogenated substances or the like can be used. The hard segment and the soft segment may each be formed of one type of monomer, or may be formed of a plurality of monomers. The block copolymer in this invention can be used individually by 1 type and can also use 2 or more types together.

The aromatic vinyl compound (monomer) forming a hard segment contains at least substituted or unsubstituted styrene. By containing substituted or unsubstituted styrene as the aromatic vinyl compound, cracks in the molded article can be suppressed when the molded article obtained from the resin composition is subjected to moist heat treatment. Moreover, by containing substituted or unsubstituted styrene as an aromatic vinyl compound, the refractive index of the block copolymer in the present invention is easily approached to the refractive index of the cyclic olefin resin, and it is easy to increase the transparency of the molded article obtained from the resin composition. .

In addition, when the content of the repeating unit derived from the aromatic vinyl-based compound in the block copolymer in the present invention is large, cracks are likely to occur inside the resin molded body when the molded body obtained from the resin composition is subjected to moist heat treatment. On the other hand, since the difference between the refractive index of the block copolymer in the present invention and the refractive index of the cyclic olefin-based resin as a matrix becomes too large when the content is small, the light from the dispersion of the block copolymer in the present invention Refraction and scattering become large, and the transparency of the molded body may be impaired. Therefore, the content of the repeating unit derived from the aromatic vinyl-based compound is adjusted while considering the above problems and the degree of cracking. The upper limit of the content (the content of the repeating unit derived from the aromatic vinyl-based polymer block in the block copolymer in the present invention) is preferably in order to prevent cracking when the resin molded body is subjected to moist heat treatment. It is 70 mass% or less, more preferably 65 mass% or less, and its lower limit is preferably 45 mass% or more, more preferably 51 mass% or more.

Styrene content in the block copolymer in the present invention (derived from substituted or unsubstituted styrene in the block copolymer in the present invention) from the viewpoint of particularly easy to suppress the occurrence of yellowing or cracking of the molded article obtained from the resin composition. With respect to the content of the repeating unit to be performed), the upper limit is preferably 70% by mass or less, more preferably 65% by mass or less, and the lower limit is preferably 45% by mass or more, more preferably 51% by mass or more.

Examples of the substituted styrene include α-alkyl substituted styrenes such as α-methylstyrene, α-ethylstyrene, and α-methyl-p-methylstyrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, 2,4,6-trimethylstyrene, ot-butylstyrene, pt-butylstyrene, p-cyclohexylstyrene, etc. Nuclear alkyl substituted styrene; and nuclear halogenated styrenes such as o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-bromostyrene, and 2-methyl-4-chlorostyrene.

As a compound (monomer) forming a soft segment, what constitutes a normal block copolymer can be used. Specifically, α-olefins (eg, α-C2-12 olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, etc.), diene-based monomers (butadiene, isoprene, etc.) and the like.

When the content of the repeating unit derived from the compound forming the soft segment in the block copolymer in the present invention is increased, cracks are less likely to occur in molding when the molded body obtained from the resin composition is subjected to moist heat treatment. On the other hand, if the content is large, the difference between the refractive index of the block copolymer in the present invention and the refractive index of the cyclic olefin-based resin as the matrix becomes too large, and thus the refractive index of light from the dispersion of the block copolymer in the present invention There is a problem in that scattering becomes large and transparency of the molded body is impaired. Therefore, the content of the repeating unit derived from the compound is adjusted while considering the above problems and the degree of cracking. As for the said content (the content of the repeating unit derived from the compound which forms a soft segment in the block copolymer in this invention), its upper limit is preferably 55 mass% or less, more preferably 49 mass% or less, and The lower limit is preferably 30% by mass or more, and more preferably 35% by mass or more.

As specific examples of the block copolymer in the present invention, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene copolymer (SBS), hydrogenated styrene-butadiene copolymer (H-SBR), hydrogenated styrene-butadiene -Styrene copolymer (SEBS), hydrogenated styrene-isoprene-styrene copolymer (SEPS), styrene-isobutylene-styrene copolymer (SIBS), hydrogenated styrene-isoprene-butadiene-styrene copolymer (SEEPS), styrene -Isoprene-styrene copolymer (SIS).

The block copolymer in the present invention is a styrene content (derived from substituted or unsubstituted styrene in the block copolymer in the present invention), from the viewpoint of particularly easily suppressing the occurrence of yellowing and cracks in molded articles obtained from the resin composition. The repeating unit content) is 45% by mass or more and 70% by mass or less, and at the same time, it is preferable to include a hydride of a block copolymer of styrene and butadiene and / or isoprene (SEBS, SEPS, SEEPS, etc.).

The content of the block copolymer in the present invention is not particularly limited. From the viewpoint of easy to impart moist heat resistance to the molded article obtained from the resin composition, the lower limit of the content of the block copolymer in the present invention is preferably 0.1 parts by mass or more, more preferably 100 parts by mass of the cyclic olefin resin. Is 0.5 part by mass or more. Although the upper limit of content of the block copolymer in this invention is not specifically limited, It is 1.0 mass part or less with respect to 100 mass parts of cyclic olefin resins. In addition, the lower limit of the content of the block copolymer in the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more in the resin composition. The upper limit of the content of the block copolymer in the present invention is preferably 1.0% by mass or less in the resin composition.

(Other ingredients)

Components other than the above can be blended into the resin composition of the present invention. Examples of such other components include thermoplastic resins other than cyclic olefin resins, additives such as lubricants, stabilizers, strengthening agents, plasticizers, and pigments. The type and amount of these resins and additives can be appropriately selected depending on the desired effect.

<Method for manufacturing resin composition>

The manufacturing method of the resin composition of this invention is not specifically limited. In general, the resin composition of the present invention can be prepared according to known equipment and methods for preparing the resin composition. For example, necessary components can be mixed and kneaded using a single-screw or twin-screw extruder or other melt-kneading apparatus to prepare a pellet for molding. It is also possible to melt-knead the entire ingredients by simultaneously feeding them into the hopper, or to melt-knead some ingredients through the side feed.

<Method of manufacturing molded products>

The molded article can be produced by a conventionally known molding method using the resin composition of the present invention. Molding methods, such as an injection molding method and an extrusion molding method, are mentioned as a conventionally well-known molding method.

The molded article obtained from the resin composition of the present invention is not particularly limited, but a camera lens, a pickup lens, a projector lens, a lens of an illuminating device (such as an LED or a cold cathode tube, etc.), a lamp cover, a light guide body, and a resin window Trees, optical films, optical sheets, and the like.

<Molded product of the present invention>

The molded article obtained from the resin composition of the present invention has good heat resistance, light resistance, and moisture heat resistance, and the occurrence of yellowing and cracks is suppressed. Evaluation of heat resistance, light resistance, heat and humidity resistance, and the occurrence of yellowing and cracks can be evaluated by the methods shown in Examples.

[ Example ]

Hereinafter, the present invention will be described by showing examples and comparative examples. However, the present invention is not limited to the following examples.

<Material of resin composition>

In the proportions of the materials shown in Tables 1 to 4, the mixture was melt-kneaded at a cylinder temperature of 260 to 300 ° C using a 30 mmΦ twin-screw extruder to obtain resin compositions of Examples and Comparative Examples. The following was used as a material for the resin composition. The proportion of each material was expressed in parts by mass relative to 100 parts by mass of the cyclic olefin resin.

(Cyclic olefin resin)

As the cyclic olefin resin, any one or more of the following four "COCs" were used. All of these cyclic olefin resins are addition copolymers of norbornene and ethylene.

COC-1: Load deflection temperature = 120 ℃, Tg = 134 ℃ , MVR = 48cm 3/10 bun, TOPAS Advanced Polymers Co.

COC-2: Load deflection temperature = 120 ℃, Tg = 142 ℃ , MVR = 13cm 3/10 bun, TOPAS Advanced Polymers Co.

COC-3: Load deflection temperature = 140 ℃, Tg = 158 ℃ , MVR = 4cm 3/10 bun, TOPAS Advanced Polymers Co.

COC-4: Load deflection temperature = 160 ℃, Tg = 178 ℃ , MVR = 1.5cm 3/10 bun, TOPAS Advanced Polymers Co.

The "load bending temperature" of the COC and "load bending temperature (° C) of the cyclic olefin resin" in Table 4 are used for each cyclic olefin resin (a resin mixture when a plurality of cyclic olefin resins are included). It shows the load bending temperature at 1.8 MPa measured by the method according to ISO 75-1,2 for the test piece produced and not subjected to annealing treatment.

The "Tg" of the COC refers to a glass transition point measured for each cyclic olefin-based resin under the conditions of a heating rate of 20 ° C / min by a method in accordance with ISO 11357-1, -2, -3.

The "MVR" of the above-mentioned COC refers to a melt volume rate measured for each cyclic olefin-based resin under a condition of a measurement temperature of 260 ° C and a load of 2160 g in a method conforming to ISO 1133.

(Compound (A))

As the compound (A) having a 3,5-di-tert-butyl-4-hydroxyphenyl group, the following was used.

Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] ("Irganox1010", manufactured by BASF Japan Co., Ltd.)

In addition, the following one hindered phenol was also used instead of the compound (A).

Ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tril) propionate] ("Irganox245", manufactured by BASF Japan Co., Ltd.)

Bis [3,3-bis (3'-t-butyl-4'-hydroxyphenyl) lactic acid] ethylene ("HostanoxO3", manufactured by Clariant Japan Co., Ltd.)

(Compound (B))

As a compound (B) having a 2,2,6,6-tetramethyl-4-piperidyl group or 1,2,2,6,6-pentamethyl-4-piperidyl group, the following was used.

Poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4- Piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] ("LA-94G" manufactured by Adeka Corporation)

Poly [{6-morpholino-1,3,5-triazine-2,4-diyl} {(1,2,2,6,6-pentamethyl-4-piperidyl) imino} hexamethylene {(1,2,2,6,6-pentamethyl-4-piperidyl) imino}] ("UV-3529", manufactured by Cytec Industries Inc.)

Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate ("Tinuvin770", manufactured by BASF Japan Co., Ltd.)

Compound represented by the following formula (1) ("Chimassorb 2020", manufactured by BASF Japan Co., Ltd.)

(Ultraviolet absorbent)

As the ultraviolet absorber, the following was used.

2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylmethyl) phenol ("Tinuvin234", manufactured by BASF Japan Co., Ltd.)

2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] ("LA-31" manufactured by Adeka Corporation)

Bis {2- [4- (4,6-diphenyl-1,3,5-triazin-2-yl) -3-hydroxyphenoxy] ethyl} dodecanedioate ("LA-1000", Inc.) ADEKA)

2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol ("CYASORB UV-1164" manufactured by CYTEC INDUSTRIES INC )

Tetra-ethyl-2,2- (1,4-phenylene-dimethylidene) -bismalonate ("Hostavin B-CAP", manufactured by Clariant Japan Co., Ltd.)

(Condensed phosphate ester)

The following was used as a condensed phosphoric acid ester.

1,3-phenylenebis (di-2,6-xylenyl phosphate) ("PX-200", manufactured by Daihachi Chemical Co., Ltd.)

(Block copolymer)

As a block copolymer containing styrene in the main chain, the following was used.

`` Septon 8104 '' (SEBS, styrene content 60 mass%, Kurarese Co., Ltd.)

`` Septon 8105 '' (SEBS, styrene content 65 mass%, Kurarese Co., Ltd.)

`` Septon 2104 '' (SEPS, styrene content 65 mass%, Kurarese Co., Ltd.)

「Hybrar KL7350」 (SEEPS, Styrene content 50% by mass, Kurarese Co., Ltd.)

「Turftech H1043」 (SEBS, styrene content 67% by mass, manufactured by Asahi Chemical Co., Ltd.)

`` DYNARON 9901P '' (SEBS, styrene content 54% by mass, manufactured by JSR Corporation)

(additive)

The following was used as an additive.

Lubricant: Pentaerythritol tetrastearate (PETS), manufactured by Nippon Co., Ltd.

In Tables 1 to 4, "Do you satisfy the ultraviolet absorber ≤ (B)?" In the composition of each resin composition, the content of the ultraviolet absorber and the content of the compound (B), "100 parts by weight of the cyclic olefin resin This item indicates whether or not the relationship of "parts by mass of the ultraviolet absorber to parts by mass of the compound (B) with respect to 100 parts by mass of the cyclic olefin resin" is satisfied. "Are (A) ≤ (B) satisfied?" In the composition of each resin composition, the content of the compound (A) and the content of the compound (B), "the compound to 100 parts by weight of the cyclic olefin resin ( This item indicates whether or not the relationship of "parts by mass of A)" by parts by mass of compound (B) relative to 100 parts by mass of cyclic olefin resin) is satisfied. In any of the items, "YES" is satisfied when satisfied, and "NO" is satisfied when not satisfied.

<Forming of resin composition>

For each resin composition obtained, a plate having a thickness of 70 mm × 70 mm × 2 mm was molded at an injection molding machine (manufactured by Sumitomo Heavy Industries Co., Ltd., trade name: SE75D) at a cylinder temperature of 260 to 300 ° C and a mold temperature of 110 to 135 ° C.

<Evaluation of yellowness and crack occurrence>

Each plate after molding was evaluated for the yellowness (YI value) before and after the test and the presence or absence of cracks by using the following three tests (heat aging test, # 320 or # 275 xenon test, and moisture heat test). . The yellowness (DIN6167) was measured using a color difference meter made by YKB-Gardnar GmbH. The results are shown in Tables 1-4. In the table, "initial YI" indicates the yellowness of each plate before the test.

(Heat aging test)

Each plate was subjected to heat treatment at 115 ° C, 125 ° C, or 130 ° C for 1000 hours, and yellowness was measured after the heat treatment ("YI @ 115 ° C x 1000h", "YI @ 125 ° C x 1000h", " YI @ 130 ℃ × 1000h ”). Then, the difference (ΔYI) in yellowness before and after heat treatment was calculated. It shows that the heat resistance of a molded article is high, so that (DELTA) YI is small.

(Xenon test)

Each plate was irradiated with light for 500 hours, and yellowness was measured after light irradiation (section of "YI @ 500 hour irradiation"). For light irradiation, using a Suga Tester Super Xenon Weather Meter, filter # 275 (cut below 275nm) or filter # 320 (cut below 320nm), black panel temperature 89 ° C, humidity 50% RH, irradiation density 162W / m ² (300 ~ 400nm), total energy was carried out under conditions of 291.5MJ / m ² . Then, the difference in yellowness (ΔYI) before and after light irradiation was calculated. It shows that the light resistance of a molded article is high, so that (DELTA) YI is small.

Moreover, the haze value after the said light irradiation was also measured. Specifically, the haze value was measured by a method in conformity with JIS K7136 using a haze meter (manufactured by Toyo Seiki Co., Ltd., trade name: Haze Guard II). It shows that the light resistance of a molded article is high, so that a haze value is small.

(Humidity heat test)

Each plate was exposed to an environment of 85 ° C and 85% humidity for 1000 hours, and the presence or absence of cracks after exposure was observed with an optical microscope. The molded article in which no crack was observed indicates that the moisture heat was high.

As shown in Table 1, the molded article obtained from the resin composition of the present invention had good heat resistance, light resistance, and heat and moisture resistance, and the occurrence of yellowing and cracks was suppressed. This tendency was confirmed irrespective of the type of ultraviolet absorber used.

On the other hand, the molded article obtained from the resin composition that does not meet the requirements of the resin composition of the present invention was inferior in heat resistance, light resistance, and heat resistance to moisture, and significant yellowing or cracking was observed after each test.

As shown in Table 2, the molded article obtained from the resin composition that did not satisfy any one of the requirements of the resin composition of the present invention was inferior in any of heat resistance, light resistance, and heat resistance to moisture. For this reason, it was found that according to the resin composition that satisfies the requirements of the resin composition of the present invention, it is possible to obtain a molded article having good properties for all of heat resistance, light resistance, and heat resistance to moisture.

As shown in Table 3, the molded article obtained from the resin composition of the present invention had good heat resistance, light resistance, and heat and moisture resistance, and the occurrence of yellowing and cracks was suppressed. In particular, as understood from the comparison with Examples and Comparative Example 17, for example, even if all the components included in the resin composition of the present invention are included, the compound for 100 parts by mass of the cyclic olefin resin ( The mass part of A) ≤ mass part of the compound (B) relative to 100 parts by mass of the cyclic olefin-based resin ”was found to be unable to realize a property with good balance as in the present invention unless the relationship is satisfied.

As shown in Table 4, it was found that, among the requirements of the resin composition of the present invention, if the requirements regarding the load bending temperature of the cyclic olefin resin were not satisfied, the resulting molded article was significantly inferior in heat resistance.

Claims (8)

Cyclic olefin resin,
Compound (A) having a 3,5-di-tert-butyl-4-hydroxyphenyl group,
A compound (B) having a 2,2,6,6-tetramethyl-4-piperidyl group or 1,2,2,6,6-pentamethyl-4-piperidyl group, and
UV absorbers,
Condensed phosphate ester,
As a resin composition comprising a block copolymer containing styrene in the main chain,
The cyclic olefin-based resin is a method according to ISO 75-1,2, and the load bending temperature at 1.8 MPa measured for a test piece without annealing is 125 ° C or higher,
The content of the compound (A) and the compound (B) is based on 100 parts by mass of the compound (A) with respect to 100 parts by mass of the cyclic olefin resin; A resin composition that satisfies parts by mass. According to claim 1,
The content of the ultraviolet absorber and the compound (B) satisfies the mass part of the compound (B) with respect to 100 parts by mass of the ultraviolet absorber with respect to 100 parts by mass of the cyclic olefin resin. , Resin composition. The method according to claim 1 or 2,
The cyclic olefin-based resin comprises a norbornene and ethylene addition copolymer, a resin composition. The method according to claim 1 or 2,
The compound (A) comprises a pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], a resin composition. The method according to claim 1 or 2,
The compound (B) is C12 To C21 fatty acid and C18 unsaturated fatty acid 2,2,6,6-tetramethyl-4-piperidyl ester, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly [{6-morpholino-1,3,5-triazine-2,4-diyl} {(1,2,2,6,6-pentamethyl-4-piperidyl) imino} hexamethylene { (1,2,2,6,6-pentamethyl-4-piperidyl) imino}], and poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4 -Piperidyl) imino}], and a resin composition comprising at least one selected from the group consisting of compounds represented by the following formula (1).
[Formula 1]

The method according to claim 1 or 2,
The ultraviolet absorber is 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylmethyl) phenol, 2,2'-methylenebis [6- (2H-benzo) Triazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-tri Azin-2-yl] -5- (octyloxy) phenol, bis {2- [4- (4,6-diphenyl-1,3,5-triazin-2-yl) -3-hydroxyphenoxy ] Ethyl} dodecanedioate, and tetra-ethyl-2,2- (1,4-phenylene-dimethylidene) -bismalonate. The method according to claim 1 or 2,
The condensed phosphoric acid ester comprises 1,3-phenylenebis (di-2,6-xylenylphosphate), a resin composition. The method according to claim 1 or 2,
The said block copolymer has a styrene content of 45 mass% or more and 70 mass% or less, and at the same time, the resin composition containing the hydride of the block copolymer of styrene and 1 or more types of butadiene and isoprene.