WO2019013174A1 - Cycloolefin resin composition - Google Patents
Cycloolefin resin composition Download PDFInfo
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- WO2019013174A1 WO2019013174A1 PCT/JP2018/025910 JP2018025910W WO2019013174A1 WO 2019013174 A1 WO2019013174 A1 WO 2019013174A1 JP 2018025910 W JP2018025910 W JP 2018025910W WO 2019013174 A1 WO2019013174 A1 WO 2019013174A1
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- cyclic olefin
- piperidyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
Definitions
- the present invention relates to cyclic olefin resin compositions.
- the cyclic olefin resin is a resin having a cyclic olefin skeleton in the main chain, and is a resin having many features such as high transparency, high thermal deformation temperature, low birefringence, hydrolysis resistance, and the like. For this reason, cyclic olefin resin is used in various fields where these characteristics are required.
- cyclic olefin resins are used as raw materials for lenses, light guide plates, optical devices such as diffraction gratings and the like because they can exhibit high heat resistance, high transparency, and low birefringence.
- Patent Document 1 discloses that a cyclic olefin resin containing a specific repeating unit at a predetermined ratio can be used as a raw material for an optical lens or the like.
- the present invention has been made to solve the above-described problems, and an object thereof is to provide a resin composition capable of producing a molded article having good heat resistance, light resistance, and moisture and heat resistance. is there.
- the present inventors have intensively studied to solve the above problems.
- the composition which contains a specific component with cyclic olefin resin which has predetermined load deflection temperature it discovers that the above-mentioned subject can be solved and came to complete the present invention. More specifically, the present invention provides the following.
- cyclic olefin resin A 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 a 1,2,2,6,6-pentamethyl-4-piperidyl group; UV absorber, Condensed phosphate ester, A resin composition comprising a block copolymer containing styrene in the main chain,
- the cyclic olefin-based resin has a deflection temperature under load of at least 125 ° C. at 1.8 MPa measured on a test piece which has not been subjected to annealing treatment by a method in accordance with ISO 75-1, 2.
- the content of the compound (A) and the compound (B) is: part by mass of the compound (A) based on 100 parts by mass of the cyclic olefin resin ⁇ mass of the compound (B) based on 100 parts by mass of the cyclic olefin resin A resin composition that fills parts.
- the content of the ultraviolet absorber and the compound (B) is, based on 100 parts by mass of the cyclic olefin resin, based on 100 parts by mass of the ultraviolet absorber based on 100 parts by mass of the cyclic olefin resin
- the compound (B) is a fatty acid (C12-21 and C18 unsaturated) 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 From the compound of formula (1)
- the resin composition in any one of (1) to
- the UV 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- Triazin-2-yl] -5- (octyloxy) phenol, bis ⁇ 2- [4- (4,6-diphenyl-1,3,5-triazin-2-yl) -3-hydroxyphenoxy] ethyl ⁇ dodecane
- the resin composition according to any one of (1) to (5), comprising one or more selected from the group consisting of geoate and tetra-ethyl-2,2- (1,4-phenylene-dimethylidene) -bismalonate object.
- the block copolymer has a styrene content of 45% by mass to 70% by mass, and includes a hydride of a block copolymer of styrene and butadiene and / or isoprene.
- the resin composition in any one of (7).
- the resin composition which can manufacture a molded article in which all of heat resistance, light resistance, and heat-and-moisture resistance are favorable is provided.
- the resin composition of the present invention is a cyclic olefin resin having a deflection temperature under load of 125 ° C. or higher at 1.8 MPa measured on a test piece which has not been subjected to annealing treatment by a method in accordance with ISO 75-1, 2.
- the resin composition comprises a compound (B) having a 4-piperidyl group, an ultraviolet light absorber, a condensed phosphoric acid ester, and a block copolymer containing styrene in the main chain.
- the structure of the resin composition of this invention is demonstrated.
- the cyclic olefin-based resin in the present invention is a deflection temperature under load of 1.8 MPa measured on a test piece which has not been subjected to annealing treatment according to ISO 75-1, 2 (hereinafter, “load deflection temperature of cyclic olefin-based resin It is not particularly limited as long as it is a polymer or copolymer containing a structural unit derived from a cyclic olefin in its main chain) at 125 ° C. or higher. When the deflection temperature under load of the cyclic olefin resin contained in the resin composition is 125 ° C.
- the lower limit value of the deflection temperature under load of the cyclic olefin resin is preferably 125 ° C. or more from the viewpoint of easily suppressing yellowing of a molded article obtained from the resin composition.
- the upper limit of the deflection temperature under load of the cyclic olefin resin is preferably 170 ° C. or less, more preferably 165 ° C. or less.
- load deflection temperature means the load deflection temperature of the resin mixture which mixed all the cyclic olefin resin.
- the cyclic olefin resin having the above deflection temperature under load for example, adjusts the ratio of monomers (for example, norbornene, ethylene etc.) constituting the cyclic olefin resin, or blends cyclic olefin resins having different glass transition points It can be produced by carrying out.
- a polymer or copolymer containing a structural unit derived from cyclic olefin in the main chain for example, an addition polymer of cyclic olefin or a hydrogenated product thereof, an addition copolymer of cyclic olefin and ⁇ -olefin or hydrogen thereof An additive etc. can be mentioned.
- the cyclic olefin resins can be used alone or in combination of two or more.
- cyclic olefin resin what the unsaturated compound which has a polar group further grafts and / or copolymerizes in the said polymer or said copolymer which contains the structural unit derived from cyclic olefin in a principal chain is also mentioned.
- a polar group a carboxyl group, an acid anhydride group, an epoxy group, an amide group, an ester group, a hydroxyl group etc.
- a unsaturated compound which has a polar group (meth) acrylic acid, maleic acid Acid, maleic anhydride, itaconic anhydride, glycidyl (meth) acrylate, alkyl (meth) acrylate (1 to 10 carbon atoms) ester, alkyl maleate (1 to 10 carbon atoms) ester, (meth) acrylamide, (meth) ) Acrylic acid 2-hydroxyethyl etc. can be mentioned.
- cyclic olefin-based resins examples include TOPAS (registered trademark) (manufactured by TOPAS Advanced Polymers), APEL (registered trademark) (manufactured by Mitsui Chemicals, Inc.), Zeonex (registered trademark) (manufactured by Nippon Zeon), Zeonor (registered trademark) (manufactured by Nippon Zeon Co., Ltd.), Arton (registered trademark) (manufactured by JSR Corporation), and the like can be mentioned.
- TOPAS registered trademark
- APEL registered trademark
- Zeonex registered trademark
- Zeonor registered trademark
- Arton registered trademark
- Particularly preferable examples of the addition copolymer of cyclic olefin and ⁇ -olefin are [1] structural units derived from ⁇ -olefin having 2 to 20 carbon atoms, and [2] represented by the following general formula (I) And a copolymer containing a structural unit derived from cyclic olefin.
- R 1 to R 12 may be the same or different, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, R 9 and R 10 and R 11 and R 12 may be united to form a divalent hydrocarbon group, R 9 or R 10 and R 11 or R 12 may form a ring with each other.
- n is 0 or a positive integer, When n is 2 or more, R 5 to R 8 may be the same or different among the respective repeating units.
- ⁇ -olefin of 2 to 20 carbon atoms The ⁇ -olefin having 2 to 20 carbon atoms is not particularly limited. For example, the same one as in JP-A-2007-302722 can be mentioned. These ⁇ -olefins may be used alone or in combination of two or more. Of these, ethylene alone is most preferred.
- 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.
- 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.
- the cyclic olefin represented by the general formula (I) the same as those described in JP-A-2007-302722 can be mentioned.
- cyclic olefins may be used alone or in combination of two or more.
- bicyclo [2.2.1] hept-2-ene (common name: norbornene) is preferably used alone.
- the polymerization method of the [1] ⁇ -olefin having 2 to 20 carbon atoms and the cyclic olefin represented by the general formula (I) and the hydrogenation method of the obtained polymer are not particularly limited. Can be carried out according to known methods.
- the polymerization catalyst to be used is also not particularly limited, and a cyclic olefin resin can be obtained by a known method using a conventionally known catalyst such as Ziegler-Natta type, metathesis type or metallocene type catalyst.
- the hydrogenation method of the obtained cyclic olefin resin is also not particularly limited, and conventionally known methods can be applied.
- other copolymerizable unsaturated monomer components may be contained.
- the unsaturated monomer which may be optionally copolymerized is not particularly limited.
- a hydrocarbon monomer containing two or more carbon-carbon double bonds in one molecule, etc. Can be mentioned.
- the hydrocarbon-based monomer containing two or more carbon-carbon double bonds in one molecule the same as those described in JP-A-2007-302722 can be mentioned.
- cyclic olefin-based resin in the present invention an addition copolymer of norbornene and ethylene is particularly preferable from the viewpoint that the effects of the present invention are easily exhibited.
- the lower limit value of the glass transition point of the cyclic olefin resin is not particularly limited, but is preferably 130 ° C. or more, more preferably 145 ° C. or more. It is easy to provide heat resistance to the molded article obtained from a resin composition as it is a range to which the glass transition point of cyclic olefin resin takes such a thing.
- the upper limit value of the glass transition point of the cyclic olefin resin is not particularly limited, but is preferably 190 ° C. or less, more preferably 185 ° C. or less. It is easy to suppress yellowing of the molded article obtained from a resin composition as it is a range which the glass transition point of cyclic olefin resin takes.
- Tg glass transition point of the cyclic olefin resin
- a value measured by a DSC method (method described in ISO 11357-1, -2, -3) under a condition of a temperature rising rate of 20 ° C / min is adopted.
- the lower limit value of the content of the cyclic olefin resin is not particularly limited, but it is preferably 65.0% by mass or more, more preferably 95.0% by mass or more in the resin composition.
- the upper limit of content of cyclic olefin resin is not specifically limited, Preferably it is 98.0 mass% or less in a 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 a 1,2,2,6,6-pentamethyl-4-piperidyl group (hereinafter, also referred to as a “compound (B)”) is a cyclic olefin resin together with a UV absorber described later Heat resistance, light resistance, and heat and humidity resistance can be imparted with good balance to molded articles obtained from the resin composition by blending in the contained composition.
- the content of the compound (A) and the compound (B) is not particularly limited as long as the relationship 1 above is satisfied, but the content of the compound (B) is preferably 1 times the content of the compound (A) Or more, more preferably 2 times or more, and further 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, the content of the compound (A).
- the compound (A) may be a hindered phenol (a compound containing a t-butyl group in the ortho position on both sides with respect to the phenolic hydroxyl group).
- a hindered phenol a compound containing a t-butyl group in the ortho position on both sides with respect to the phenolic hydroxyl group.
- the compound (A) is not particularly limited as long as it is a compound having a 3,5-di-tert-butyl-4-hydroxyphenyl group, and examples thereof include monocyclic compounds (eg, 2,6-di-t- (B-butyl-p-cresol etc.), polycyclic compounds linked by a hydrocarbon group or a group containing a sulfur atom (eg, 4,4′-methylenebis (2,6-di-t-butylphenol), 1,3, 5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene etc., compounds having an ester group or an amide group (eg, n-octadecyl-3- (4) '-Hydroxy-3', 5'-di-t-butylphenyl) propionate, n-octadecyl-2- (4'-hydroxy-3 ', 5'-di-t-butylphenyl)
- pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] is preferable from the viewpoint that the effects of the present invention are easily exhibited.
- 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 a 1,2,2,6,6-pentamethyl-4-piperidyl group.
- the compound (B) can be used alone or in combination of two or more.
- Examples of compounds having a 2,2,6,6-tetramethyl-4-piperidyl group include 2,2,6,6-tetramethyl-4-piperidine stearin, fatty acids (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 succinate -1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [ ⁇ 6- (1,1,3,3-tetramethylbutyl) amino-1 , 3,5- Liazine-2,4-d
- Examples of the compound having a 1,2,2,6,6-pentamethyl-4-piperidyl group include 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-butyl malonate Bis (1,2,2,6,6-pentamethyl-4-piperidyl) ⁇ [3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl ⁇ butyl malonate, bis- ( N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly [ ⁇ 6-morpholino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (1,2,2,2,7 6, 6 pen Methyl-4-piperidyl) im
- fatty acids C12-21 and C18 unsaturated 2,2,6,6-tetramethyl-4-piperidyl ester, bis, among the above-described ones, in particular, from the viewpoint that the effects of the present invention are easily exhibited.
- the content of the compounds (A) and (B) is not particularly limited as long as the relationship 1 above is satisfied.
- the lower limit value of the content of the compound (A) is preferably 0.01 parts by mass or more, and more preferably 0.10 parts by mass with respect to 100 parts by mass of the cyclic olefin resin, from the viewpoint of easily achieving the effects of the present invention. Part or more.
- the upper limit of content of a compound (A) is not specifically limited, It is 2.00 mass parts or less with respect to 100 mass parts of cyclic olefin resin.
- the lower limit value of the content 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 content of a compound (B) is not specifically limited, Preferably it is 2.00 mass parts or less with respect to 100 mass parts of cyclic olefin resin.
- the lower limit of the content of the compound (A) 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 compound (A) is not particularly limited, but it is preferably 2.00% by mass or less in the resin composition.
- the lower limit of the content 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.
- the upper limit of the content of the compound (B) is not particularly limited, but it is preferably 2.00% by mass or less in the resin composition.
- UV absorber imparts heat resistance, light resistance, and moist heat resistance to the molded article obtained from the resin composition in a well-balanced manner by combining the compound (A) and (B) with the cyclic olefin resin-containing composition. it can.
- UV absorber is not particularly limited, but benzotriazole-based UV 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., and other UV absorbers (tetra-ethyl-2,2- (1,4-phenylene-dimethylidene)) Bismalonate, etc.) and
- the ultraviolet absorber may be used alone or in combination of two or more.
- the content of the ultraviolet absorber is not particularly limited.
- the lower limit of the content of the ultraviolet absorber is preferably 0.01 parts by mass or more, more preferably 100 parts by mass of the cyclic olefin resin, from the viewpoint of easily enhancing heat resistance, light resistance, and moist heat resistance in a well-balanced manner. Is 0.10 parts by mass or more.
- the upper limit of content of a ultraviolet absorber is not specifically limited, It is 2.00 mass parts or less with respect to 100 mass parts of cyclic olefin resin.
- the lower limit of the content of the ultraviolet absorber is preferably 0.01% by mass or more, and 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.
- the content of the ultraviolet absorber and the compound (B) should satisfy the following relational expression 2, that is, the content of the ultraviolet absorber and It is preferable to combine so that content of a compound (B) may be equal, or content of a compound (B) may become larger than content of a ultraviolet absorber.
- the content of the ultraviolet absorber and the compound (B) is preferably such that the content of the compound (B) is 1 or more times, more preferably 2 or more times, still more preferably 3 times the content of the ultraviolet light absorber It may be more than.
- the content of the compound (B) may be preferably 5 times or less, more preferably 3 times or less, the content of the ultraviolet light absorber.
- condensed phosphate ester imparts good light resistance to molded articles obtained from the cyclic olefin resin-containing composition without inhibiting the effects of the compound (A), the compound (B), and the ultraviolet light absorber as described above. It is possible to suppress yellowing of the molded article.
- 1,3 phenylene bis (diphenyl phosphate), 1,3 phenylene bis (di-4 methyl phenyl phosphate), 1,3 phenylene bis (di-2,6 xylenyl) as the condensed phosphoric acid ester Phosphate), 1,4 phenylene bis (diphenyl phosphate), 1,4 phenylene bis (di-2,6 xylenyl phosphate), 4,4 'biphenylene bis (diphenyl phosphate), 4,4' biphenylene bis (di-) 2, 6 xylenyl phosphates); hydroquinone phosphates corresponding to these phosphates, biphenol phosphates; condensed phosphate esters such as biphenol-A phosphates.
- 1,3 phenylene bis (di-2,6 xylenyl phosphate) is preferable from the viewpoint of particularly easily enhancing light resistance.
- the condensed phosphoric acid ester can 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 easily imparting light resistance to a molded article obtained from the resin composition, the lower limit value of the content of the condensed phosphate is preferably 0.05 parts by mass or more with respect to 100 parts by mass of the cyclic olefin resin, More preferably, it is 0.10 mass part or more.
- the upper limit of content of condensation phosphoric acid ester is not specifically limited, It is 1.00 mass parts or less with respect to 100 mass parts of cyclic olefin resin.
- the lower limit of the content of the condensed phosphate is preferably 0.05% by mass or more, and more preferably 0.10% by mass or more in the resin composition.
- the upper limit value of the content of the condensed phosphoric acid ester is preferably 1.00% by mass or less in the resin composition.
- the block copolymer containing styrene in the main chain (hereinafter, also referred to as “the block copolymer in the present invention”) does not inhibit the action of the above compound (A), compound (B) and ultraviolet absorber.
- the block copolymer in the present invention does not inhibit the action of the above compound (A), compound (B) and ultraviolet absorber.
- good moisture and heat resistance can be imparted to a molded article obtained from the cyclic olefin-based resin-containing composition, and cracking in a molded article under moist and heat resistant environment 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 polymer block (hard segment) and a rubber block (soft segment), or the like A water additive etc. 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 the present invention can be used singly or in combination of two or more.
- the aromatic vinyl compound (monomer) forming the hard segment contains at least substituted or unsubstituted styrene.
- substituted or unsubstituted styrene as the aromatic vinyl compound, it is possible to suppress the formation of cracks in the molded product when the molded product obtained from the resin composition is subjected to wet heat treatment.
- the substituted or unsubstituted styrene is contained as the aromatic vinyl compound, the refractive index of the block copolymer in the present invention can be easily brought close to the refractive index of the cyclic olefin resin, and can be obtained from the resin composition. It is easy to increase the transparency of molded articles.
- the molded product obtained from the resin composition is cracked in the inside of the resin molded product when subjected to wet heat treatment Is easy to enter.
- the content is too small, the difference between the refractive index of the block copolymer in the present invention and the refractive index of the cyclic olefin resin as a matrix becomes too large, so from the dispersion of the block copolymer in the present invention The refraction and scattering of light may increase, and the transparency of the molded body may be impaired.
- the content of the repeating unit derived from the aromatic vinyl compound is adjusted in consideration of the above problem and the degree of the crack.
- the above content (the content of the repeating unit derived from the aromatic vinyl polymer block in the block copolymer of the present invention) in order to make it difficult for the crack to occur when the resin molded product is wet heat treated
- the upper limit thereof is preferably 70% by mass or less, more preferably 65% by mass or less, and the lower limit thereof is preferably 45% by mass or more, more preferably 51% by mass or more.
- the styrene content in the block copolymer of the present invention (substituted or unsubstituted in the block copolymer of the present invention, from the viewpoint of particularly easily suppressing the yellowing and the occurrence of cracks of molded articles obtained from the resin composition
- the upper limit of the content of the repeating unit derived from styrene 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 is there.
- substituted styrene As substituted styrene, ⁇ -alkyl substituted styrene such as ⁇ -methylstyrene, ⁇ -ethylstyrene, ⁇ -methyl-p-methylstyrene, etc .; o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4- Nuclear alkyl substituted styrenes such as dimethylstyrene, ethylstyrene, 2,4,6-trimethylstyrene, o-t-butylstyrene, p-t-butylstyrene, p-cyclohexylstyrene, etc.
- ⁇ -alkyl substituted styrene such as ⁇ -methylstyrene, ⁇ -ethylstyrene, ⁇ -methyl-p-methylstyrene, etc
- o-chlorostyrene o-chlorostyrene, m-chlorostyrene, Nuclear halogenated styrenes such as p-chlorostyrene, p-bromostyrene, 2-methyl-4-chlorostyrene and the like can be mentioned.
- ⁇ -olefins ethylene, propylene, 1-butene, 1-hexene, ⁇ -C 2-12 olefins such as 1-octene etc.
- diene monomers butadiene, isoprene etc.
- the molded product obtained from the resin composition is less likely to be cracked when subjected to wet heat treatment.
- the difference between the refractive index of the block copolymer in the present invention and the refractive index of the cyclic olefin resin as a matrix becomes too large, so from the dispersion of the block copolymer in the present invention There is a problem in that the light refraction and scattering of the light are increased, and the transparency of the molded body is impaired.
- the content of the repeating unit derived from the above compound is adjusted in consideration of the above problem and the degree of the crack.
- the upper limit of the content is preferably 55% by mass or less, more preferably 49% by mass or less
- the lower limit thereof is preferably 30% by mass or more, more preferably 35% by mass or more.
- block copolymer in the present invention examples include styrene-butadiene copolymer (SBR), styrene-butadiene-styrene copolymer (SBS), hydrogenated styrene-butadiene copolymer (H-SBR), hydrogen Additive Styrene-Butadiene-Styrene Copolymer (SEBS), Hydrogenated Styrene-Isoprene-Styrene Copolymer (SEPS), Styrene-isobutylene-Styrene Copolymer (SIBS), Hydrogenated Styrene-Isoprene-Butadiene-Styrene Copolymer And coalesced (SEEPS), styrene-isoprene-styrene copolymer (SIS).
- SBR styrene-butadiene copolymer
- SBS hydrogenated styrene-but
- the styrene content (substituted or non-substituted in the block copolymer in the present invention, from the viewpoint of particularly easily suppressing the occurrence of yellowing and cracking of molded articles obtained from the resin composition).
- the content of repeating units derived from substituted styrene is 45% by mass or more and 70% by mass or less, and a hydrogenated block copolymer of styrene and butadiene and / or isoprene (SEBS, SEPS, SEEPS, etc. Those containing) are preferred.
- the content of the block copolymer in the present invention is not particularly limited.
- the lower limit value of the content of the block copolymer in the present invention is preferably 0.1 mass to 100 mass parts of the cyclic olefin resin from the viewpoint of easily imparting moist heat resistance to a molded article obtained from the resin composition.
- the content is at least part, more preferably at least 0.5 parts by mass.
- 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 resin.
- 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.
- the resin composition of the present invention may contain components other than the above.
- examples of such other components include thermoplastic resins other than cyclic olefin resins, and additives such as lubricants, stabilizers, reinforcing agents, plasticizers and pigments.
- additives such as lubricants, stabilizers, reinforcing agents, plasticizers and pigments.
- the types and amounts of these resins and additives can be appropriately selected according to the effect to be obtained.
- the method for producing the resin composition of the present invention is not particularly limited.
- the resin composition of the present invention can be prepared by using equipment and methods known as a method for preparing a resin composition.
- necessary components can be mixed and kneaded using a single- or twin-screw extruder or other melt-kneading apparatus to prepare molding pellets. All components may be simultaneously fed from the hopper and melt-kneaded may be good, or some components may be fed from the side feed port and melt-kneaded.
- a molded article can be manufactured by a conventionally known molding method using the resin composition of the present invention.
- conventionally known molding methods include molding methods such as injection molding and extrusion molding.
- 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 illumination device (such as an LED or a cold cathode tube), a lamp cover, a conductor A light, a resin window, an optical film, an optical sheet etc. are mentioned.
- the molded article obtained from the resin composition of the present invention is good in all of heat resistance, light resistance, and heat and humidity resistance, and generation of yellowing and cracks is suppressed.
- the heat resistance, light resistance, moisture heat resistance, and evaluation of yellowing and occurrence of cracks can be evaluated by the methods shown in the examples.
- ⁇ Material of Resin Composition> The resin compositions of Examples and Comparative Examples were obtained by melt-kneading at a cylinder temperature of 260 to 300 ° C. using a 30 mm ⁇ twin-screw extruder at a material ratio as shown in Tables 1-4. The following was used as a material of the resin composition. In addition, the ratio of each material was shown as a mass part with respect to 100 mass parts of cyclic olefin resin.
- Cyclic olefin resin As cyclic olefin resin, any 1 or more types of following 4 types of "COC" were used. All of these cyclic olefin resins are addition copolymers of norbornene and ethylene.
- the “load deflection temperature” of the above COC and “load deflection temperature (° C.) of cyclic olefin resin” in Table 4 refer to each cyclic olefin resin (resin mixture in the case of containing multiple cyclic olefin resins).
- the deflection temperature under load of 1.8 MPa measured by the method according to ISO 75-1 and 2 is shown for a test piece prepared by using and not subjected to annealing treatment.
- the "Tg" of the above-mentioned COC indicates the glass transition point of each cyclic olefin resin measured by the method according to ISO 11357-1, -2, -3 under the condition of a temperature rising rate of 20 ° C / min.
- MVR of the above-mentioned COC shows the melt volume rate measured on the conditions of measurement temperature 260 ° C, and load 2160g by the method based on ISO1133 about each cyclic olefin system resin.
- Compound (A) The following was used as a compound (A) having a 3,5-di-tert-butyl-4-hydroxyphenyl group. Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] ("Irganox 1010", manufactured by BASF Japan Ltd.) Also, in place of the compound (A), the following hindered phenols were also used.
- UV absorber The following was used as an ultraviolet absorber.
- 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylmethyl) phenol ("Tinuvin 234", manufactured by BASF Japan Ltd.)
- 2,2'-Methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] ("LA-31", manufactured by ADEKA Corporation)
- LA-31 manufactured by ADEKA Corporation
- Bis ⁇ 2- [4- (4,6-diphenyl-1,3,5-triazin-2-yl) -3-hydroxyphenoxy] ethyl ⁇ dodecanedioate ("LA-1000", manufactured by ADEKA Corporation)
- 2- [4,6-Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol (CYASORB UV-1164” from CYTEC IN
- Condensed phosphate ester (Condensed phosphate ester) The following was used as condensed phosphoric acid ester. 1,3 phenylene bis (di-2,6 xylenyl phosphate) ("PX-200" manufactured by Daihachi Chemical Industry Co., Ltd.)
- Block copolymer The following was used as a block copolymer containing styrene in the main chain.
- "Septon 8104" SEBS, styrene content 60% by mass, Kuraray Co., Ltd.
- Septon 8105 SEBS, styrene content 65% by mass, Kuraray Co., Ltd.
- "Septon 2104" SEPS, styrene content 65% by mass, Kuraray Co., Ltd.
- Hybrar KL 7350 SEEPS, styrene content 50% by mass, Kuraray Co., Ltd.
- "Tough Tech H1043 SEBS, styrene content 67% by mass, manufactured by Asahi Kasei Corporation
- "DYNARON 9901P SEBS, 54% by mass styrene content, manufactured by JSR Corporation
- Lubricant Pentaerythritol tetrastearate (PETS), manufactured by NOF Corporation
- the haze value after said light irradiation was also measured.
- the haze value was measured by a method according to JIS K7136 using a haze meter (manufactured by Toyo Seiki Seisaku-sho, trade name: Haze Guard II). The smaller the haze value, the higher the light resistance of the molded article.
- the molded articles obtained from the resin composition of the present invention were all good in heat resistance, light resistance and moisture and heat resistance, and the occurrence of yellowing and cracks was suppressed. Such a tendency was observed regardless of the type of UV absorber used.
- molded articles obtained from a resin composition which does not satisfy the requirements of the resin composition of the present invention are inferior in heat resistance, light resistance and moisture and heat resistance, and remarkable yellowing and cracks are observed after each test.
- the molded articles obtained from the resin composition of the present invention were all good in heat resistance, light resistance and moisture and heat resistance, and the occurrence of yellowing and cracks was suppressed.
- the compound (A) it was found that, as in the present invention, it is not possible to realize well-balanced properties as in the present invention, unless the relationship of “parts by mass of part) ⁇ parts by mass of compound (B) to 100 parts by mass of cyclic olefin resin”.
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Abstract
Description
3,5-ジ-tert-ブチル-4-ヒドロキシフェニル基を有する化合物(A)と、
2,2,6,6-テトラメチル-4-ピペリジル基又は1,2,2,6,6-ペンタメチル-4-ピペリジル基を有する化合物(B)と、
紫外線吸収剤と、
縮合リン酸エステルと、
主鎖にスチレンを含むブロック共重合体と、を含む樹脂組成物であって、
前記環状オレフィン系樹脂は、ISO75-1,2に準拠する方法で、アニール処理を施していない試験片について測定した1.8MPaにおける荷重たわみ温度が125℃以上であり、
前記化合物(A)及び前記化合物(B)の含有量が、前記環状オレフィン系樹脂100質量部に対する前記化合物(A)の質量部≦前記環状オレフィン系樹脂100質量部に対する前記化合物(B)の質量部を満たす、樹脂組成物。 (1) cyclic olefin resin,
A 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 a 1,2,2,6,6-pentamethyl-4-piperidyl group;
UV absorber,
Condensed phosphate ester,
A resin composition comprising a block copolymer containing styrene in the main chain,
The cyclic olefin-based resin has a deflection temperature under load of at least 125 ° C. at 1.8 MPa measured on a test piece which has not been subjected to annealing treatment by a method in accordance with ISO 75-1, 2.
The content of the compound (A) and the compound (B) is: part by mass of the compound (A) based on 100 parts by mass of the cyclic olefin resin ≦ mass of the compound (B) based on 100 parts by mass of the cyclic olefin resin A resin composition that fills parts.
本発明の樹脂組成物は、ISO75-1,2に準拠する方法で、アニール処理を施していない試験片について測定した1.8MPaにおける荷重たわみ温度が125℃以上である環状オレフィン系樹脂を、3,5-ジ-tert-ブチル-4-ヒドロキシフェニル基を有する化合物(A)と、2,2,6,6-テトラメチル-4-ピペリジル基又は1,2,2,6,6-ペンタメチル-4-ピペリジル基を有する化合物(B)と、紫外線吸収剤と、縮合リン酸エステルと、主鎖にスチレンを含むブロック共重合体とともに含む樹脂組成物である。以下、本発明の樹脂組成物の構成について説明する。 <Resin composition>
The resin composition of the present invention is a cyclic olefin resin having a deflection temperature under load of 125 ° C. or higher at 1.8 MPa measured on a test piece which has not been subjected to annealing treatment by a method in accordance with ISO 75-1, 2. A compound (A) having a 5, 5-di-tert-butyl-4-hydroxyphenyl group, and a 2,2,6,6-tetramethyl-4-piperidyl group or 1,2,2,6,6-pentamethyl- The resin composition comprises a compound (B) having a 4-piperidyl group, an ultraviolet light absorber, a condensed phosphoric acid ester, and a block copolymer containing styrene in the main chain. Hereinafter, the structure of the resin composition of this invention is demonstrated.
本発明における環状オレフィン系樹脂は、ISO75-1,2に準拠する方法で、アニール処理を施していない試験片について測定した1.8MPaにおける荷重たわみ温度(以下、「環状オレフィン系樹脂の荷重たわみ温度」ともいう。)が125℃以上であり、環状オレフィンに由来する構造単位を主鎖に含む重合体又は共重合体であれば、特に限定されない。樹脂組成物に含まれる環状オレフィン系樹脂の荷重たわみ温度が125℃以上であると、樹脂組成物から得られる成形品に十分な耐熱性、耐湿熱性を付与できる。環状オレフィン系樹脂の荷重たわみ温度の下限値は、樹脂組成物から得られる成形品の黄変を抑制しやすいという観点から、好ましくは125℃以上である。環状オレフィン系樹脂の荷重たわみ温度の上限値は、好ましくは170℃以下、より好ましくは165℃以下である。なお、本発明において2種以上の環状オレフィン系樹脂を併用した場合は、荷重たわみ温度とは、全ての環状オレフィン系樹脂を混合した樹脂混合物の荷重たわみ温度を意味する。 (Cyclic olefin resin)
The cyclic olefin-based resin in the present invention is a deflection temperature under load of 1.8 MPa measured on a test piece which has not been subjected to annealing treatment according to ISO 75-1, 2 (hereinafter, “load deflection temperature of cyclic olefin-based resin It is not particularly limited as long as it is a polymer or copolymer containing a structural unit derived from a cyclic olefin in its main chain) at 125 ° C. or higher. When the deflection temperature under load of the cyclic olefin resin contained in the resin composition is 125 ° C. or more, sufficient heat resistance and moist heat resistance can be imparted to a molded article obtained from the resin composition. The lower limit value of the deflection temperature under load of the cyclic olefin resin is preferably 125 ° C. or more from the viewpoint of easily suppressing yellowing of a molded article obtained from the resin composition. The upper limit of the deflection temperature under load of the cyclic olefin resin is preferably 170 ° C. or less, more preferably 165 ° C. or less. In addition, when using 2 or more types of cyclic olefin resin together in this invention, load deflection temperature means the load deflection temperature of the resin mixture which mixed all the cyclic olefin resin.
R9とR10、R11とR12は、一体化して2価の炭化水素基を形成してもよく、
R9又はR10と、R11又はR12とは、互いに環を形成していてもよい。
また、nは、0又は正の整数を示し、
nが2以上の場合には、R5~R8は、それぞれの繰り返し単位のなかで、それぞれ同一でも異なっていてもよい。) Particularly preferable examples of the addition copolymer of cyclic olefin and α-olefin are [1] structural units derived from α-olefin having 2 to 20 carbon atoms, and [2] represented by the following general formula (I) And a copolymer containing a structural unit derived from cyclic olefin.
R 9 and R 10 and R 11 and R 12 may be united to form a divalent hydrocarbon group,
R 9 or R 10 and R 11 or R 12 may form a ring with each other.
And n is 0 or a positive integer,
When n is 2 or more, R 5 to R 8 may be the same or different among the respective repeating units. )
炭素数2~20のα-オレフィンは、特に限定されるものではない。例えば、特開2007-302722と同様のものを挙げることができる。また、これらのα-オレフィンは、1種単独でも2種以上を同時に使用してもよい。これらのなかでは、エチレンの単独使用が最も好ましい。 [[1] α-olefin of 2 to 20 carbon atoms]
The α-olefin having 2 to 20 carbon atoms is not particularly limited. For example, the same one as in JP-A-2007-302722 can be mentioned. These α-olefins may be used alone or in combination of two or more. Of these, ethylene alone is most preferred.
一般式(I)で示される環状オレフィンについて説明する。一般式(I)におけるR1~R12は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、及び、炭化水素基からなる群より選ばれるものである。一般式(I)で示される環状オレフィンの具体例としては、特開2007-302722と同様のものを挙げることができる。 [[2] cyclic olefin represented by formula (I)]
The cyclic olefin represented by formula (I) will be described. 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 specific examples of the cyclic olefin represented by the general formula (I), the same as those described in JP-A-2007-302722 can be mentioned.
3,5-ジ-tert-ブチル-4-ヒドロキシフェニル基を有する化合物(A)(以下、「化合物(A)」ともいう。)、及び、2,2,6,6-テトラメチル-4-ピペリジル基又は1,2,2,6,6-ペンタメチル-4-ピペリジル基を有する化合物(B)(以下、「化合物(B)」ともいう。)は、後述する紫外線吸収剤とともに環状オレフィン系樹脂含有組成物に配合することにより、樹脂組成物から得られる成形品に、耐熱性、耐光性、及び耐湿熱性をバランスよく付与できる。 (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 a 1,2,2,6,6-pentamethyl-4-piperidyl group (hereinafter, also referred to as a “compound (B)”) is a cyclic olefin resin together with a UV absorber described later Heat resistance, light resistance, and heat and humidity resistance can be imparted with good balance to molded articles obtained from the resin composition by blending in the contained composition.
環状オレフィン系樹脂100質量部に対する化合物(A)の質量部≦環状オレフィン系樹脂100質量部に対する化合物(B)の質量部・・・関係式1 Furthermore, as a result of examination of the present inventor, the contents of compound (A) and compound (B) are satisfied so as to satisfy the following relational expression 1, that is, the contents of compound (A) and the contents of compound (B) By blending so that the content of compound (B) is equal to or greater than the content of compound (A), particularly well-balanced heat resistance, light resistance, and moist heat resistance from the resin composition It has been found that it can be applied to the resulting molded articles.
Mass part of compound (A) to 100 mass parts of cyclic olefin resin ≦ mass part of compound (B) to 100 mass parts of cyclic olefin resin Relational formula 1
紫外線吸収剤は、化合物(A)及び(B)とともに環状オレフィン系樹脂含有組成物に配合することにより、樹脂組成物から得られる成形品に、耐熱性、耐光性、及び耐湿熱性をバランスよく付与できる。 (UV absorber)
The ultraviolet absorber imparts heat resistance, light resistance, and moist heat resistance to the molded article obtained from the resin composition in a well-balanced manner by combining the compound (A) and (B) with the cyclic olefin resin-containing composition. it can.
環状オレフィン系樹脂100質量部に対する紫外線吸収剤の質量部≦環状オレフィン系樹脂100質量部に対する化合物(B)の質量部・・・関係式2 From the viewpoint of enhancing heat resistance, light resistance, and moisture heat resistance particularly well with a good balance, the content of the ultraviolet absorber and the compound (B) should satisfy the following relational expression 2, that is, the content of the ultraviolet absorber and It is preferable to combine so that content of a compound (B) may be equal, or content of a compound (B) may become larger than content of a ultraviolet absorber.
Mass part of UV absorber to 100 parts by mass of cyclic olefin resin ≦ mass part of compound (B) to 100 parts by mass of cyclic olefin resin Relational formula 2
縮合リン酸エステルは、上記の化合物(A)、化合物(B)、及び紫外線吸収剤の作用を阻害せずに、環状オレフィン系樹脂含有組成物から得られる成形品に、良好な耐光性を付与でき、成形品の黄変を抑制できる。 (Condensed phosphate ester)
The condensed phosphate ester imparts good light resistance to molded articles obtained from the cyclic olefin resin-containing composition without inhibiting the effects of the compound (A), the compound (B), and the ultraviolet light absorber as described above. It is possible to suppress yellowing of the molded article.
主鎖にスチレンを含むブロック共重合体(以下、「本発明におけるブロック共重合体」ともいう。)は、上記の化合物(A)、化合物(B)、及び紫外線吸収剤の作用を阻害せずに、環状オレフィン系樹脂含有組成物から得られる成形品に、良好な耐湿熱性を付与でき、成形品における耐湿熱環境下でのクラック発生を抑制できる。 (Block copolymer containing styrene in main chain)
The block copolymer containing styrene in the main chain (hereinafter, also referred to as “the block copolymer in the present invention”) does not inhibit the action of the above compound (A), compound (B) and ultraviolet absorber In addition, good moisture and heat resistance can be imparted to a molded article obtained from the cyclic olefin-based resin-containing composition, and cracking in a molded article under moist and heat resistant environment can be suppressed.
本発明の樹脂組成物には上記以外の成分を配合してもよい。このような他の成分としては、環状オレフィン系樹脂以外の熱可塑性樹脂や、滑剤、安定剤、強化剤、可塑剤、顔料等の添加剤が例示される。これらの樹脂や添加剤の種類や量は、得ようとする効果等に応じて適宜選択できる。 (Other ingredients)
The resin composition of the present invention may contain components other than the above. Examples of such other components include thermoplastic resins other than cyclic olefin resins, and additives such as lubricants, stabilizers, reinforcing agents, plasticizers and pigments. The types and amounts of these resins and additives can be appropriately selected according to the effect to be obtained.
本発明の樹脂組成物の製造方法は特に限定されない。一般に樹脂組成物の調製法として公知の設備と方法により、本発明の樹脂組成物を調製することができる。例えば、必要な成分を混合し、1軸又は2軸の押出機又はその他の溶融混練装置を使用して混練し、成形用ペレットとして調製することができる。全ての成分をホッパから同時に投入して溶融混練もよいし、一部の成分をサイドフィード口から投入して溶融混練してもよい。 <Method for Producing Resin Composition>
The method for producing the resin composition of the present invention is not particularly limited. In general, the resin composition of the present invention can be prepared by using equipment and methods known as a method for preparing a resin composition. For example, necessary components can be mixed and kneaded using a single- or twin-screw extruder or other melt-kneading apparatus to prepare molding pellets. All components may be simultaneously fed from the hopper and melt-kneaded may be good, or some components may be fed from the side feed port and melt-kneaded.
成形品は、本発明の樹脂組成物を用いて、従来公知の成形方法で製造することができる。従来公知の成形方法としては、射出成形法、押出成形法等の成形方法を挙げることができる。 <Production method of molded article>
A molded article can be manufactured by a conventionally known molding method using the resin composition of the present invention. Examples of conventionally known molding methods include molding methods such as injection molding and extrusion molding.
本発明の樹脂組成物から得られる成形品は、耐熱性、耐光性、及び耐湿熱性のいずれもが良好であり、黄変やクラックの発生が抑制されている。耐熱性、耐光性、耐湿熱性、並びに、黄変及びクラックの発生の評価は実施例に示した方法で評価できる。 <Molded Product of the Present Invention>
The molded article obtained from the resin composition of the present invention is good in all of heat resistance, light resistance, and heat and humidity resistance, and generation of yellowing and cracks is suppressed. The heat resistance, light resistance, moisture heat resistance, and evaluation of yellowing and occurrence of cracks can be evaluated by the methods shown in the examples.
表1~4に示す材料と割合で、30mmΦ二軸押出機を用いてシリンダ温度260~300℃にて溶融混練し、実施例及び比較例の樹脂組成物を得た。樹脂組成物の材料として、下記を用いた。なお、各材料の割合は、環状オレフィン系樹脂100質量部に対する質量部として示した。 <Material of Resin Composition>
The resin compositions of Examples and Comparative Examples were obtained by melt-kneading at a cylinder temperature of 260 to 300 ° C. using a 30 mm 二 twin-screw extruder at a material ratio as shown in Tables 1-4. The following was used as a material of the resin composition. In addition, the ratio of each material was shown as a mass part with respect to 100 mass parts of cyclic olefin resin.
環状オレフィン系樹脂として、下記4種の「COC」のいずれか1種以上を使用した。これらの環状オレフィン系樹脂はいずれもノルボルネンとエチレンとの付加共重合体である。
COC-1:荷重たわみ温度=120℃、Tg=134℃、MVR=48cm3/10分、TOPAS Advanced Polymers社製
COC-2:荷重たわみ温度=120℃、Tg=142℃、MVR=13cm3/10分、TOPAS Advanced Polymers社製
COC-3:荷重たわみ温度=140℃、Tg=158℃、MVR=4cm3/10分、TOPAS Advanced Polymers社製
COC-4:荷重たわみ温度=160℃、Tg=178℃、MVR=1.5cm3/10分、TOPAS Advanced Polymers社製 (Cyclic olefin resin)
As cyclic olefin resin, any 1 or more types of following 4 types of "COC" were used. All of these cyclic olefin resins are addition copolymers of norbornene and ethylene.
COC-1: heat deflection temperature = 120 ℃, Tg = 134 ℃ , MVR = 48cm 3/10 minutes, TOPAS Advanced Polymers, Inc. COC-2: heat deflection temperature = 120 ℃, Tg = 142 ℃ , MVR = 13cm 3 / 10 minutes, TOPAS Advanced Polymers, Inc. COC-3: heat deflection temperature = 140 ℃, Tg = 158 ℃ , MVR = 4cm 3/10 min, TOPAS Advanced Polymers, Inc. COC-4: heat deflection temperature = 160 ℃, Tg = 178 ℃, MVR = 1.5cm 3/ 10 minutes, TOPAS Advanced Polymers, Inc.
3,5-ジ-tert-ブチル-4-ヒドロキシフェニル基を有する化合物(A)として、下記を用いた。
ペンタエリスリトールテトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート](「Irganox1010」、BASFジャパン株式会社製)
また、化合物(A)の代わりに、下記の片ヒンダードフェノールも用いた。
エチレンビス(オキシエチレン)ビス[3-(5-tert-ブチル-4-ヒドロキシ-m-トリル)プロピオネート](「Irganox245」、BASFジャパン株式会社製)
ビス[3,3-ビス(3’-t-ブチル-4’-ヒドロキシフェニル)酪酸]エチレン(「HostanoxO3」、クラリアントジャパン株式会社製) (Compound (A))
The following was used as a compound (A) having a 3,5-di-tert-butyl-4-hydroxyphenyl group.
Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] ("Irganox 1010", manufactured by BASF Japan Ltd.)
Also, in place of the compound (A), the following hindered phenols were also used.
Ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] ("Irganox 245", manufactured by BASF Japan Ltd.)
Bis [3,3-bis (3'-t-butyl-4'-hydroxyphenyl) butyric acid] ethylene ("Hostanoxo O3," Clariant Japan KK)
2,2,6,6-テトラメチル-4-ピペリジル基又は1,2,2,6,6-ペンタメチル-4-ピペリジル基を有する化合物(B)として、下記を用いた。
ポリ[{6-(1,1,3,3-テトラメチルブチル)アミノ-1,3,5-トリアジン-2,4-ジイル}{(2,2,6,6-テトラメチル-4-ピペリジル)イミノ}ヘキサメチレン{(2,2,6,6-テトラメチル-4-ピペリジル)イミノ}](「LA-94G」、株式会社ADEKA製)
ポリ[{6-モルフォリノ-1,3,5-トリアジン-2,4-ジイル}{(1,2,2,6,6-ペンタメチル-4-ピペリジル)イミノ}ヘキサメチレン{(1,2,2,6,6-ペンタメチル-4-ピペリジル)イミノ}](「UV-3529」、CYTEC INDUSTRIES INC製)
ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート(「Tinuvin770」、BASFジャパン株式会社製)
以下の式(1)で表される化合物(「Chimassorb 2020」、BASFジャパン株式会社製)
The following was used as a compound (B) having a 2,2,6,6-tetramethyl-4-piperidyl group or a 1,2,2,6,6-pentamethyl-4-piperidyl group.
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 (“Tinuvin 770”, manufactured by BASF Japan Ltd.)
A compound represented by the following formula (1) ("Chimassorb 2020", manufactured by BASF Japan Ltd.)
紫外線吸収剤として、下記を用いた。
2-(2H-ベンゾトリアゾール-2-イル)-4-6-ビス(1-メチル-1-フェニルメチル)フェノール(「Tinuvin234」、BASFジャパン株式会社製)
2,2’-メチレンビス[6-(2H-ベンゾトリアゾール-2-イル)-4-(1,1,3,3-テトラメチルブチル)フェノール](「LA-31」、株式会社ADEKA製)
ビス{2-[4-(4,6-ジフェニル-1,3,5-トリアジン-2-イル)-3-ヒドロキシフェノキシ]エチル}ドデカンジオエート(「LA-1000」、株式会社ADEKA製)
2-[4,6-ビス(2,4-ジメチルフェニル)-1,3,5-トリアジン-2-イル]-5-(オクチルオキシ)フェノール(「CYASORB UV-1164」、CYTEC INDUSTRIES INC製)
テトラ-エチル-2,2-(1,4-フェニレン-ジメチリデン)-ビスマロネート(「Hostavin B-CAP」、クラリアントジャパン株式会社製) (UV absorber)
The following was used as an ultraviolet absorber.
2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylmethyl) phenol ("Tinuvin 234", manufactured by BASF Japan 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", manufactured by ADEKA Corporation)
2- [4,6-Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol ("CYASORB UV-1164" from CYTEC INDUSTRIES INC)
Tetra-ethyl-2,2- (1,4-phenylene-dimethylidene) -bismalonate ("Hostavin B-CAP", manufactured by Clariant Japan Ltd.)
縮合リン酸エステルとして、下記を用いた。
1,3フェニレンビス(ジ-2,6キシレニルホスフェート)(「PX-200」、大八化学工業株式会社製) (Condensed phosphate ester)
The following was used as condensed phosphoric acid ester.
1,3 phenylene bis (di-2,6 xylenyl phosphate) ("PX-200" manufactured by Daihachi Chemical Industry Co., Ltd.)
主鎖にスチレンを含むブロック共重合体として、下記を用いた。
「Septon 8104」(SEBS、スチレン含量60質量%、株式会社クラレ製)
「Septon 8105」(SEBS、スチレン含量65質量%、株式会社クラレ製)
「Septon 2104」(SEPS、スチレン含量65質量%、株式会社クラレ製)
「Hybrar KL7350」(SEEPS、スチレン含量50質量%、株式会社クラレ製)
「タフテック H1043」(SEBS、スチレン含量67質量%、旭化成株式会社製)
「DYNARON 9901P」(SEBS、スチレン含量54質量%、JSR株式会社製) (Block copolymer)
The following was used as a block copolymer containing styrene in the main chain.
"Septon 8104" (SEBS, styrene content 60% by mass, Kuraray Co., Ltd.)
"Septon 8105" (SEBS, styrene content 65% by mass, Kuraray Co., Ltd.)
"Septon 2104" (SEPS, styrene content 65% by mass, Kuraray Co., Ltd.)
"Hybrar KL 7350" (SEEPS, styrene content 50% by mass, Kuraray Co., Ltd.)
"Tough Tech H1043" (SEBS, styrene content 67% by mass, manufactured by Asahi Kasei Corporation)
"DYNARON 9901P" (SEBS, 54% by mass styrene content, manufactured by JSR Corporation)
添加剤として、下記を用いた。
滑剤:ペンタエリスリトールテトラステアレート(PETS)、日油株式会社製 (Additive)
The following was used as an additive.
Lubricant: Pentaerythritol tetrastearate (PETS), manufactured by NOF Corporation
得られた各樹脂組成物について、射出成形機(住友重機械社製、商品名:SE75D)にて、シリンダ温度260~300℃、金型温度110~135℃で、70mm×70mm×厚み2mmの平板を成形した。 <Molding of resin composition>
About each obtained resin composition, 70 mm x 70 mm x thickness 2 mm with cylinder temperature 260-300 degreeC, mold temperature 110-135 degreeC by injection molding machine (Sumitomo Heavy Industries, Ltd. make, brand name: SE75D) A flat plate was formed.
成形後の各平板を、下記3種の試験(ヒートエージング試験、#320又は#275キセノン試験、耐湿熱試験)に供し、試験前後の黄色度(YI値)、及びクラックの有無について評価した。黄色度(DIN6167)は、YKB-Gardnar GmbH製色差計color-sphereを用いて測定した。その結果を表1~4に示す。なお、表中、「初期YI」とは、試験前の各平板の黄色度を示す。 <Evaluation of yellowness and occurrence of cracks>
Each flat plate after molding was subjected to the following three types of tests (heat aging test, # 320 or # 275 xenon test, wet heat resistance test) to evaluate yellowness (YI value) before and after the test, and the presence or absence of cracks. The degree of yellowness (DIN 6167) was measured using a color difference meter color-sphere manufactured by YKB-Gardnar GmbH. The results are shown in Tables 1 to 4. In the table, "initial YI" indicates the degree of yellowness of each flat plate before the test.
各平板に対して115℃、125℃、又は130℃、1000時間の条件の熱処理を行い、熱処理後に黄色度を測定した(「YI@115℃×1000h」、「YI@125℃×1000h」、「YI@130℃×1000h」の項)。さらに、熱処理前後での黄色度の差(ΔYI)を算出した。ΔYIが小さいほど、成形品の耐熱性が高いことを示す。 (Heat aging test)
Each flat plate was heat-treated at 115 ° C., 125 ° C., or 130 ° C. for 1000 hours, and the yellowness was measured after the heat treatment (“YI @ 115 ° C. × 1000 h”, “YI @ 125 ° C. × 1000 h”, "YI @ 130 ° C x 1000 h"). Furthermore, the difference (ΔYI) in yellowness before and after heat treatment was calculated. The smaller the ΔYI, the higher the heat resistance of the molded article.
各平板に対して、500時間の光照射を行い、光照射後に黄色度を測定した(「YI @500時間照射」の項)。光照射は、スガ試験機スーパーキセノンウェザーメーターを用い、フィルター#275(275nm以下をカット)又はフィルター#320(320nm以下をカット)、ブラックパネル温度89℃、湿度50%RH、照射密度162W/m2(300~400nm)、トータルエネルギー量291.5MJ/m2の条件で行った。さらに、光照射の前後での黄色度の差(ΔYI)を算出した。ΔYIが小さいほど、成形品の耐光性が高いことを示す。 (Xenon test)
Each flat plate was irradiated with light for 500 hours, and the degree of yellowness was measured after light irradiation (section of “YI @ 500 hours irradiation”). For light irradiation, filter # 275 (cut at 275 nm or less) or filter # 320 (cut at 320 nm or less) using a Suga tester Super Xenon Weather Meter, black panel temperature 89 ° C., humidity 50% RH, irradiation density 162 W / m 2 (300 to 400 nm), and the total energy amount was 291.5 MJ / m 2 . Furthermore, the difference (ΔYI) in yellowness before and after light irradiation was calculated. The smaller the ΔYI, the higher the light resistance of the molded article.
各平板を、温度85℃、湿度85%環境中に1000時間暴露し、暴露後のクラックの有無を光学顕微鏡で観察した。クラックが認められなかった成形品は、耐湿熱が高いことを示す。 (Moisture resistance test)
Each plate was exposed to an environment at a temperature of 85 ° C. and a humidity of 85% for 1000 hours, and the presence or absence of cracks after the exposure was observed with an optical microscope. Molded articles in which no cracks were observed show that the heat and humidity resistance is high.
Claims (8)
- 環状オレフィン系樹脂と、
3,5-ジ-tert-ブチル-4-ヒドロキシフェニル基を有する化合物(A)と、
2,2,6,6-テトラメチル-4-ピペリジル基又は1,2,2,6,6-ペンタメチル-4-ピペリジル基を有する化合物(B)と、
紫外線吸収剤と、
縮合リン酸エステルと、
主鎖にスチレンを含むブロック共重合体と、を含む樹脂組成物であって、
前記環状オレフィン系樹脂は、ISO75-1,2に準拠する方法で、アニール処理を施していない試験片について測定した1.8MPaにおける荷重たわみ温度が125℃以上であり、
前記化合物(A)及び前記化合物(B)の含有量が、前記環状オレフィン系樹脂100質量部に対する前記化合物(A)の質量部≦前記環状オレフィン系樹脂100質量部に対する前記化合物(B)の質量部を満たす、樹脂組成物。 Cyclic olefin resin,
A 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 a 1,2,2,6,6-pentamethyl-4-piperidyl group;
UV absorber,
Condensed phosphate ester,
A resin composition comprising a block copolymer containing styrene in the main chain,
The cyclic olefin-based resin has a deflection temperature under load of at least 125 ° C. at 1.8 MPa measured on a test piece which has not been subjected to annealing treatment by a method in accordance with ISO 75-1, 2.
The content of the compound (A) and the compound (B) is: part by mass of the compound (A) based on 100 parts by mass of the cyclic olefin resin ≦ mass of the compound (B) based on 100 parts by mass of the cyclic olefin resin A resin composition that fills parts. - 前記紫外線吸収剤及び前記化合物(B)の含有量が、前記環状オレフィン系樹脂100質量部に対する前記紫外線吸収剤の質量部≦前記環状オレフィン系樹脂100質量部に対する前記化合物(B)の質量部を満たす、請求項1に記載の樹脂組成物。 The content of the ultraviolet absorber and the compound (B) is: part by mass of the ultraviolet absorber based on 100 parts by mass of the cyclic olefin resin ≦ part by mass of the compound (B) based on 100 parts by mass of the cyclic olefin resin The resin composition according to claim 1, which satisfies the condition.
- 前記環状オレフィン系樹脂はノルボルネンとエチレンとの付加共重合体を含む、請求項1又は2に記載の樹脂組成物。 The resin composition according to claim 1, wherein the cyclic olefin resin comprises an addition copolymer of norbornene and ethylene.
- 前記化合物(A)はペンタエリスリトールテトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]を含む、請求項1から3のいずれかに記載の樹脂組成物。 The resin composition according to any one of claims 1 to 3, wherein the compound (A) contains pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate].
- 前記化合物(B)は、脂肪酸(C12-21及びC18不飽和)2,2,6,6-テトラメチル-4-ピペリジルエステル、ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート、ポリ[{6-モルフォリノ-1,3,5-トリアジン-2,4-ジイル}{(1,2,2,6,6-ペンタメチル-4-ピペリジル)イミノ}ヘキサメチレン{(1,2,2,6,6-ペンタメチル-4-ピペリジル)イミノ}]、及び、ポリ[{6-(1,1,3,3-テトラメチルブチル)アミノ-1,3,5-トリアジン-2,4-ジイル}{(2,2,6,6-テトラメチル-4-ピペリジル)イミノ}ヘキサメチレン{(2,2,6,6-テトラメチル-4-ピペリジル)イミノ}]、及び以下の式(1)で表される化合物からなる群から選択される1以上を含む、請求項1から4のいずれかに記載の樹脂組成物。
- 前記紫外線吸収剤は、2-(2H-ベンゾトリアゾール-2-イル)-4-6-ビス(1-メチル-1-フェニルメチル)フェノール、2,2’-メチレンビス[6-(2H-ベンゾトリアゾール-2-イル)-4-(1,1,3,3-テトラメチルブチル)フェノール]、2-[4,6-ビス(2,4-ジメチルフェニル)-1,3,5-トリアジン-2-イル]-5-(オクチルオキシ)フェノール、ビス{2-[4-(4,6-ジフェニル-1,3,5-トリアジン-2-イル)-3-ヒドロキシフェノキシ]エチル}ドデカンジオエート、及びテトラ-エチル-2,2-(1,4-フェニレン-ジメチリデン)-ビスマロネートからなる群から選択される1以上を含む、請求項1から5のいずれかに記載の樹脂組成物。 The said ultraviolet absorber is 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylmethyl) phenol, 2,2'-methylenebis [6- (2H-benzotriazole) -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-hydroxyphenoxy] ethyl} dodecanedioate, The resin composition according to any one of claims 1 to 5, comprising one or more selected from the group consisting of and tetra-ethyl-2,2- (1,4-phenylene-dimethylidene) -bismalonate.
- 前記縮合リン酸エステルは1,3フェニレンビス(ジ-2,6キシレニルホスフェート)を含む、請求項1から6のいずれかに記載の樹脂組成物。 The resin composition according to any one of claims 1 to 6, wherein the condensed phosphoric acid ester comprises 1,3 phenylene bis (di-2,6 xylenyl phosphate).
- 前記ブロック共重合体は、スチレン含量が45質量%以上70質量%以下であり、かつ、スチレンと、ブタジエン及び/又はイソプレンとのブロック共重合体の水素化物を含む、請求項1から7のいずれかに記載の樹脂組成物。 The block copolymer according to any one of claims 1 to 7, wherein the block copolymer has a styrene content of 45% by mass to 70% by mass, and includes a hydride of a block copolymer of styrene and butadiene and / or isoprene. Resin composition according to any one of the preceding claims.
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TWI735789B (en) | 2021-08-11 |
JP6469331B1 (en) | 2019-02-13 |
JPWO2019013174A1 (en) | 2019-07-11 |
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