WO2016052302A1 - 環状オレフィン開環重合体水素化物、樹脂成形体、および光学部材 - Google Patents
環状オレフィン開環重合体水素化物、樹脂成形体、および光学部材 Download PDFInfo
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- WO2016052302A1 WO2016052302A1 PCT/JP2015/076944 JP2015076944W WO2016052302A1 WO 2016052302 A1 WO2016052302 A1 WO 2016052302A1 JP 2015076944 W JP2015076944 W JP 2015076944W WO 2016052302 A1 WO2016052302 A1 WO 2016052302A1
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- MCOYKUVVMLKFJK-UHFFFAOYSA-N CCC(CC1[NH+]([NH+](C(C)(C)CC)[N-]=C)[N-]=C)C(C2)C1C1C2CCCC1 Chemical compound CCC(CC1[NH+]([NH+](C(C)(C)CC)[N-]=C)[N-]=C)C(C2)C1C1C2CCCC1 MCOYKUVVMLKFJK-UHFFFAOYSA-N 0.000 description 1
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Definitions
- the present invention has a heat-resistant yellowing property (a property that does not easily change to yellow even when kept at a high temperature for a long time), a dimensional stability at a high temperature (it is a size even when kept at a high temperature for a long time). And a cyclic olefin ring-opened polymer hydride excellent in moldability, a molded body obtained using the cyclic olefin ring-opened polymer hydride, and an optical member comprising the resin molded body.
- Patent Document 1 contains a repeating unit (A) derived from tetracyclododecene containing 55 mol% to 100 mol% based on the total repeating units, and repeating units (B) derived from other norbornene compounds. Further, a tetracyclododecene ring-opening polymer hydride containing 0 mol% to 45 mol% with respect to all repeating units and having excellent solubility in an organic solvent is described. This tetracyclododecene ring-opened polymer hydride is excellent in dimensional stability at high temperatures as shown by having a high glass transition temperature.
- the tetracyclododecene ring-opening polymer hydride generally has a high glass transition temperature and is excellent in dimensional stability at high temperatures.
- tetracyclododecene ring-opening polymer hydride tends to be inferior in moldability, and when a resin molded body is produced, a weld line (in resin molding, molten resin flows merged in a mold and fused together). A thin line generated in the part may be noticeable.
- polymer hydrides obtained by copolymerizing tetracyclododecene and other cyclic olefin monomers or reducing the molecular weight are resistant to heat yellowing and strength. It may be inferior or the dimensional stability at high temperature may be lowered.
- the present invention has been made in view of the above-described prior art, and is a cyclic olefin ring-opening polymer hydride excellent in all of heat-resistant yellowing, high temperature dimensional stability, and moldability, and this cyclic olefin ring-opening polymer.
- An object is to provide a resin molded body obtained by using a hydride and an optical member made of the resin molded body.
- a cyclic olefin ring-opening polymer hydride having a repeating unit derived from tetracyclododecene As a result, it consists of a repeating unit derived from tetracyclododecene and a repeating unit derived from other norbornene-based monomer, and the content of the repeating unit derived from tetracyclododecene is 55% by weight based on all repeating units.
- the content of repeating units derived from other norbornene-based monomers is more than 0% by weight and 45% by weight or less with respect to all repeating units.
- Mw weight average molecular weight
- cyclic olefin ring-opened polymer hydrides [1] and [2], [3] resin moldings, and [4] optical members.
- Mw weight average molecular weight
- the glass transition temperature is 140-165 ° C.
- the temperature is 280 ° C.
- the load is 21.1 based on JIS K6719.
- a resin molded body having a melt flow rate measured under the condition of 8N of 8 g / 10 min or more and a bending strength measured by a bending test performed at a test speed of 2 mm / min based on JIS K7171 is 60 MPa or more. What is obtained is a hydrogenated cyclic olefin ring-opening polymer.
- the glass transition temperature is 140 to 165 ° C., based on JIS K6719, the melt flow rate measured at a temperature of 280 ° C. and a load of 21.18 N is 8 g / 10 min or more, and based on JIS K7171.
- the resin molded product according to [3], wherein a bending strength measured by a bending test performed at a test speed of 2 mm / min is 60 MPa or more.
- An optical member comprising the resin molded product according to [3] or [4]
- a cyclic olefin ring-opening polymer hydride that is excellent in all of heat-resistant yellowing, dimensional stability under high temperature, and moldability, a resin molded body obtained by using this cyclic olefin ring-opening polymer hydride, In addition, an optical member made of the resin molded body is provided.
- Cyclic olefin ring-opening polymer hydride The cyclic olefin ring-opening polymer hydride of the present invention comprises a repeating unit derived from tetracyclododecene and a repeating unit derived from another norbornene monomer.
- the content of repeating units derived from cyclododecene is 55% by weight or more and less than 100% by weight based on all repeating units, and the content of repeating units derived from the other norbornene-based monomers is based on all repeating units.
- Olefin ring-opening polymer hydride, the glass transition temperature by molding the cyclic oleophine ring-opening polymer hydride However, the melt flow rate measured under the conditions of 140 to 165 ° C. under a temperature of 280 ° C. and a load of 21.18 N based on JIS K6719 is 8 g / 10 min or more, and based on JIS K7171, the test speed is 2 mm / min.
- a resin molded body having a bending strength of 60 MPa or more as measured in a bending test performed in is obtained.
- the cyclic olefin ring-opening polymer hydride of the present invention has a repeating unit derived from tetracyclododecene (hereinafter sometimes referred to as “repeating unit (A)”) and a repeating unit derived from another norbornene monomer. (Hereinafter, also referred to as “repeating unit (B)”).
- the repeating unit (A) constituting the cyclic olefin ring-opening polymer hydride of the present invention is represented by the following formula (1):
- the repeating unit (A) is represented by the following formula (2)
- the content of the repeating unit (A) is 55% by weight or more and less than 100% by weight, preferably 55 to 90% by weight, more preferably 60 to 85% by weight, based on all the repeating units.
- the cyclic olefin ring-opened polymer hydride of the present invention is excellent in heat-resistant yellowing and dimensional stability under high temperature because the content of the repeating unit (A) is 55% by weight or more.
- the ratio of the racemodiat of the repeating unit (A) is 65% or more, preferably 70% or more, more preferably 75% or more. Since the cyclic olefin ring-opened polymer hydride of the present invention has such a controlled steric structure, it has excellent solubility in organic solvents and excellent productivity on an industrial scale.
- the ratio of racemodyad in the cyclic olefin ring-opening polymer hydride was determined by comparing the signal from racemodyad (51.82 ppm) and the signal from mesodyad (51.51 ppm) in a 13 C-NMR spectrum measured at 100 ° C. using deuterated orthodichlorobenzene as a solvent. .77 ppm).
- the signal position may be slightly different from that described above, but can be basically calculated by the above method.
- the cyclic olefin ring-opening polymer in which the ratio of the racemodiat of the repeating unit (A) is 65% or more is efficiently obtained by using a polymer containing a transition metal imide compound described later as a polymerization catalyst used when the ring-opening polymerization reaction is performed. Can be manufactured.
- the repeating unit (B) constituting the cyclic olefin ring-opening polymer hydride of the present invention is a repeating unit derived from a norbornene monomer other than tetracyclododecene.
- the norbornene monomer is represented by the following formula (3).
- R 1 to R 4 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a substituent containing a halogen atom, a silicon atom, an oxygen atom or a nitrogen atom; 2 and R 3 may be bonded to form a ring. R 1 and R 2 or R 3 and R 4 may be combined to form an alkylidene group.
- m represents an integer of 0-2. However, when m is 1 and all of R 1 to R 4 are hydrogen atoms, they are excluded because they are repeating units derived from tetracyclododecene.
- Examples of the hydrocarbon group having 1 to 20 carbon atoms of R 1 to R 4 include methyl group, ethyl group, n-propyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n
- An alkyl group such as a decyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; an alkylidene group such as a methylidene group or an ethylidene group; an alkenyl group such as a vinyl group or a propenyl group; a cycloalkenyl such as a cyclohexenyl group or a cyclopentenyl group Groups; alkynyl groups such as ethynyl group and propargyl group; aryl groups such as phenyl group; and the like.
- Examples of the substituent containing a halogen atom, silicon atom, oxygen atom or nitrogen atom include alkoxyl groups such as methoxy group and ethoxy group; hydroxyl group; hydroxyalkyl group such as hydroxymethyl group and 2-hydroxyethyl group; carboxyl group; Alkoxycarbonyl groups such as carbonyl groups and ethoxycarbonyl groups; cyano groups; trialkylsilyl groups such as trimethylsilyl groups; trialkoxysilyl groups such as trimethoxysilyl groups; halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms and iodine atoms And the like.
- the repeating unit (B) is formed, for example, by ring-opening polymerization of one or more of the corresponding norbornene monomers and then hydrogenating the carbon-carbon double bonds in the main chain and side chains.
- bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethylidene-bicyclo [2.2.1] hept-2-ene (common name: Bicyclic norbornene monomers such as ethylidene norbornene); Tricyclo [4.3.0 1,6 .
- deca-3,7-diene (common name: dicyclopentadiene) and the like tricyclic norbornene monomers; 6-ethylidene-2-tetracyclododecene, 7,8-benzotricyclo [4.3.0.1 2,5 ] dec-3-ene (common name: methanotetrahydrofluorene: 1,4-methano-1 , 4,4a, 9a-tetrahydrofluorene) and the like.
- the content of the repeating unit (B) is more than 0% by weight and 45% by weight or less, preferably 10 to 45% by weight, more preferably 15 to 40% by weight, based on all repeating units. Since the cyclic olefin ring-opened polymer hydride of the present invention contains the repeating unit (B), the balance between strength and moldability is excellent. Moreover, it is excellent in heat-resistant yellowing and dimensional stability under high temperature because content of a repeating unit (B) is 45 weight% or less.
- the cyclic olefin ring-opened polymer hydride of the present invention contains a repeating unit derived from a polycyclic norbornene-based monomer having a polycyclic structure of three or more rings (including a repeating unit derived from tetracyclododecene). However, it is preferable that it is 95 weight% or more with respect to all the repeating units, It is more preferable that it is 98 weight% or more, It is further more preferable that it is 100 weight%.
- the polycyclic norbornene monomer having a polycyclic structure of three or more rings a monomer selected from the group consisting of a tricyclic norbornene monomer and a tetracyclic norbornene monomer is preferable.
- the cyclic olefin ring-opening polymer hydride of the present invention has a content of repeating units derived from tetracyclic norbornene monomers (including repeating units derived from tetracyclododecene) relative to all repeating units. Thus, it is preferably 90% by weight or more, and more preferably 95% by weight or more. Cyclic olefin ring-opening polymer hydrides satisfying these requirements are excellent in balance between heat-resistant yellowing, high temperature dimensional stability, and moldability.
- the manufacturing method of the cyclic olefin ring-opening polymer hydride of the present invention is not particularly limited.
- tetracyclododecene and other norbornene-based monomers are subjected to a ring-opening polymerization reaction in the presence of a polymerization catalyst, and then the carbon-carbon double bond of the obtained cyclic olefin ring-opening polymer is hydrogenated.
- the desired cyclic olefin ring-opening polymer hydride can be obtained by hydrogenation in the presence of a fluorination catalyst.
- the polymerization catalyst to be used is not particularly limited, but it is easy to obtain a cyclic olefin ring-opening polymer hydride having a ratio of racemodiat of the repeating unit (A) of 65% or more.
- a transition metal imide compound having a structure in which alkylimide or arylimide is bonded is preferable.
- transition metal imide compound examples include a compound represented by the following formula (6).
- M 1 represents a Group 6 transition metal atom in the periodic table
- L 1 represents a neutral ligand
- X 1 represents an anionic ligand.
- R 5 represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.
- a is 0, 1 or 2
- b is an integer of 1 to 4.
- L 1 may be the same or different from each other, and L 1 may be bonded together to form a chelate ligand.
- b is 2 or more
- X 1 may be the same or different, and X 1 may be bonded together to form a chelate ligand.
- R 5 may bind to L 1 and / or X 1 to form a chelate ligand.
- the Group 1 transition metal of M 1 is a metal selected from chromium (Cr), molybdenum (Mo), and tungsten (W). Among these, molybdenum and tungsten are preferable, and tungsten is particularly preferable.
- the neutral ligand of L 1 is a ligand that has a neutral charge when pulled away from the central metal.
- Specific examples include ethers such as diethyl ether and tetrahydrofuran; ketones such as acetone and cyclohexanone; nitriles such as acetonitrile and benzonitrile; amines such as triethylamine and N, N-diethylaniline; pyridine and lutidine and the like.
- phosphines such as triphenylphosphine
- amides such as dimethylformamide
- sulfoxides such as dimethylsulfoxide
- cyclooctadiene water
- carbon monoxide arenes such as toluene and xylene
- phosphines such as triphenylphosphine oxide
- oxides include, but are not limited to, oxides; carbonates such as ethylene carbonate; esters such as ethyl acetate;
- ethers, pyridines, and nitriles are preferable from the viewpoint of forming a stable transition metal imide compound.
- Anionic ligand of X 1 is a ligand having a negative charge when separated from the central metal.
- Specific examples thereof include halogen atoms such as F, Br, Cl and I; hydrides; diketonate groups such as acetylacetonate; cyclopentadienyl groups which may have a substituent; Allyl group; alkenyl group; alkyl group; aryl group which may have a substituent; alkoxy group; aryloxy group which may have a substituent; alkoxycarbonyl group; carboxyl group; An aryl sulfonate group which may have a substituent; an alkylthio group; an alkenylthio group; an arylthio group which may have a substituent; an alkylsulfonyl group; an alkylsulfinyl group; However, it is not limited to these. Among these, a halogen atom, an alkyl group, an aryl group
- alkyl group of the alkyl group having 1 to 20 carbon atoms which may have a substituent for R 5 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group.
- substituents include halogen atoms such as fluorine atom, chlorine atom and bromine atom; aryl groups such as phenyl group; and the like.
- Examples of the aryl group of the aryl group which may have a substituent for R 5 include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenyl group, and a 4-biphenyl group.
- substituents include alkyl groups such as a methyl group, an ethyl group, and an isopropyl group; halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom;
- Examples of the compound represented by the formula (6) include tungsten (ethylimide) (tetrachloride) (diethyl ether), tungsten (ethylimide) (t-butoxide) (trichloride), tungsten (ethylimide) [di (t-butoxide)] ( Dichloride), tungsten (ethylimide) [tri (t-butoxide)] (chloride), tungsten (ethylimide) [tetra (t-butoxide)], tungsten (ethylimide) (phenoxide) (tetrachloride) (diethyl ether), tungsten ( n-Butylimide) (tetrachloride) (tetrahydrofuran), tungsten (n-hexylimide) (tetrachloride) (diethyl ether), tungsten (i-propylimide) (tetrachloride) (diethyl ether) Tungsten (cyclo
- the compound represented by the formula (6) can be synthesized by a known method, for example, a method described in JP-A-5-345817. Taking a tungsten imide compound as an example, a tungsten imide compound can be synthesized by reacting tungsten oxytetrachloride with an isocyanate having a target substituent. In the present invention, after isolating and purifying the compound represented by the formula (6), it can be used as a polymerization catalyst, or without isolating and purifying the compound represented by the formula (6). Can also be used as a polymerization catalyst solution.
- the amount of the transition metal imide compound used is a molar ratio of (central metal of transition metal imide compound) :( norbornene monomer), usually 1: 100 to 1: 2,000,000, preferably 1: 200 to 1,000,000, more preferably 1: 500 to 1: 500,000. If the amount of the transition metal imide compound is too large, it is difficult to remove the catalyst, and if it is too small, sufficient polymerization activity cannot be obtained.
- the transition metal imide compound may be used in combination with an organometallic reducing agent.
- an organometallic reducing agent By combining with an organometallic reducing agent, the catalytic activity can be improved.
- organometallic reducing agent include organometallic compounds of Groups 1, 2, 12, 13 and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms. Of these, organic lithium, organic magnesium, organic zinc, organic aluminum, and organic tin are preferable, and organic lithium, organic aluminum, and organic tin are particularly preferable.
- Examples of the organic lithium include methyl lithium, n-butyl lithium, neopentyl lithium, neophyl lithium, and phenyl lithium.
- Examples of the organic magnesium include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, allylmagnesium bromide, neopentylmagnesium chloride, neophyllmagnesium chloride and the like.
- Examples of the organic zinc include dimethyl zinc, diethyl zinc, and diphenyl zinc.
- alkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum; dimethylaluminum methoxide, methylaluminum dimethoxide, dimethylaluminum butoxide, diethylaluminum ethoxide, ethylaluminum diethoxide, diisobutylaluminum isobutoxide, etc.
- Alkylaluminum alkoxides alkylaluminum alkoxides; alkylaluminum aryloxides such as dimethylaluminum phenoxide, diethylaluminum phenoxide, diisobutylaluminum phenoxide; alkylaluminum halides such as diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride; methylaluminoxane, ethylaluminum Hexane, aluminoxanes such as isobutyl aluminoxane; and the like.
- the organic tin include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin.
- the amount of the organometallic reducing agent used varies depending on the type of the organometallic reducing agent used, but is preferably 0.1 to 1,000 times mol, preferably 0.2 to 500 times the central metal of the transition metal imide compound. Mole is more preferable, and 0.5 to 200 times mol is particularly preferable. If the amount used is less than 0.1 times mol, the polymerization activity may not be sufficiently improved, and if it is more than 1,000 times mol, side reactions may easily occur.
- a Lewis base may be added to the polymerization reaction system for the purpose of controlling the polymerization rate and the molecular weight distribution of the resulting ring-opening polymer.
- the Lewis base is not particularly limited, but ethers such as diethyl ether and tetrahydrofuran; ketones such as acetone and cyclohexanone; nitriles such as acetonitrile and benzonitrile; amines such as triethylamine and N, N-diethylaniline; pyridine Pyridines such as lutidine; phosphines such as triphenylphosphine; amides such as dimethylformamide; sulfoxides such as dimethylsulfoxide; phosphine oxides such as triphenylphosphine oxide; esters such as ethyl acetate; .
- the addition amount of the Lewis base is preferably 0.1 to 1,000 moles, more preferably 0.2 to 500 moles, with respect to the central metal of the transition metal imide compound.
- the ring-opening polymerization reaction is usually performed in an organic solvent.
- the organic solvent to be used is not particularly limited as long as it does not affect the polymerization reaction and can dissolve or disperse the obtained polymer under predetermined conditions.
- Organic solvents include aliphatic hydrocarbons such as pentane, hexane and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydro Cycloaliphatic hydrocarbons such as indenecyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as dichloromethane
- a molecular weight regulator such as a vinyl compound or a diene compound can be added to the polymerization reaction system for the purpose of adjusting the molecular weight of the resulting ring-opening polymer.
- the vinyl compound used for molecular weight adjustment is not particularly limited as long as it is an organic compound having a vinyl group.
- ⁇ -olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene
- styrenes such as styrene and vinyltoluene
- ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether
- allyl chloride and the like Halogen-containing vinyl compounds
- oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol, and glycidyl methacrylate
- nitrogen-containing vinyl compounds such as acrylamide
- Examples of the diene compound used for adjusting the molecular weight include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, and 2,5-dimethyl-1
- Non-conjugated dienes such as 1,5-hexadiene; 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, etc. Conjugated dienes; and the like.
- the amount added can be arbitrarily selected between 0.1 and 10 mol% with respect to the norbornene monomer, for example.
- the concentration of the norbornene monomer is not particularly limited, but is usually 1 to 50% by weight, preferably 2 to 45% by weight, more preferably 3 to 40% by weight.
- the polymerization temperature is not particularly limited, but is usually ⁇ 30 ° C. to + 200 ° C., preferably 0 ° C. to 180 ° C.
- the polymerization time is usually 1 minute to 100 hours.
- the cyclic olefin ring-opened polymer hydride of the present invention is obtained by hydrogenating the carbon-carbon double bond of the cyclic olefin ring-opened polymer obtained by the ring-opening polymerization reaction in the presence of a hydrogenation catalyst. be able to.
- the hydrogenation catalyst may be a homogeneous catalyst or a heterogeneous catalyst.
- the homogeneous catalyst can be easily dispersed in the hydrogenation reaction solution, so that the amount of catalyst added can be suppressed.
- the cyclic olefin ring-opening polymer and its hydride are hardly decomposed or gelled. For this reason, it is preferable to use a homogeneous catalyst from the viewpoint of cost and product quality.
- the heterogeneous catalyst exhibits particularly excellent activity under high temperature and high pressure, the cyclic olefin ring-opening polymer can be hydrogenated in a short time.
- Wilkinson complex chlorotris (triphenylphosphine) rhodium (I)]; cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyl
- a catalyst comprising a combination of a transition metal compound and an alkyl metal compound, such as a combination of lithium, tetrabutoxytitanate / dimethylmagnesium, and the like.
- heterogeneous catalyst examples include those in which a metal such as Ni, Pd, Pt, Ru, Rh is supported on a carrier.
- a metal such as Ni, Pd, Pt, Ru, Rh
- an adsorbent such as alumina or diatomaceous earth as the carrier.
- the hydrogenation reaction is usually performed in an organic solvent.
- the organic solvent is not particularly limited as long as it is inert to the hydrogenation reaction.
- a hydrocarbon solvent is usually used because it easily dissolves the hydride produced.
- hydrocarbon solvents include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and n-heptane; cyclohexane, methylcyclohexane, decalin, and bicyclononane. Alicyclic hydrocarbon-based solvents; and the like. These organic solvents can be used alone or in combination of two or more.
- the solvent used in the ring-opening polymerization reaction is also suitable as a solvent for the hydrogenation reaction. Therefore, after adding a hydrogenation catalyst to the ring-opening polymerization reaction solution, it can be used for the hydrogenation reaction.
- the reaction temperature is usually ⁇ 20 to + 250 ° C., preferably ⁇ 10 to + 220 ° C., more preferably 0 to 200 ° C.
- the pressure of hydrogen is usually 0.01 to 10.0 MPa, preferably 0.05 to 8.0 MPa, more preferably 0.1 to 5.0 MPa.
- the time for the hydrogenation reaction is appropriately selected in order to control the hydrogenation rate, but is usually in the range of 0.1 to 50 hours.
- the catalyst residue can be removed by performing a treatment such as centrifugation or filtration. If necessary, a catalyst deactivator such as water or alcohol may be used, or an adsorbent such as activated clay or alumina may be added.
- a catalyst deactivator such as water or alcohol may be used, or an adsorbent such as activated clay or alumina may be added.
- the weight average molecular weight of the cyclic olefin ring-opened polymer hydride of the present invention is 10,000 to 40,000, preferably 13,000 to 35,000, more preferably 15,000 to 30,000.
- the weight average molecular weight is too low, the mechanical strength of the obtained resin molded product tends to be inferior.
- the weight average molecular weight is too high, the fluidity at the time of melting is not sufficient, and the moldability tends to be poor.
- the molecular weight distribution (Mw / Mn) of the cyclic olefin ring-opened polymer hydride is not particularly limited, but is preferably 1 to 5, more preferably 1 to 4.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) of the cyclic olefin ring-opened polymer hydride are standard isoprene conversion values by gel permeation chromatography (GPC) using cyclohexane as an eluent.
- the cyclic olefin ring-opened polymer hydride of the present invention has a relatively high glass transition temperature, and is excellent in fluidity and mechanical strength upon melting.
- the glass transition temperature of a resin molded product obtained by molding the cyclic olefin ring-opened polymer hydride of the present invention (hereinafter sometimes referred to as “resin molded product ( ⁇ )”) is 140 to 165 ° C., preferably Is 145 to 165 ° C, more preferably 145 to 160 ° C.
- the cyclic olefin polymer in which the glass transition temperature of the resin molded body ( ⁇ ) is 140 ° C. or higher is excellent in dimensional stability at high temperatures.
- the cyclic olefin polymer in which the glass transition temperature of the resin molded body ( ⁇ ) is 160 ° C. or less is excellent in moldability.
- the glass transition temperature of the resin molding ( ⁇ ) can be adjusted by the kind and amount of the norbornene-based monomer used for the production of the cyclic olefin ring-opening polymer hydride.
- a resin using a cyclic olefin ring-opening polymer hydride containing a large number of repeating units derived from a tetracyclic norbornene monomer such as tetracyclododecene, 6-ethylidene-2-tetracyclododecene, methanotetrahydrofluorene, etc.
- the molded body ( ⁇ ) tends to have a high glass transition temperature.
- the melt flow rate of the resin molded body ( ⁇ ) measured under the conditions of a temperature of 280 ° C. and a load of 21.18 N (load of 2.16 kgf) based on JIS K6719 is 8 g / 10 min or more, preferably 10 g / 10 min. As mentioned above, More preferably, it is 15 g / 10min or more. There is no particular upper limit for the melt flow rate, but it is usually 80 g / 10 min or less.
- the cyclic olefin ring-opening polymer hydride having a melt flow rate of 8 g / 10 min or more is excellent in moldability.
- This melt flow rate can be adjusted by the kind and amount of the norbornene-based monomer used for the production of the cyclic olefin ring-opening polymer hydride.
- a resin molded product ( ⁇ ) using a cyclic olefin ring-opening polymer hydride containing a large number of repeating units derived from methanotetrahydrofluorene has a melt flow. The rate tends to be high.
- a synthetic resin can increase the melt flow rate by lowering its weight average molecular weight, and this property can also be used in the present invention.
- the weight average molecular weight is too low as described above, the mechanical strength of the resulting resin molded article is inferior. Therefore, in the present invention, avoid lowering the molecular weight more than necessary, and other than tetracyclododecene. It is preferable to increase the melt flow rate by adjusting the type and amount of the norbornene monomer.
- the bending strength measured by a bending test (details of this test are as described in Examples) of the resin molded body ( ⁇ ) based on JIS K7171 at a test speed of 2 mm / min is 60 MPa or more. , Preferably 62 MPa or more, more preferably 65 MPa or more. Although there is no upper limit value for this bending strength, it is usually 150 MPa or less.
- the cyclic olefin ring-opened polymer hydride having a bending strength of 60 MPa or more is excellent in dimensional stability at high temperatures.
- This bending strength can be adjusted by the kind and amount of the norbornene monomer used for the production of the cyclic olefin ring-opening polymer hydride.
- a resin molded product ( ⁇ ) using a cyclic olefin ring-opening polymer hydride containing many repeating units derived from methanotetrahydrofluorene has a bending strength. Tend to be higher.
- the resin molding used as a measurement sample of said glass transition temperature, a melt flow rate, and bending strength may contain an additive in the range which does not affect these measured values.
- the cyclic olefin ring-opened polymer hydride of the present invention satisfies the above-mentioned requirements regarding the structural characteristics and physical properties. Therefore, heat yellowing, dimensional stability under high temperature, and moldability (the weld line is inconspicuous) Excellent properties).
- the heat-resistant yellowing of the cyclic olefin ring-opening polymer hydride was evaluated by conducting a test based on JIS K7103 (details of this test are as described in the Examples) and determining the yellowness difference ( ⁇ YI). can do.
- the yellowness difference ( ⁇ YI) of the cyclic olefin ring-opened polymer hydride of the present invention is usually 20 or less, preferably 15 or less. Since the cyclic olefin ring-opened polymer hydride of the present invention contains many repeating units derived from tetracyclododecene, it is excellent in heat-resistant yellowing. In addition, by not excessively increasing the amount of repeating units derived from methanotetrahydrofluorene, there is a tendency to be more excellent in heat-resistant yellowing.
- the high temperature dimensional stability and moldability of the cyclic olefin ring-opened polymer hydride of the present invention can be evaluated by the methods described in the Examples.
- the cyclic olefin ring-opening polymer hydride of the present invention contains many repeating units derived from tetracyclododecene. And the fluidity
- the cyclic olefin ring-opened polymer hydride of the present invention is useful as a raw material for producing optical members that are required to have heat resistance.
- Resin molded body and optical member The resin molded body of the present invention is obtained by molding a resin composition containing the hydrogenated cyclic olefin ring-opened polymer of the present invention.
- the resin composition to be used may contain other components such as additives as long as the effects of the present invention are not impaired.
- other components include an antioxidant, an ultraviolet absorber, a light stabilizer, a near infrared absorber, a plasticizer, and an antistatic agent.
- the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.
- phenolic antioxidants include 3,5-di-t-butyl-4-hydroxytoluene, dibutylhydroxytoluene, 2,2'-methylenebis (6-t-butyl-4-methylphenol), 4,4 ' -Butylidenebis (3-t-butyl-3-methylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), ⁇ -tocophenol, 2,2,4-trimethyl-6-hydroxy -7-t-butylchroman, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, pentaerythrityl-tetrakis [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate] and the like.
- pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is particularly preferred.
- the resin composition contains a phenolic antioxidant, the content thereof is preferably 0.01 to 5 parts by weight, more preferably 0.1 parts by weight with respect to 100 parts by weight of the cyclic olefin ring-opening polymer hydride. ⁇ 2 parts by weight, more preferably 0.2 to 1 part by weight.
- phosphorus antioxidants include distearyl pentaerythritol diphosphite, bis (2,4-ditertiarybutylphenyl) pentaerythritol diphosphite, tris (2,4-ditertiarybutylphenyl) phosphite, tetrakis (2 , 4-ditertiary butylphenyl) 4,4′-biphenyl diphosphite, trinonylphenyl phosphite and the like.
- sulfur-based antioxidants examples include distearyl thiodipropionate and dilauryl thiodipropionate.
- Examples of the ultraviolet absorber include benzotriazole ultraviolet absorbers, benzoate ultraviolet absorbers, benzophenone ultraviolet absorbers, acrylate ultraviolet absorbers, and metal complex ultraviolet absorbers.
- Examples of the light stabilizer include hindered amine light stabilizers.
- near infrared absorbers cyanine-based near infrared absorbers; pyrylium-based infrared absorbers; squarylium-based near infrared absorbers; croconium-based infrared absorbers; azulenium-based near infrared absorbers; phthalocyanine-based near infrared absorbers; System near infrared absorbers; naphthoquinone near infrared absorbers; anthraquinone near infrared absorbers; indophenol near infrared absorbers;
- the plasticizer include a phosphoric acid triester plasticizer, a fatty acid monobasic acid ester plasticizer, a dihydric alcohol ester plasticizer, and an oxyacid ester plasticizer.
- the antistatic agent include fatty acid esters of polyhydric alcohols.
- the content of these components can be appropriately determined according to the purpose.
- the content is usually in the range of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the cyclic olefin ring-opening polymer hydride.
- Resin composition can be obtained by mixing each component according to a conventional method.
- the mixing method include a method of mixing each component in an appropriate solvent and a method of kneading in a molten state.
- Kneading can be performed using a melt kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, or a feeder ruder.
- the kneading temperature is preferably in the range of 200 to 400 ° C, more preferably 240 to 350 ° C.
- the components may be added together and kneaded, or may be kneaded while adding in several times.
- the molding method for producing the resin molded body of the present invention is not particularly limited, and examples thereof include injection molding, press molding, and extrusion molding. Among these, when the resin molded body is an optical member or the like, injection molding is preferable because the desired resin molded body can be obtained with high accuracy.
- the melting temperature at the time of molding varies depending on the resin composition used, but is usually 200 to 400 ° C, preferably 210 to 350 ° C.
- the mold temperature in the case of using a mold is usually 20 ° C. to (Tg + 15) ° C., preferably (Tg ⁇ 30) ° C. to (Tg + 10) ° C., more preferably when the glass transition temperature of the resin composition is Tg. Is a temperature from (Tg ⁇ 20) ° C. to (Tg + 5) ° C.
- the cyclic olefin ring-opened polymer hydride of the present invention used as a raw material for producing the resin molded body of the present invention is excellent in heat-resistant yellowing, high temperature dimensional stability, and moldability.
- This resin molded product is also excellent in these characteristics.
- the resin molded body of the present invention has a glass transition temperature of 140 to 165 ° C., a melt flow rate measured under the conditions of a temperature of 280 ° C. and a load of 21.18 N (load of 2.16 kgf) based on JIS K6719. It is preferable that the bending strength measured by a bending test conducted at a test speed of 2 mm / min based on JIS K7171 for 10 minutes or more is 60 MPa or more.
- the resin molding of the present invention is suitably used as an optical member such as an optical lens, a prism, or a light guide. Among them, it is particularly preferably used as an optical member such as a lens used in a camera installed in a car.
- Weight average molecular weight The weight average molecular weight (Mw) of the cyclic olefin ring-opening polymer hydride is measured by gel permeation chromatography (GPC) using cyclohexane as an eluent and obtained as a standard polyisoprene conversion value. It was.
- the measurement was performed under the conditions of using three columns (manufactured by Tosoh Corporation, TSKgel G5000HXL, TSKgel G4000HXL, and TSKgel G2000HXL) connected in series, a flow rate of 1.0 mL / min, a sample injection amount of 100 ⁇ L, and a column temperature of 40 ° C.
- Tg Glass transition temperature
- Ratio of racemodyad The ratio of racemodyad as a repeating unit derived from tetracyclododecene in the cyclic olefin ring-opening polymer hydride was derived from racemodyad in a 13 C-NMR spectrum measured using deuterated orthodichlorobenzene as a solvent. It calculated and calculated
- melt flow rate (MFR) The melt flow rate of the resin composition containing the cyclic olefin ring-opening polymer hydride was measured under the conditions of a temperature of 280 ° C. and a load of 21.18 N (load of 2.16 kgf) based on JIS K6719.
- the yellowness (YI: yellow index) of this test piece was measured using a color difference meter in accordance with JIS K7103 as a blank as air.
- a value obtained by subtracting the yellowness YI of only air from the obtained yellowness YI was defined as the yellowness difference ( ⁇ YI) of the test piece.
- ⁇ YI yellowness difference
- Injection molding was performed under the conditions of 300 ° C., mold temperature (Tg ⁇ 5) ° C., and injection pressure of 40 MPa to produce a resin molded body (lens).
- the obtained lens is measured in the range of 1 mm from the center of the lens, and the dimensional difference from the design value R A value [PV value ( ⁇ m)] obtained by subtracting the minimum value from the maximum value was calculated.
- this lens was put in an oven and heated at 130 ° C. for 170 hours, and then the PV value was calculated by the same method as described above, and the difference in PV value before and after heating was compared. The smaller the difference between the PV value before heating and the PV value after heating, the smaller the dimensional change at high temperature.
- Formability evaluation (weld line observation) The surface of the resin molded body (lens) obtained by the above method (7) is observed with a microscope, the length of the weld line generated in the anti-gate direction is measured, and the moldability is evaluated according to the following criteria. did.
- Example 1 Into a polymerization reactor dried inside and purged with nitrogen, 2.0 parts of a monomer mixture consisting of 30% 6-ethylidene-2-tetracyclododecene (ETD) and 70% tetracyclododecene (TCD) (polymerization) 1% based on the total amount of monomers used), dehydrated cyclohexane 785 parts, molecular weight regulator (1-hexene) 1.21 parts, diethylaluminum ethoxide n-hexane solution (concentration: 19%) 0.98 parts, Then, 11.7 parts of a toluene solution (concentration: 2.0%) of tungsten (phenylimide) tetrachloride ⁇ tetrahydrofuran was added and stirred at 50 ° C.
- ETD 6-ethylidene-2-tetracyclododecene
- TCD tetracyclododecene
- a diatomaceous earth (“Radiolite (registered trademark) # 500") is used as a filter bed and a pressure filter (Ishikawajima-Harima Heavy Industries Co., Ltd .; "Hunda filter”) is used at a pressure of 0.25 MPa. Filtration under pressure gave a clear and colorless solution.
- the filtrate obtained above is put into a cylindrical concentration dryer (manufactured by Hitachi, Ltd.), and the solvent cyclohexane and other volatile components are removed under the conditions of a temperature of 290 ° C. and a pressure of 1 kPa or less.
- a temperature of 290 ° C. and a pressure of 1 kPa or less Extruded into a strand form in a molten state from a directly connected die, cooled with water, and cut with a pelletizer (manufactured by Nagata Seisakusho; “OSP-2”) to obtain pellets.
- OSP-2 pelletizer
- the results are shown in Table 1.
- the hydrogenation rate in the hydrogenation reaction was 99% or more. (The same applies to the following examples and comparative examples)
- Example 2 In Example 1, pellets were obtained in the same manner as in Example 1 except that a monomer mixture having a composition of 80% TCD, 10% ETD, and 10% dicyclopentadiene (DCPD) was used. And evaluated. The results are shown in Table 1.
- Example 3 In Example 1, pellets were obtained in the same manner as in Example 1 except that a monomer mixture having a composition of 80% TCD, 10% DCPD, and 10% methanotetrahydrofluorene (MTF) was used. And evaluated. The results are shown in Table 1.
- Example 4 In Example 1, pellets were obtained and tested and evaluated in the same manner as in Example 1 except that a monomer mixture having a composition of TCD 70%, DCPD 10%, and MTF 20% was used. The results are shown in Table 1.
- Example 1 a monomer mixture having a composition of 92% TCD and 8% norbornene (NB) was used, except that the amount of 1-hexene as a molecular weight regulator was changed to 0.8 parts. Pellets were obtained in the same manner as in Example 1 and tested and evaluated. The results are shown in Table 1.
- Example 2 In Example 1, pellets were obtained and tested and evaluated in the same manner as in Example 1 except that a monomer mixture having a composition of 90% TCD and 10% NB was used. The results are shown in Table 1.
- Comparative Example 4 In Comparative Example 3, the amount of 1-hexene as a molecular weight regulator was changed to 0.6 part, and 5 parts of alumina-supported nickel catalyst (N163A, manufactured by JGC Chemical Co., Ltd.) was used in place of the diatomite-supported nickel catalyst. Except that the hydrogenation reaction was carried out for 8 hours under the conditions of a reaction temperature of 230 ° C. and a hydrogen pressure of 4.5 MPa, pellets were obtained and tested and evaluated in the same manner as in Comparative Example 3. The results are shown in Table 1.
- Comparative Example 5 In Comparative Example 3, a monomer mixture having a composition of TCD 25%, MTF 70% and NB 5% was used instead of MTF, and the amount of 1-hexene as a molecular weight regulator was changed to 1.2 parts. Except for the above, pellets were obtained in the same manner as in Comparative Example 3, and tested and evaluated. The results are shown in Table 1.
- the cyclic olefin ring-opened polymer hydrides obtained in Examples 1 to 4 are highly balanced in heat yellowing resistance, dimensional stability at high temperature, and moldability.
- the cyclic olefin ring-opened polymer hydride obtained in Comparative Example 1 has an excessively high weight average molecular weight, and thus has excellent mechanical strength, but has a low melt flow rate and poor moldability.
- a polymerization average molecular weight is made low, it will be inferior to mechanical strength (comparative example 2).
- the cyclic olefin ring-opened polymer hydrides obtained in Comparative Examples 2, 4, and 5 have low glass transition temperatures and poor dimensional stability at high temperatures.
- the cyclic olefin ring-opening polymer hydride obtained in Comparative Examples 3 and 5 contains many repeating units derived from methanotetrahydrofluorene and is inferior in heat-resistant yellowing. In addition, this can be improved by changing the reaction conditions of the hydrogenation reaction as shown in Comparative Example 4, but in this case, the glass transition temperature is lowered as described above, and the dimensional stability at high temperature is poor. .
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Abstract
Description
しかしながら、季節によっては、自動車等の車内は非常に高温になるため、そのようなカメラに用いられるレンズの製造原料には、透明性等の光学特性に優れることに加えて、耐熱黄変性や高温下寸法安定性にも優れることが求められる。
例えば、特許文献1には、テトラシクロドデセン由来の繰り返し単位(A)を、全繰り返し単位に対して、55モル%~100モル%含有し、その他のノルボルネン化合物由来の繰り返し単位(B)を、全繰り返し単位に対して、0モル%~45モル%含有するテトラシクロドデセン開環重合体水素化物であって、有機溶媒に対する溶解性に優れるものが記載されている。
このテトラシクロドデセン開環重合体水素化物は、高いガラス転移温度を有することから示されるように、高温下寸法安定性に優れるものである。
しかしながら、テトラシクロドデセン開環重合体水素化物は成形性に劣る傾向があり、樹脂成形体を製造すると、ウェルドライン(樹脂成形において、金型内で溶融樹脂の流れが合流して融着した部分に発生する細い線)が目立つことがあった。また、成形性や、その他の性能の向上を目的として、テトラシクロドデセンとその他の環状オレフィンモノマーとを共重合させたり、分子量を低くしたりした重合体水素化物は、耐熱黄変性や強度に劣ったり、高温下寸法安定性が低下したりすることがあった。
〔1〕テトラシクロドデセン由来の繰り返し単位と、その他のノルボルネン系単量体由来の繰り返し単位とからなり、前記テトラシクロドデセン由来の繰り返し単位の含有量が、全繰り返し単位に対して55重量%以上100重量%未満、前記その他のノルボルネン系単量体由来の繰り返し単位の含有量が、全繰り返し単位に対して0重量%超45重量%以下であり、前記テトラシクロドデセン由来の繰り返し単位のラセモダイアットの割合が、65%以上であり、かつ、重量平均分子量(Mw)が10,000~40,000の環状オレフィン開環重合体水素化物であって、前記環状オレオフィン開環重合体水素化物を成形することにより、ガラス転移温度が、140~165℃、JIS K6719に基いて、温度280℃、荷重21.18Nの条件で測定したメルトフローレートが、8g/10分以上、かつ、JIS K7171に基いて、試験速度2mm/分で行った曲げ試験で測定した曲げ強度が、60MPa以上、の樹脂成形体が得られるものであることを特徴とする、環状オレフィン開環重合体水素化物。
〔2〕3環以上の多環構造を有する多環式ノルボルネン系単量体に由来する繰り返し単位を、全繰り返し単位に対して95重量%以上含む、〔1〕に記載の環状オレフィン開環重合体水素化物。
〔3〕前記〔1〕または〔2〕に記載の環状オレフィン開環重合体水素化物を含有する樹脂組成物を成形して得られる樹脂成形体。
〔4〕ガラス転移温度が、140~165℃、JIS K6719に基いて、温度280℃、荷重21.18Nの条件で測定したメルトフローレートが、8g/10分以上、かつ、JIS K7171に基いて、試験速度2mm/分で行った曲げ試験で測定した曲げ強度が、60MPa以上である、〔3〕に記載の樹脂成形体。
〔5〕前記〔3〕又は〔4〕に記載の樹脂成形体からなる光学部材
本発明の環状オレフィン開環重合体水素化物は、テトラシクロドデセン由来の繰り返し単位と、その他のノルボルネン系単量体由来の繰り返し単位とからなり、前記テトラシクロドデセン由来の繰り返し単位の含有量が、全繰り返し単位に対して55重量%以上100重量%未満、前記その他のノルボルネン系単量体由来の繰り返し単位の含有量が、全繰り返し単位に対して0重量%超45重量%以下であり、前記テトラシクロドデセン由来の繰り返し単位のラセモダイアットの割合が、65%以上であり、かつ、重量平均分子量(Mw)が10,000~40,000の環状オレフィン開環重合体水素化物であって、前記環状オレオフィン開環重合体水素化物を成形することにより、ガラス転移温度が、140~165℃、JIS K6719に基いて、温度280℃、荷重21.18Nの条件で測定したメルトフローレートが、8g/10分以上、かつ、JIS K7171に基いて、試験速度2mm/分で行った曲げ試験で測定した曲げ強度が、60MPa以上、の樹脂成形体が得られるものであることを特徴とする。
本発明の環状オレフィン開環重合体水素化物は、テトラシクロドデセン由来の繰り返し単位(以下、「繰り返し単位(A)」ということがある。)と、その他のノルボルネン系単量体由来の繰り返し単位(以下、「繰り返し単位(B)」ということがある。)とからなる。
繰り返し単位(A)は、下記式(2)
本発明の環状オレフィン開環重合体水素化物は、繰り返し単位(A)の含有量が55重量%以上であることで、耐熱黄変性、及び高温下寸法安定性に優れる。
本発明の環状オレフィン開環重合体水素化物は、このように立体構造が制御されたものであるため、有機溶媒に対する溶解性に優れ、工業的規模での生産性に優れる。
なお、繰り返し単位(B)の種類や測定条件によっては、シグナルの位置は上記のものとは若干異なることがあるが、基本的には上記の方法により計算することができる。
繰り返し単位(B)としては、下記式(4)、(5)
但し、mが1であって、かつ、R1~R4が全て水素原子である場合は、テトラシクロドデセン由来の繰り返し単位となるため除かれる。
トリシクロ[4.3.01,6.12,5]デカ-3,7-ジエン(慣用名:ジシクロペンタジエン)等の3環式ノルボルネン系単量体;
6-エチリデン-2-テトラシクロドデセン、7,8-ベンゾトリシクロ[4.3.0.12,5]デカ-3-エン(慣用名:メタノテトラヒドロフルオレン:1,4-メタノ-1,4,4a,9a-テトラヒドロフルオレンともいう)等の4環式ノルボルネン系単量体;等が挙げられる。
本発明の環状オレフィン開環重合体水素化物は、繰り返し単位(B)を含むことで、強度と成形性のバランスに優れる。また、繰り返し単位(B)の含有量が45重量%以下であることで、耐熱黄変性、及び高温下寸法安定性に優れる。
さらに、本発明の環状オレフィン開環重合体水素化物は、4環式ノルボルネン系単量体に由来する繰り返し単位(テトラシクロドデセン由来の繰り返し単位を含む)の含有量が、全繰り返し単位に対して、90重量%以上であるのが好ましく、95重量%以上であるのがより好ましい。
これらの要件を満たす環状オレフィン開環重合体水素化物は、耐熱黄変性、高温下寸法安定性、及び成形性のバランスにより優れたものとなる。
本発明の環状オレフィン開環重合体水素化物の製造方法は特に限定されない。例えば、テトラシクロドデセンとその他のノルボルネン系単量体とを、重合触媒の存在下に開環重合反応を行い、次いで、得られた環状オレフィン開環重合体の炭素-炭素二重結合を水素化触媒の存在下に水素化することで目的の環状オレフィン開環重合体水素化物を得ることができる。
aは0、1又は2であり、bは1~4の整数である。
aが2のとき、L1同士は同一であっても相異なっていてもよく、L1同士が一緒になって結合してキレート配位子を形成していてもよい。
bが2以上のとき、X1同士は同一であっても相異なっていてもよく、X1同士が一緒になって結合してキレート配位子となっていてもよい。
また、R5がL1、及び/又はX1と結合してキレート配位子となっていてもよい。
これらの中でも、安定な遷移金属イミド化合物を形成する観点から、エーテル類、ピリジン類、ニトリル類が好ましい。
これらの中でも、安定な遷移金属イミド化合物を形成する観点から、ハロゲン原子、アルキル基、アリール基、アルコキシ基又はアリールオキシ基が好ましい。
これらの置換基としては、フッ素原子、塩素原子、臭素原子等のハロゲン原子;フェニル基等のアリール基;等が挙げられる。
これらの置換基としては、メチル基、エチル基、イソプロピル基等のアルキル基;フッ素原子、塩素原子、臭素原子等のハロゲン原子;等が挙げられる。
本発明においては、式(6)で示される化合物を単離精製した後、これを重合触媒として用いることもできるし、式(6)で示される化合物を単離精製することなく、合成反応液を重合触媒液として用いることもできる。
有機金属還元剤としては、炭素数1~20の炭化水素基を有する周期表第1、2、12、13、14族の有機金属化合物が挙げられる。なかでも、有機リチウム、有機マグネシウム、有機亜鉛、有機アルミニウム、有機スズが好ましく、有機リチウム、有機アルミニウム、有機スズが特に好ましい。
有機マグネシウムとしては、ブチルエチルマグネシウム、ブチルオクチルマグネシウム、ジヘキシルマグネシウム、エチルマグネシウムクロリド、n-ブチルマグネシウムクロリド、アリルマグネシウムブロミド、ネオペンチルマグネシウムクロリド、ネオフィルマグネシウムクロリド等が挙げられる。
有機亜鉛としては、ジメチル亜鉛、ジエチル亜鉛、ジフェニル亜鉛等が挙げられる。
有機スズとしては、テトラメチルスズ、テトラ(n-ブチル)スズ、テトラフェニルスズ等が挙げられる。
ルイス塩基の添加量は、遷移金属イミド化合物の中心金属に対して、0.1~1,000倍モルが好ましく、0.2~500倍モルがより好ましい。
有機溶媒としては、ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素;シクロペンタン、シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサン、トリメチルシクロヘキサン、エチルシクロヘキサン、ジエチルシクロヘキサン、デカヒドロナフタレン、ビシクロヘプタン、トリシクロデカン、ヘキサヒドロインデンシクロヘキサン、シクロオクタン等の脂環族炭化水素;ベンゼン、トルエン、キシレン等の芳香族炭化水素;ジクロロメタン、クロロホルム、1,2-ジクロロエタン等のハロゲン系脂肪族炭化水素;クロロベンゼン、ジクロロベンゼン等のハロゲン系芳香族炭化水素;ニトロメタン、ニトロベンゼン、アセトニトリル等の含窒素炭化水素系溶媒;ジエチルエーテル、テトラヒドロフラン等のエーテル系溶媒;アニソール、フェネトール等の芳香族エーテル系溶媒;等が挙げられる。
これらの中でも、工業的に汎用な芳香族炭化水素系溶媒、脂肪族炭化水素系溶媒、脂環族炭化水素系溶媒、エーテル系溶媒、芳香族エーテル系溶媒が好ましい。
分子量調整剤を用いる場合、その添加量は、例えば、ノルボルネン系単量体に対して、0.1~10モル%の間で任意に選択することができる。
重合時間は、通常1分間~100時間である。
均一系触媒は、水素化反応液中で分散しやすいため、触媒の添加量を抑えることができる。また、高温高圧にしなくても十分な活性を有するため、環状オレフィン開環重合体やその水素化物の分解やゲル化が起こりにくい。このため、費用面や生成物の品質の観点からは、均一系触媒を用いることが好ましい。
一方、不均一触媒は、高温高圧下において特に優れた活性を示すため、短時間で環状オレフィン開環重合体を水素化することができる。
これらの有機溶媒は、1種単独で、あるいは2種以上を組み合わせて用いることができる。また、通常は、開環重合反応に用いた溶媒は、水素化反応の溶媒としても適するため、開環重合反応液に水素化触媒を添加した後、それを水素化反応に供することができる。
水素の圧力は、通常0.01~10.0MPa、好ましくは0.05~8.0MPa、より好ましくは0.1~5.0MPaである。
水素化反応の時間は、水素化率をコントロールするために適宜選択されるが、通常0.1~50時間の範囲である。
本発明の環状オレフィン開環重合体水素化物の重量平均分子量は10,000~40,000、好ましくは13,000~35,000、より好ましくは、15,000~30,000である。重量平均分子量が低すぎると得られる樹脂成形体の機械強度が劣り易くなる。また、重量平均分子量が高すぎると、溶融時の流動性が十分でなく、成形性に劣り易くなる。
環状オレフィン開環重合体水素化物の分子量分布(Mw/Mn)は、特に限定されないが、好ましくは1~5、より好ましくは1~4である。
環状オレフィン開環重合体水素化物の重量平均分子量(Mw)及び数平均分子量(Mn)は、シクロヘキサンを溶離液とするゲル・パーミエーション・クロマトグラフィー(GPC)による標準イソプレン換算値である。
本発明の環状オレフィン開環重合体水素化物を成形して得られた樹脂成形体(以下、「樹脂成形体(α)」ということがある。)のガラス転移温度は、140~165℃、好ましくは145~165℃、より好ましくは145~160℃である。
樹脂成形体(α)のガラス転移温度が140℃以上になる環状オレフィン重合体は、高温下寸法安定性に優れる。また、樹脂成形体(α)のガラス転移温度が160℃以下になる環状オレフィン重合体は、成形性に優れる。
このメルトフローレートが8g/10分以上になる環状オレフィン開環重合体水素化物は、成形性に優れる。
また、一般に、合成樹脂は、その重量平均分子量を低くすることでメルトフローレートを高くすることができ、本発明においてもこの性質を利用することができる。ただし、上記のように重量平均分子量を低くし過ぎると、得られる樹脂成形体の機械的強度が劣るため、本発明においては、必要以上に低分子量化することは避け、テトラシクロドデセン以外のノルボルネン系単量体の種類や使用量を調節して、メルトフローレートを高めることが好ましい。
この曲げ強度が60MPa以上になる環状オレフィン開環重合体水素化物は、高温下寸法安定性に優れる。
なお、上記のガラス転移温度、メルトフローレート、曲げ強度の測定試料として用いる樹脂成形体は、これらの測定値に影響を与えない範囲において、添加剤を含有するものであってもよい。
本発明の環状オレフィン開環重合体水素化物の黄色度差(ΔYI)は、通常、20以下、好ましくは15以下である。
本発明の環状オレフィン開環重合体水素化物は、テトラシクロドデセン由来の繰り返し単位を多く含むため耐熱黄変性に優れる。また、メタノテトラヒドロフルオレン由来の繰り返し単位の量を多くし過ぎないことで、耐熱黄変性により優れる傾向がある。
本発明の環状オレフィン開環重合体水素化物は、テトラシクロドデセン由来の繰り返し単位を多く含む。そして、ガラス転移温度を低下させることなく、溶融時の流動性を向上させたものである。したがって、本発明の環状オレフィン開環重合体水素化物は、高温下寸法安定性に優れる。
また、本発明の環状オレフィン開環重合体水素化物は、重量平均分子量を高くし過ぎることなく、曲げ強度を高めたものである。したがって、本発明の環状オレフィン開環重合体水素化物は、成形性に優れる。
本発明の樹脂成形体は、本発明の環状オレフィン開環重合体水素化物を含有する樹脂組成物を成形して得られるものである。
その他の成分としては、酸化防止剤、紫外線吸収剤、光安定剤、近赤外線吸収剤、可塑剤、帯電防止剤等が挙げられる。
酸化防止剤としては、フェノール系酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤等が挙げられる。
樹脂組成物がフェノール系酸化防止剤を含有する場合、その含有量は、環状オレフィン開環重合体水素化物100重量部に対して、好ましくは0.01~5重量部、より好ましくは0.1~2重量部、さらに好ましくは0.2~1重量部である。
光安定剤としては、ヒンダードアミン系光安定剤が挙げられる。
可塑剤としては、燐酸トリエステル系可塑剤、脂肪酸一塩基酸エステル系可塑剤、二価アルコールエステル系可塑剤、オキシ酸エステル系可塑剤等が挙げられる。
帯電防止剤としては、多価アルコールの脂肪酸エステル等が挙げられる。
本発明の樹脂成形体は、ガラス転移温度が、140~165℃、JIS K6719に基いて、温度280℃、荷重21.18N(荷重2.16kgf)の条件で測定したメルトフローレートが、8g/10分以上、かつ、JIS K7171に基いて、試験速度2mm/分で行った曲げ試験で測定した曲げ強度が、60MPa以上であるものが好ましい。
なかでも、自動車の車内に設置されるカメラに用いられるレンズ等の光学部材として特に好ましく用いられる。
(1)重量平均分子量
環状オレフィン開環重合体水素化物の重量平均分子量(Mw)は、シクロヘキサンを溶離液とするゲル・パーミエーション・クロマトグラフィー(GPC)により測定し、標準ポリイソプレン換算値として求めた。
標準ポリイソプレンとしては、東ソー社製標準ポリイソプレン(Mw=602、1390、3920、8050、13800、22700、58800、71300、109000、280000)を用いた。
測定は、カラム(東ソー社製、TSKgelG5000HXL、TSKgelG4000HXL及びTSKgel G2000HXL)を3本直列に繋いで用い、流速1.0mL/分、サンプル注入量100μL、カラム温度40℃の条件で行った。
環状オレフィン開環重合体水素化物のガラス転移温度は、示差走査熱量分析計(ナノテクノロジー社製、DSC6220SII)を用いて、JISK6911に基き昇温速度10℃/minの条件で測定した。
環状オレフィン開環重合体水素化物の、テトラシクロドデセン由来の繰り返し単位のラセモダイアッドの割合は、重水素化オルトジクロロベンゼンを溶媒として測定した13C-NMRスペクトルにおけるラセモダイアッド由来のシグナル(51.7ppm)とメソダイアッド由来のシグナル(51.6ppm)の強度比から計算して求めた。
環状オレフィン開環重合体水素化物を含む樹脂組成物のメルトフローレートは、JIS K6719に基いて、温度280℃、荷重21.18N(荷重2.16kgf)の条件で測定した。
環状オレフィン開環重合体水素化物を含む樹脂組成物のペレットを射出成形機(ファナック社製、ロボショットα-100B)に投入し、樹脂温度280℃、金型温度(Tg-15)℃、射出圧力100MPaの条件で射出成形し、長さ80mm×幅10mm×厚さ4mmの樹脂板を作製した。
次いで、この樹脂板を試験片として、オートグラフ(島津製作所社製、製品名「AGS-5kNJ・TCR2」)を用いて、JIS K7171に準じて、試験速度2mm/分の条件で曲げ試験を行い、曲げ強度(MPa)を求めた。
環状オレフィン開環重合体水素化物を含む樹脂組成物のペレットを射出成形機(ファナック社製、ロボショットα-100B)に投入し、樹脂温度280℃、金型温度(Tg-15)℃、射出圧力100MPaの条件で射出成形し、長さ70mm×幅30mm×厚さ3mmの樹脂板を作製した。
次いで、この樹脂板を試験片として、以下の方法により耐熱黄変性を評価した。
まず、試験片をオーブンに入れ、125℃で1000時間加熱した。
次いで、この試験片の黄色度(YI:イエローインデックス)を、JIS K7103に準じて、色差計を用いて、ブランクを空気として測定した。得られた黄色度YIから、空気のみの黄色度YIを差し引いた値を、試験片の黄色度差(△YI)とした。△YIが小さいほど、高温下での黄変が少なく耐熱黄変性が良好であることを意味する。
環状オレフィン開環重合体水素化物を含む樹脂組成物のペレットを射出成形機(ファナック社製、ロボショットα-100B)に投入し、凸面の曲率半径が5.73mm、凹面の曲率半径が3.01mm、大きさが直径4.5mm、レンズ部分の直径が3mm、レンズの中心厚が0.20mmのレンズを形成する金型(図1)を用い、樹脂温度300℃、金型温度(Tg-5)℃、射出圧力40MPaの条件で射出成形し、樹脂成形体(レンズ)を作製した。
得られたレンズについて、非接触三次元測定器(三鷹光機社製、製品名「NH-3SP」)を用いて、レンズの中心から1mmの範囲で寸法測定し、設計値Rからの寸法差の最大値から最小値を差し引いた値〔PV値(μm)〕を算出した。
次いで、このレンズをオーブンに入れ、130℃で170時間加熱した後、上記と同様の方法で、PV値を算出し、加熱前後のPV値の差を比較した。
加熱前のPV値と加熱後のPV値の差が小さいほど高温下での寸法変化が小さいことを意味する。
上記(7)の方法により得られた樹脂成形体(レンズ)の表面を、顕微鏡を用いて観察し、反ゲート方向に生じたウェルドラインの長さを測定し、以下の基準により成形性を評価した。
◎:ウェルドラインの長さが1.0mm未満
○:ウェルドラインの長さが1.0mm以上1.5mm未満
×:ウェルドラインの長さが1.5mm以上
内部を乾燥し、窒素置換した重合反応器に、6-エチリデン-2-テトラシクロドデセン(ETD)30%、テトラシクロドデセン(TCD)70%からなる単量体混合物2.0部(重合に使用するモノマー全量に対して1%)、脱水シクロヘキサン785部、分子量調節剤(1-ヘキセン)1.21部、ジエチルアルミニウムエトキシドのn-ヘキサン溶液(濃度:19%)0.98部、及びタングステン(フェニルイミド)テトラクロリド・テトラヒドロフランのトルエン溶液(濃度:2.0%)11.7部を入れ、50℃で10分間攪拌した。
次いで、全容を50℃に保持し、攪拌しながら、前記重合反応器中に、前記組成と同じ単量体混合物198.0部を150分かけて連続的に滴下した。滴下終了後30分間攪拌を継続した後、イソプロピルアルコール4部を添加して重合反応を停止させた。ガスクロマトグラフィーによって重合反応溶液を測定したしたところ、単量体の重合体への転化率は100%であった。
水素化反応終了後、珪藻土(「ラヂオライト(登録商標)♯500」)を濾過床として、加圧濾過器(石川島播磨重工社製;「フンダフィルタ-」)を使用し、圧力0.25MPaで加圧濾過して、無色透明の溶液を得た。
この溶液に、重合体水素化物100部当り、酸化防止剤として、ペンタエリスリチル-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](チバ・スペシャルティ・ケミカルズ社製、製品名「イルガノックス(登録商標)1010」)0.5部を加えた後、フィルター(キュノーフィルター社製;「ゼータプラス(登録商標)30H」、孔径0.5~1μm)、及び金属ファイバー製フィルター(ニチダイ社製、孔径0.4μm)を用いて異物を濾別除去した。
このペレットを用いて、上記の試験、評価を行った。結果を第1表に示す。
なお、水素化反応における水添率は99%以上であった。(以下の、実施例、比較例においても同じ)
実施例1において、単量体混合物として、TCD80%、ETD10%、ジシクロペンタジエン(DCPD)10%の組成を有するものを用いたこと以外は、実施例1と同様にしてペレットを得て、試験、評価を行った。結果を第1表に示す。
実施例1において、単量体混合物として、TCD80%、DCPD10%、メタノテトラヒドロフルオレン(MTF)10%の組成を有するものを用いたこと以外は、実施例1と同様にしてペレットを得て、試験、評価を行った。結果を第1表に示す。
実施例1において、単量体混合物として、TCD70%、DCPD10%、MTF20%の組成を有するものを用いたこと以外は、実施例1と同様にしてペレットを得て、試験、評価を行った。結果を第1表に示す。
実施例1において、単量体混合物として、TCD92%、ノルボルネン(NB)8%の組成を有するものを用い、分子量調節剤である1-ヘキセンの量を0.8部に変更したこと以外は、実施例1と同様にしてペレットを得て、試験、評価を行った。結果を第1表に示す。
実施例1において、単量体混合物として、TCD90%、NB10%の組成を有するものを用いたこと以外は、実施例1と同様にしてペレットを得て、試験、評価を行った。結果を第1表に示す。
内部を乾燥し、窒素置換した重合反応器に、MTF2.0部(重合に使用するモノマー全量に対して1%)、脱水シクロヘキサン785部、分子量調節剤(1-ヘキセン)0.86部、ジイソプロピルエ-テル0.42部、イソブチルアルコール0.11部、トリイソブチルアルミニウムのn-ヘキサン溶液(濃度:15%)1.80部、及び六塩化タングステンのシクロヘキサン溶液(濃度:0.65%)13.4部を入れ、55℃で10分間攪拌した。
次いで、全容を50℃に保持し、攪拌しながら、前記重合反応器中にMTF198.0部と六塩化タングステン0.65%シクロヘキサン溶液20.1部を各々150分かけて連続的に滴下した。滴下終了後30分間攪拌を継続した後、イソプロピルアルコール0.4部を添加して重合反応を停止させた。
この後の工程は、実施例1と同様にしてペレットを得て、試験、評価を行った。結果を第1表に示す。
比較例3において、分子量調節剤である1-ヘキセンの量を0.6部に変更したことと、珪藻土担持ニッケル触媒の代わりにアルミナ担持ニッケル触媒(N163A、日揮化学社製)5部を使用し、反応温度230℃、水素圧力4.5MPaの条件で8時間水素化反応を行ったこと以外は、比較例3と同様にしてペレットを得て、試験、評価を行った。結果を第1表に示す。
比較例3において、MTFの代わりに、TCD25%、MTF70%、NB5%の組成の単量体混合物を使用し、さらに、分子量調節剤である1-ヘキセンの量を1.2部に変更したこと以外は、比較例3と同様にしてペレットを得て、試験、評価を行った。結果を第1表に示す。
実施例1~4で得られた環状オレフィン開環重合体水素化物は、耐熱黄変性、高温下寸法安定性、成形性が高度にバランスされている。
一方、比較例1で得られた環状オレフィン開環重合体水素化物は重量平均分子量が高すぎるため、機械的強度に優れるものの、メルトフローレートが低く、成形性に劣っている。また、この成形性を向上させるために、重合平均分子量を低くすると、機械的強度に劣る(比較例2)。
比較例2、4、5で得られた環状オレフィン開環重合体水素化物はガラス転移温度が低く、高温下寸法安定性に劣っている。
比較例3、5で得られた環状オレフィン開環重合体水素化物はメタノテトラヒドロフルオレン由来の繰り返し単位を多く含むものであり、耐熱黄変性に劣っている。また、これは、比較例4で示されるように、水素化反応の反応条件を変えることで改善が図れるものの、この場合、上記のようにガラス転移温度が低くなり、高温下寸法安定性に劣る。
Claims (5)
- テトラシクロドデセン由来の繰り返し単位と、その他のノルボルネン系単量体由来の繰り返し単位とからなり、
前記テトラシクロドデセン由来の繰り返し単位の含有量が、全繰り返し単位に対して55重量%以上100重量%未満、前記その他のノルボルネン系単量体由来の繰り返し単位の含有量が、全繰り返し単位に対して0重量%超45重量%以下であり、
前記テトラシクロドデセン由来の繰り返し単位のラセモダイアットの割合が、65%以上であり、かつ、
重量平均分子量(Mw)が10,000~40,000の、
環状オレフィン開環重合体水素化物であって、
前記環状オレオフィン開環重合体水素化物を成形することにより、
ガラス転移温度が、140~165℃、
JIS K6719に基いて、温度280℃、荷重21.18Nの条件で測定したメルトフローレートが、8g/10分以上、かつ、
JIS K7171に基いて、試験速度2mm/分で行った曲げ試験で測定した曲げ強度が、60MPa以上、
の樹脂成形体が得られるものであることを特徴とする、環状オレフィン開環重合体水素化物。 - 3環以上の多環構造を有する多環式ノルボルネン系単量体に由来する繰り返し単位を、全繰り返し単位に対して95重量%以上含む、請求項1に記載の環状オレフィン開環重合体水素化物。
- 請求項1または2に記載の環状オレフィン開環重合体水素化物を含有する樹脂組成物を成形して得られる樹脂成形体。
- ガラス転移温度が、140~165℃、
JIS K6719に基いて、温度280℃、荷重21.18Nの条件で測定したメルトフローレートが、8g/10分以上、かつ、
JIS K7171に基いて、試験速度2mm/分で行った曲げ試験で測定した曲げ強度が、60MPa以上である、請求項3に記載の樹脂成形体。 - 請求項3又は4に記載の樹脂成形体からなる光学部材。
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