CN103237843B - Resin combination and molding thereof - Google Patents

Resin combination and molding thereof Download PDF

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Publication number
CN103237843B
CN103237843B CN201180053111.3A CN201180053111A CN103237843B CN 103237843 B CN103237843 B CN 103237843B CN 201180053111 A CN201180053111 A CN 201180053111A CN 103237843 B CN103237843 B CN 103237843B
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ring
opening polymerization
resin combination
polymerization polymer
molding
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CN103237843A (en
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角替靖男
三井郁
高山昭弘
池田进太郎
田形纯正
宫泽慎介
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Zeon Corp
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Nippon Zeon Co Ltd
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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
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/72—Derivatisation
    • C08G2261/724—Hydrogenation
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/483—Containers
    • H01L33/486—Containers adapted for surface mounting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements

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Abstract

The invention provides a kind of containing have the repeating unit being derived from polycycle Norbornene derivative crystalline cyclic olefin ring-opening polymerization polymer hydride, be the wax of 1 ~ 4 weight part and the resin combination of nucleator relative to this hydride 100 weight part and the molding that melt-shaping obtains carried out to this resin combination.According to the present invention, even if can obtain with good plasticity providing carries out injection forming under compared with the die temperature of low temperature, crystallization also fully carries out, the resin combination of the molding of the distortion not easily causing the impact because of heat to cause and molding, particularly luminous reflectance factor excellence thereof, even if under the high temperature conditions, the luminous reflectance factor of its excellence also can not reduce and the LED light tamper that can maintain for a long time.

Description

Resin combination and molding thereof
Technical field
The present invention relates to a kind of resin combination and molding thereof, even if described resin combination can provide carry out injection forming under compared with the die temperature of low temperature, also fully can carry out crystallization, and not easily cause the molding of distortion due to the impact of heat.
Background technology
The film be made up of the cyclic olefin polymer of crystallinity (namely there is fusing point) or sheet material; the excellences such as its chemical proofing, water vapor barrier, thermotolerance, the transparency; therefore, be widely used in wrapping material or protective membrane etc. (patent documentation 1).
In addition, the monomer using 2-norbornylene as main component is made to carry out ring-opening polymerization and carry out hydrogenation, obtain crystallizing cyclic olefin polymer hydride, in this hydride, coordinate nucleator to obtain composition, the known film obtained by said composition can realize lower steam breathability (patent documentation 2).
On the other hand, although aliphatic polyester resin is crystalline resin, crystallization rate slowly, therefore, use mould carry out injection forming obtain molding time, exist and need high temperature and long problem.In order to solve this problem, propose following scheme: add on a small quantity as the adipic acid ester of softening agent, thus make die temperature also can not cause distortion (patent documentation 3) when the demoulding below 80 DEG C.
But LED (photodiode: Light Emitting Diode) is the light source with following feature: electric energy is directly converted to light and carries out luminescence, therefore, energy efficiency is good, and, relative to incandescent-lamp bulb or luminescent lamp etc., can long lifetime and miniaturization.Therefore, in recent years, be used as the back light of the electronicss such as portable phone or large-scale liquid crystal indicator, road traffic display panel light source, replace the general illumination utensil of incandescent-lamp bulb or luminescent lamp.
Generally speaking, LED, by the semi-conductor chip as luminous element, protects its sealing material and forms for the light reflector in the direction adjusting light.The light that light reflector reflective semiconductor chip sends, uses in order to light is come together in the direction of needs, is the vitals playing the brightness improving LED.
The light reflector (LED light tamper) forming LED requires higher luminous reflectance factor.In addition, LED light tamper when it is shaped (heating for melt-shaping), when manufacturing (heating be cured for making sealing material or welding) and when using (heat release of semi-conductor chip) etc. be subject to the impact of heat.Therefore, as the material of LED light tamper, be widely used in the composition (patent documentation 4,5 etc.) coordinating the white pigments such as titanium oxide in the polyamide resin of excellent heat resistance.
But even by the LED light tamper that forms of composition recorded in patent documentation 4,5, can not say that thermotolerance is abundant, luminous reflectance factor reduces because of the impact of heat be subject to when being shaped etc. sometimes.In addition, with regard to coordinate the composition of the white pigments such as titanium oxide in polyamide resin with regard to, in order to form it, need higher temperature, and viscosity during melting is high, therefore, the problem had difficulties when also there is the shaping to light reflector.Therefore, be strongly required the shaped material of the following LED light tamper of exploitation, the shaped material of described light reflector can provide light reflector with good plasticity, and, the reduction of luminous reflectance factor is not easily caused due to the impact of heat.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2002-194067 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-084332 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2010-006893 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2-288274 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2006-257314 publication
Summary of the invention
The technical problem that invention will solve
The present invention completes in view of above-mentioned prior art, its technical problem is, a kind of resin combination and molding thereof are provided, even if described resin combination can provide carry out injection forming under compared with the die temperature of low temperature, also fully crystallization can be carried out, and the molding of the distortion not easily causing the impact because of heat to cause.And then technical problem of the present invention is, utilize this resin combination, provide a kind of and can realize good plasticity, and the LED light tamper that the luminous reflectance factor not easily causing the impact because of heat to cause reduces.
For the scheme of technical solution problem
The present inventor etc. concentrate on studies to solve the problems of the technologies described above.First, according to the record of described patent documentation 3, carry out injection forming to having coordinated the crystalline cyclic olefin polymer of the organic acid acetic being typically used as softening agent, result shows when die temperature is low temperature, crystallinity is insufficient, therefore, deforms when the demoulding.Therefore, carried out further research, found that, coordinated the resin combination of a small amount of wax and nucleator to carry out injection forming if be used in crystalline cyclic olefin polymer hydride, can solve the above problems.
Finding in addition, by using this resin combination, the LED light tamper not easily causing because of the impact of heat luminous reflectance factor to reduce can be obtained with good plasticity, so that complete the present invention.
Therefore, according to the present invention, the molding of the resin combination of following (1) ~ (5), (6), (7) can be provided.
(1) a kind of resin combination, it contains crystalline cyclic olefin ring-opening polymerization polymer hydride, is wax and the nucleator of 1 ~ 4 weight part relative to this hydride of 100 weight parts, and described cyclic olefin ring-opening polymerization polymer hydride has the repeating unit being derived from polycycle Norbornene derivative.
(2) resin combination Gen Ju (1), wherein, described cyclic olefin ring-opening polymerization polymer hydride is the cyclic olefin ring-opening polymerization polymer hydride with syndiotactic regularity.
(3) resin combination Gen Ju (1), wherein, described wax is hydrocarbon wax.
(4) resin combination Gen Ju (1), wherein, described nucleator is the metal-salt of talcum or organic phosphoric acid.
(5) resin combination Gen Ju (1), wherein, relative to cyclic olefin ring-opening polymerization polymer hydride described in 100 weight parts, the content of described nucleator is 0.001 ~ 5 weight part.
(6) molding, it carries out melt-shaping to the resin combination according to any one of (1) ~ (5) and obtains.
(7) molding Gen Ju (6), it is LED light tamper.
Invention effect
According to resin combination of the present invention, even if can obtain carrying out injection forming under compared with the die temperature of low temperature, also fully can carry out crystallization, and the molding of distortion can not be caused because of the impact of heat.
According to resin combination of the present invention, even if the luminous reflectance factor that can obtain luminous reflectance factor excellence its excellence under the high temperature conditions with good plasticity also can maintain and the LED light tamper do not reduced for a long time.
Molding of the present invention not easily causes distortion because of the impact of heat.
Embodiment
Below, the present invention is divided into 1) resin combination and 2) molding two is described in detail.
1) resin combination
The feature of resin combination of the present invention is, (following containing crystalline cyclic olefin ring-opening polymerization polymer hydride, sometimes referred to as " crystallizing cyclic alkene ring-opening polymerization polymer hydride "), be wax and the nucleator of 1 ~ 4 weight part relative to this hydride of 100 weight parts, described cyclic olefin ring-opening polymerization polymer hydride has the repeating unit being derived from polycycle Norbornene derivative.
< crystallizing cyclic alkene ring-opening polymerization polymer hydride >
The crystallizing cyclic alkene ring-opening polymerization polymer hydride used in the present invention by the monomer at least containing polycycle Norbornene derivative is carried out ring-opening polymerization and carries out hydrogenation to the main chain double bond of the ring-opening polymerization polymer obtained and obtain, and has crystallinity.
The method obtaining above-mentioned crystallizing cyclic alkene ring-opening polymerization polymer hydride is not particularly limited, and can enumerate method described in such as Japanese Unexamined Patent Publication 2006-52333 publication.According to the method, obtaining the cyclic olefin ring-opening polymerization polymer with syndiotactic regularity, by carrying out hydrogenation to it, target cyclic olefin ring-opening polymerization polymer hydride can be obtained efficiently.
The cyclic olefin ring-opening polymerization polymer used in the present invention by the ring using having more than 3 rings polycycle Norbornene derivative as monomer use at least partially and obtain.
As long as polycycle Norbornene derivative has the norbornylene compounds of norbornylene skeleton and the ring structure of more than 1 of condensation on this norbornylene skeleton in molecule.Good especially from the viewpoint of the thermotolerance of the molding be made up of resin combination, as polycycle Norbornene derivative, particularly preferably following formula (1) or the compound shown in (2).
[chemical formula 1]
[chemical formula 2]
In formula (1), (2), R 1, R 2, R 4~ R 7separately represent hydrogen atom; Halogen atom; The alkyl of substituent carbonatoms 1 ~ 20 can be had; Or the substituting group containing Siliciumatom, Sauerstoffatom or nitrogen-atoms.In addition, R 1and R 2, R 4and R 6bonding can be distinguished and form ring.R 3for the bivalent hydrocarbon radical of substituent carbonatoms 1 ~ 20 can be had.M is 1 or 2.
As R 1, R 2, R 4~ R 7halogen atom, can enumerate: fluorine atom, chlorine atom, bromine atoms etc.
As the alkyl that can have in the alkyl of substituent carbonatoms 1 ~ 20, can enumerate: the alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, hexyl, heptyl, octyl group, nonyl, decyl; The cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl; The alkenyls such as vinyl, 1-propenyl, allyl group, 1-butylene base, crotyl, pentenyl, hexenyl, cyclohexenyl; The alkynyls such as ethynyl, 1-proyl, 2-propynyl (propargyl), 3-butynyl, pentynyl, hexin base; The aryl such as phenyl, tolyl, xylyl, xenyl, 1-naphthyl, 2-naphthyl, anthryl, phenanthryl; The aralkyl such as benzyl, styroyl etc.
As these substituting groups, can enumerate: the halogen atoms such as fluorine atom, chlorine atom; The alkoxyl group such as methoxyl group, oxyethyl group etc.
As R 3in can have bivalent hydrocarbon radical in the bivalent hydrocarbon radical of substituent carbonatoms 1 ~ 20, can enumerate: the alkylidene group such as methylene radical, ethylidene; The alkylene groups such as vinylidene; The alkynylenes such as ethynylene; The arylidene such as phenylene; Their combination etc.As its substituting group, can enumerate with as R 1, R 2, R 4~ R 7the same substituting group of the illustrative substituting group of substituting group of alkyl.
As the concrete example of the polycycle Norbornene derivative shown in formula (1), can enumerate: Dicyclopentadiene (DCPD), methyl dicyclopentadiene, three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-alkene, Fourth Ring [9.2.1.0 2,10.0 3,8] 14 carbon-3,5,7,12-tetraenes (also referred to as Isosorbide-5-Nitrae-endo-methylene group-Isosorbide-5-Nitrae, 4a, 9a-tetrahydrochysene-9H-fluorenes), Fourth Ring [10.2.1.0 2,11.0 4,9] 15 carbon-4,6,8,13-tetraenes (also referred to as Isosorbide-5-Nitrae-endo-methylene group-Isosorbide-5-Nitrae, 4a, 9,9a, 10-six hydrogen anthracene).
In addition, as the polycycle Norbornene derivative shown in formula (2), can enumerate: six ring ten heptaeneses when the m of the tetracyclododecane when m of formula (2) is 1 and formula (2) is 2.
As the concrete example of tetracyclododecane, can enumerate: tetracyclododecane, 8-methyl tetracyclododecane, 8-ethyltetracyclo dodecylene, 8-cyclohexyl tetracyclododecane, 8-cyclopentyl tetracyclododecane etc. are without the tetracyclododecane replacing or have alkyl; 8-methene base tetracyclododecane, 8-ethidine tetracyclododecane, 8-vinyl tetracyclododecane, 8-propenyl tetracyclododecane, 8-cyclohexenyl tetracyclododecane, 8-cyclopentenyl tetracyclododecane etc. have the tetracyclododecane of double bond outside ring; 8-phenyl tetracyclododecane etc. has the tetracyclododecane of aromatic nucleus; 8-methoxycarbonyl tetracyclododecane, 8-methyl-8-methoxycarbonyl tetracyclododecane, 8-hydroxymethyl tetracyclododecane, 8-carboxyl tetracyclododecane, tetracyclododecane-8,9-dicarboxylic acid, tetracyclododecane-8,9-dicarboxylic anhydride etc. have the substituent tetracyclododecane containing Sauerstoffatom; 8-cyano group tetracyclododecane, tetracyclododecane-8,9-dicarboxylic acid imides etc. have the substituent tetracyclododecane of nitrogen atom; 8-chlorotetracyclin dodecylene etc. has the substituent tetracyclododecane of halogen atom-containing; 8-trimethoxysilyl tetracyclododecane etc. has the substituent tetracyclododecane of silicon atoms.
As the concrete example of six ring heptadecene classes, can enumerate: six ring heptadecenes, 12-methyl six ring heptadecene, 12-ethyl six ring heptadecene, 12-cyclohexyl six ring heptadecene, 12-cyclopentyl six ring heptadecene etc. are without the six ring heptadecene classes replacing or have alkyl; 12-methene base six ring heptadecene, 12-ethidine six ring heptadecene, 12-vinyl six ring heptadecene, 12-propenyl six ring heptadecene, 12-cyclohexenyl six ring heptadecene, 12-cyclopentenyl six ring heptadecene etc. have six ring heptadecene classes of double bond outside ring; 12-phenyl six ring heptadecene etc. has six ring heptadecene classes of aromatic nucleus; 12-methoxycarbonyl six ring heptadecene, 12-methyl isophthalic acid 2-methoxycarbonyl six ring heptadecene, 12-hydroxymethyl six ring heptadecene, 12-carboxyl six ring heptadecene, six ring heptadecenes 12,13-dicarboxylic acid, six ring heptadecene 12,13-dicarboxylic anhydrides etc. have the substituent six ring heptadecene classes containing Sauerstoffatom; 12-cyano group six ring heptadecene, six ring heptadecene 12,13-dicarboxylic acid imides etc. have the substituent six ring heptadecene classes of nitrogen atom; 12-chlorine six ring heptadecene etc. has the substituent six ring heptadecene classes of halogen atom-containing; 12-trimethoxysilyl six ring heptadecene etc. has the substituent six ring heptadecene classes of silicon atoms.
These polycycle Norbornene derivatives can be used alone a kind, or combinationally use two or more.
Wherein, from the crystallinity improving cyclic olefin ring-opening polymerization polymer hydride, the viewpoint that the thermotolerance of the molding obtained is good is especially considered, preferred use contains the material of more than 50 % by weight Dicyclopentadiene (DCPD) relative to polycycle Norbornene derivative total amount, is particularly preferably used alone Dicyclopentadiene (DCPD).
In addition, there is the steric isomer of inner mold and external form in polycycle Norbornene derivative, it all can be used as monomer, can be used alone a kind of isomer, also can use the isomer mixture that inner mold and external form exist with arbitrary ratio.But, from the crystallinity improving cyclic olefin ring-opening polymerization polymer hydride, the viewpoint that the thermotolerance of the resin combination obtained is good is especially considered, the ratio of preferred raising wherein a kind of steric isomer, such as preferably the ratio of inner mold or external form is more than 80%, be more preferably more than 90%, be particularly preferably more than 95%.In addition, from the viewpoint of the viewpoint of synthesis easiness, carry a high proportion of steric isomer and be preferably inner mold.
When obtaining cyclic olefin ring-opening polymerization polymer, can the monomer beyond polycycle Norbornene derivative and polycycle Norbornene derivative be made to carry out copolymerization in the scope obtaining having crystalline polymkeric substance.As can with the monomer of polycycle Norbornene derivative copolymerization, can enumerate: not there is 2 ring norbornylene compounds of the ring structure of condensation on norbornylene skeleton, single cyclic olefin and cyclic diene and their derivative.
As the concrete example of 2 ring norbornylene compounds without the ring structure of condensation on norbornylene skeleton, can enumerate: norbornylene, 5-methyinorbornene, 5-ethyl norbornene, 5-butyl norbornylene, 5-hexyl norbornylene, 5-decyl norbornene, 5-cyclohexyl norbornylene, 5-cyclopentyl norbornylene etc. are without the norbornylene class replacing or have alkyl; 5-ethylidene norbornene, 5-vinyl norbornene, 5-propenyl norbornylene, 5-cyclohexenylnorbornenes, 5-cyclopentenyl norbornylene etc. have the norbornylene class of alkenyl; 5-phenyl norbornene etc. has the norbornylene class of aromatic nucleus; 5-methoxycarbonyl norbornylene, 5-ethoxy carbonyl norbornylene, 5-methyl-5-methoxycarbonyl norbornylene, 5-methyl-5-ethoxy carbonyl norbornylene, norbornene-2 Methylpropionic acid ester, norbornene-2-methyloctanoic acid ester, 5-hydroxymethyl norbornylene, 5,6-bis-(hydroxymethyl) norbornylene, 5,5-bis-(hydroxymethyl) norbornylene, 5-hydroxy-iso-propyl norbornylene, 5,6-dicarboxyl norbornylenes, 5-methoxycarbonyl-6-carboxyl norbornylene etc. have the norbornylene class of the polar group containing Sauerstoffatom; 5-Cyanonorbornene etc. has the norbornylene class of the polar group of nitrogen atom.
As the concrete example of single cyclic olefin, can enumerate: tetrahydrobenzene, suberene, cyclooctene.
In addition, as the concrete example of cyclic diene, can enumerate: cyclohexadiene, cycloheptadiene.
Wherein, from the crystallinity improving cyclic olefin ring-opening polymerization polymer hydride, the viewpoint that the thermotolerance of the molding obtained is good is especially considered, as the monomer for obtaining the cyclic olefin ring-opening polymerization polymer being supplied in hydrogenation, preferably contain the polycycle Norbornene derivative of more than 80 % by weight relative to the monomer total amount used, the monomer particularly preferably used in fact only is made up of polycycle Norbornene derivative.
In order to obtain the cyclic olefin ring-opening polymerization polymer hydride with syndiotactic regularity, need to there is the cyclic olefin ring-opening polymerization polymer of syndiotactic regularity for hydrogenation.
Therefore, when by the ring-opening polymerization of polycycle Norbornene derivative, need to use the ring-opening polymerization catalyst can giving syndiotactic regularity to cyclic olefin ring-opening polymerization polymer.As such ring-opening polymerization catalyst, as long as syndiotactic regularity can be given to cyclic olefin ring-opening polymerization polymer, be not particularly limited, ring-opening polymerization catalyst preferably containing the metallic compound (following, to be sometimes referred to as " metallic compound (3) ") shown in following formula (3).
[chemical formula 3]
M(NR 8)X 4-a(OR 9) a·L b(3)
In formula, M is the atoms metal being selected from the periodic table of elements the 6th group 4 transition metal atom, R 8for can 3, in 4,5, at least 1 position has substituent phenyl or uses CH 2r 10the group represented, R 9for being selected from the group that can have substituent alkyl and can have substituent aryl, X is the group being selected from halogen atom, alkyl, aryl and aIkylsilyl groups, and L is to electro neutral ligand, a be 0 or 1, b be the integer of 0 ~ 2.R 10for being selected from hydrogen atom, substituent alkyl can being had and the group of substituent aryl can be had.
The atoms metal (M) forming metallic compound (3) is selected from the periodic table of elements the 6th group 4 transition metal atom (chromium, molybdenum, tungsten).Wherein, can preferably use molybdenum or tungsten, particularly preferably can use tungsten.
Metallic compound (3) is containing metal imide bond.R 8for forming the substituting group on the nitrogen-atoms of metal imide bond.
As 3, in 4,5, at least 1 position can having the substituting group that substituent phenyl has, can enumerating: the alkyl such as methyl, ethyl; The halogen atoms such as fluorine atom, chlorine atom, bromine atoms; The alkoxyl groups such as methoxyl group, oxyethyl group, isopropoxy, in addition, the substituting group being present at least 2 positions of 3,4,5 can bonding mutually.
As can 3, at least 1 position of 4,5 has the concrete example of substituent phenyl, can enumerate: phenyl; One substituted-phenyls such as 4-aminomethyl phenyl, 4-chloro-phenyl-, 3-p-methoxy-phenyl, 4-cyclohexyl phenyl, 4-p-methoxy-phenyl; The di-substituted-phenyls such as 3,5-3,5-dimethylphenyl, 3,5-dichlorophenyls, 3,4-3,5-dimethylphenyls, 3,5-Dimethoxyphenyls; The tri-substituted phenyls such as 3,4,5-trimethylphenyl, 3,4,5-trichlorophenyl; 2-naphthyl, 3-methyl-2-naphthyl, 4-methyl-2-naphthyl etc. can have substituent 2-naphthyl.
In metallic compound (3), can be used for the substituting group (R in formula (3) on nitrogen-atoms 8) and with-CH 2r 10r in the group represented 10in, the carbonatoms can with substituent alkyl is not particularly limited, and is generally 1 ~ 20, is preferably 1 ~ 10.In addition, this alkyl can be straight-chain, also can be branched.The substituting group that this alkyl can have is not particularly limited, such as, can enumerate: phenyl, 4-aminomethyl phenyl etc. can have substituent phenyl; The alkoxyl group such as methoxyl group, oxyethyl group.
As R 10in can have substituent aryl, can enumerate: phenyl, 1-naphthyl, 2-naphthyl etc.As the substituting group of this aryl, be not particularly limited, such as, can enumerate: phenyl, 4-aminomethyl phenyl etc. can have substituent phenyl; The alkoxyl group such as methoxyl group, oxyethyl group etc.
As R 10, the alkyl of the carbonatomss 1 ~ 20 such as preferable methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, octyl group, decyl.
Metallic compound (3) has the group that 3 or 4 are selected from halogen atom, alkyl, aryl and aIkylsilyl groups.That is, in formula (3), X represents the group being selected from halogen atom, alkyl, aryl and aIkylsilyl groups.In addition, when the group shown in X is more than 2 in the metallic compound (3), these groups can bonding mutually.
As the halogen atom that can become the group shown in X, can enumerate: chlorine atom, bromine atoms, atomic iodine.As alkyl, can enumerate: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, benzyl, 2-methyl-2-phenyl propyl (ネ オ Off ィ Le, neophyl) etc.As aryl, can enumerate: phenyl, 4-aminomethyl phenyl, 2,6-3,5-dimethylphenyls, 1-naphthyl, 2-naphthyl etc.As aIkylsilyl groups, can enumerate: trimethyl silyl, triethylsilyl, t-butyldimethylsilyl etc.
Metallic compound (3) can have the aryloxy metallic bond of 1 metal alkoxides key or 1.Form the substituting group (R in formula (3) on the Sauerstoffatom of this metal alkoxides key or aryloxy metallic bond 9) for being selected from the group that can have substituent alkyl and substituent aryl can be had.As becoming R 9can having substituent alkyl and maybe can having substituent aryl of shown group, can use and above-mentioned R 10the group that those groups in shown group are same.
Metallic compound (3) can have 1 or 2 to electro neutral ligand.As this give electro neutral ligand (L in formula (3), such as can enumerate the atom containing the periodic table of elements the 14th race or the 15th race to electro compound.As its concrete example, can enumerate: the phosphine classes such as trimethyl-phosphine, tri isopropyl phosphine, tricyclohexyl phosphine, triphenylphosphine; The ethers such as diethyl ether, dibutyl ether, 1,2-glycol dimethyl ether, tetrahydrofuran (THF); The amines such as Trimethylamine, triethylamine, pyridine, two picolins.Wherein, particularly preferably ethers can be used.
As the ring-opening polymerization catalyst for obtaining the cyclic olefin ring-opening polymerization polymer with syndiotactic regularity, the metallic compound (3) that can particularly preferably use, as this metallic compound (3), can enumerate: there is the tungsten compound of phenyl imide (in formula (3), M is tungsten atom, and R 8compound for during phenyl), wherein, particularly preferably monoethyl imide tungsten (tetrahydrofuran (THF)).
Metallic compound (3) by by the oxyhalogenation thing of the 6th group 4 transition metal, can 3, at least 1 position of 4,5 has substituent phenyl isocyanate class or a substituent methyl isocyanates, synthesize to electro neutral ligand (L) and alcohols as required, metal alkoxides, aryloxy metal etc. (method described in such as Japanese Unexamined Patent Publication 5-345817 publication).The metallic compound (3) of synthesis can use the compound being carried out purifies and separates by crystallization etc., also can not carry out purifying, and catalyst synthesis solution is directly used as ring-opening polymerization catalyst.
Usage quantity as the metallic compound (3) of ring-opening polymerization catalyst is generally 1:100 ~ 1:2 with the molar ratio computing of (metallic compound (3): use monomer entirety), 000,000, be preferably 1:500 ~ 1:1,000,000, be more preferably 1:1,000 ~ 1:500, the amount of 000.If catalytic amount is too much, is then likely difficult to remove catalyzer, if very few, then sometimes cannot obtains sufficient polymerization activity.
By metallic compound (3) as ring-opening polymerization catalyst time, can be used alone metallic compound (3), but from the viewpoint of raising polymerization activity, preferably in metallic compound (3), combinationally use organo-metallic reductive agent.
As the organo-metallic reductive agent used, can enumerate the periodic table of elements the 1st of the alkyl with carbonatoms 1 ~ 20,2,12,13,14 races.Wherein, organolithium, organic-magnesium, organic zinc, organoaluminum or organotin can be preferably used, organoaluminum or organotin can be particularly preferably used.
As organolithium, can enumerate: n-Butyl Lithium, lithium methide, phenyl lithium etc.As organic-magnesium, can enumerate: butyl ethyl magnesium, butyl octyl magnesium, dihexyl magnesium, ethylmagnesium chloride, n-butylmagnesium chloride magnesium, allylic bromination magnesium.As organic zinc, can enumerate: zinc methide, zinc ethyl, phenylbenzene zinc etc.As organoaluminum, trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, diethyl aluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum ethoxide, diisobutyl aluminum isopropylate, ethyl diethyl aluminium alcoholates, isobutyl-aluminum-diisopropoxide etc.As organotin, can enumerate: tin tetramethide, four (normal-butyl) tin, tin tetraphenyl etc.
The usage quantity of organo-metallic reductive agent preferably relative to metallic compound (3) be 0.1 ~ 100 mole doubly, more preferably 0.2 ~ 50 mole doubly, particularly preferably 0.5 ~ 20 mole doubly.If usage quantity is very few, then polymerization activity can not improve sometimes, if too much, then likely easily causes side reaction.
Polyreaction for obtaining crystallizing cyclic alkene ring-opening polymerization polymer is carried out usually in organic solvent.As long as the organic solvent used can make target ring-opening polymerization polymer or its hydride dissolve under defined terms or disperse, and does not hinder polyreaction or hydrogenation, there is no particular limitation.
As the concrete example of organic solvent, can enumerate: the aliphatic hydrocarbons such as pentane, hexane, heptane; The clicyclic hydrocarbon such as pentamethylene, hexanaphthene, methylcyclohexane, dimethyl cyclohexane, trimethyl-cyclohexane, ethylcyclohexane, diethyl cyclohexane, perhydronaphthalene, norbornane, tristane, six hydrogen indenes, cyclooctane; The aromatic hydrocarbonss such as benzene,toluene,xylene; The halogen aliphatic hydrocarbons such as dichloro hexane, chloroform, 1,2-ethylene dichloride; The halogen such as chlorobenzene, dichlorobenzene aromatic hydrocarbons; The nitrogen-containing hydrocarbons kind solvents such as Nitromethane 99Min., oil of mirbane, acetonitrile; The ethers such as Anaesthetie Ether, tetrahydrofuran (THF); Or their mixed solvent.In these solvents, can preferably use aromatic hydrocarbons, aliphatic hydrocarbon, clicyclic hydrocarbon, ethers.
Ring-opening polymerization is by causing the mixing of monomer, metallic compound (3) and organo-metallic reductive agent as required.The order of adding these compositions is not particularly limited.The mixture that such as can add metallic compound (3) and organo-metallic reductive agent in monomer mixes, the mixture that also can add monomer and metallic compound (3) in organo-metallic reductive agent mixes, in addition, metallic compound (3) can also be added in the mixture of monomer and organo-metallic reductive agent to mix.
When mixing each composition, once can add the total amount of each composition, also can divide and adding for several times, can also adding continuously through the longer time (such as more than 1 minute).Wherein, from the viewpoint of controlling polymerization temperature and the molecular weight of ring-opening polymerization polymer that obtains and obtaining plasticity resin combination excellent especially, preference score is secondary or add monomer or metallic compound (3) continuously, particularly preferably divides for several times or adds monomer continuously.
Monomer concentration during polyreaction in organic solvent is not particularly limited, and is preferably 1 ~ 50 % by weight, is more preferably 2 ~ 45 % by weight, and particularly preferably 3 ~ 40 % by weight.If the concentration of monomer is too low, then likely the productivity of polymkeric substance is deteriorated, and when too high, the soltion viscosity after polymerization is too high, the hydrogenation after being likely difficult to carry out.
Also active regulator can be added in polyreaction system.Active regulator can use in order to divided ring polymerizing catalyst carries out stabilization, the adjustment speed of polyreaction and the molecular weight distribution of polymkeric substance.As long as active regulator is just not particularly limited for the organic compound with functional group, preferred oxygen-containing organic compound, organic compounds containing nitrogen, organic phosphorus compound.Specifically, can enumerate: the ethers such as Anaesthetie Ether, Di Iso Propyl Ether, dibutyl ether, methyl-phenoxide, furans, tetrahydrofuran (THF); The ketones such as acetone, benzophenone, pimelinketone; The ester classes such as vinyl acetic monomer; The nitrile such as acetonitrile, cyanobenzene; The amines such as triethylamine, triisopropylamine, rubane, N, N-Diethyl Aniline; The pyridines such as pyridine, 2,4-bis-picolins, 2,6-bis-picolins, 2-tert .-butylpyridine; The phosphine such as triphenylphosphine, tricyclohexyl phosphine class; The phosphoric acid ester such as trimethyl phosphite 99, triphenylphosphate; The phosphinoxidess etc. such as triphenylphosphine oxide.These active regulators can be used alone a kind or be mixed with two or more.The amount of the active regulator added is not particularly limited, as long as be carry out between 0.01 ~ 100 % by mole selecting relative to the metallic compound as ring-opening polymerization catalyst usually.
In addition, in order to regulate the molecular weight of ring-opening polymerization polymer, also molecular weight regulator can be added in polyreaction system.As molecular weight regulator, can enumerate: the alpha-olefines such as 1-butylene, 1-amylene, 1-hexene, 1-octene; The aromatic ethenyl compound such as vinylbenzene, Vinyl toluene; Ethyl vinyl ether, IVE, glycidyl allyl ether, allyl acetate, allyl alcohol, glycidyl methacrylate etc. are containing oxyethylene group compound; The halogen-containing vinyl compound such as allyl chloride; The nitrogenous vinyl compound such as acrylamide; Isosorbide-5-Nitrae-pentadiene, Isosorbide-5-Nitrae-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl isophthalic acid, the non-conjugated dienes such as 4-pentadiene, 2,5-dimethyl-1,5-hexadienes; 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene equiconjugate diene.
As long as the amount of the molecular weight regulator added is determined according to target molecular weight, usually select in the scope that the monomer relative to use is 0.1 ~ 50 % by mole.
Polymerization temperature is not particularly limited, and is generally the scope of-78 DEG C ~+200 DEG C, is preferably the scope of-30 DEG C ~+180 DEG C.Polymerization time depends on anti-scale, but is also not particularly limited, and is generally the scope of 1 minute ~ 1000 hours.
By the ring-opening polymerization using the ring-opening polymerization catalyst containing metallic compound as above (3) to carry out the monomer containing polycycle Norbornene derivative under conditions, as described above, the cyclic olefin ring-opening polymerization polymer with syndiotactic regularity can be obtained.
Ratio for the racemize diad (ラ セ モ ダ イ ア ッ De) in the cyclic olefin ring-opening polymerization polymer of hydrogenation is not particularly limited, and is generally more than 60%, is preferably more than 65%, is more preferably 70 ~ 99%.The ratio (degree of syndiotactic regularity) of the racemize diad of cyclic olefin ring-opening polymerization polymer regulates by selecting the kind etc. of ring-opening polymerization catalyst.
Cyclic olefin ring-opening polymerization polymer for hydrogenation is not particularly limited by the weight-average molecular weight (Mw) of gel permeation chromatography, preferably converts with polyisoprene and counts 10,000 ~ 100,000, be more preferably 15,000 ~ 80,000.When using the cyclic olefin ring-opening polymerization polymer hydride obtained by the cyclic olefin ring-opening polymerization polymer with such weight-average molecular weight, having excellent formability, the excellent heat resistance of molding that obtains in consider, be preferred.The weight-average molecular weight of cyclic olefin ring-opening polymerization polymer can regulate by regulating the addition etc. of the molecular weight regulator used when being polymerized.
Molecular weight distribution [ratio (Mw/Mn) of the number-average molecular weight converted by the polyisoprene of gel permeation chromatography and weight-average molecular weight] for the cyclic olefin ring-opening polymerization polymer of hydrogenation is not particularly limited, be generally 1.5 ~ 4.0, be preferably 1.6 ~ 3.5.When using the cyclic olefin ring-opening polymerization polymer hydride obtained by the cyclic olefin ring-opening polymerization polymer with such molecular weight distribution, considering in having excellent formability, is preferred.
The molecular weight distribution of cyclic olefin ring-opening polymerization polymer hydride regulates by the addition means of monomer during ring-opening polymerization and the concentration of monomer.
The hydrogenation (hydrogenation of main chain double bond) of cyclic olefin ring-opening polymerization polymer can supply hydrogen to carry out in the presence of a hydrogenation catalyst in reaction system.As hydrogenation catalyst, as long as the catalyzer generally used when the hydrogenation of olefin(e) compound, be not particularly limited, such as, can enumerate catalyzer as described below.
As homogeneous catalyst, can enumerate: the combination of catalyst system, the such as Cobaltous diacetate/triethyl aluminum, nickel acetylacetonate/triisobutyl aluminium, cyclopentadienyl titanium dichloride/n-Butyl Lithium, bis cyclopentadienyl zirconium dichloride/s-butyl lithium, four titanium butoxide acid esters/dimethyl magnesiums etc. that are made up of the combination of transistion metal compound and alkali metal compound.And then, can enumerate: the noble metal complexes catalyzer such as dichloro two (triphenylphosphine) palladium, chlorine hydrogen carbonyl three (triphenylphosphine) ruthenium, two (tricyclohexyl phosphine) chloro-benzal ruthenium (IV), chlorine three (triphenylphosphine) rhodiums.
As heterogeneous catalyst, can enumerate: nickel, palladium, platinum, rhodium, ruthenium or these metals are supported in the catalyst system such as the solid catalyst of the carriers such as carbon, silicon-dioxide, diatomite, aluminum oxide, titanium oxide, such as nickel/silicon-dioxide, nickel/diatomite, nickel/aluminum oxide, palladium/carbon, palladium/silicon-dioxide, palladium/diatomite, palladium/aluminum oxide.
Hydrogenation carries out usually in inert organic solvents.As such inert organic solvents, can enumerate: the aromatic hydrocarbons such as benzene, toluene; The aliphatic hydrocarbon such as pentane, hexane; The clicyclic hydrocarbon such as hexanaphthene, perhydronaphthalene; The ethers such as tetrahydrofuran (THF), glycol dimethyl ether etc.Inert organic solvents is usually same with the solvent phase for polyreaction, carries out reacting as long as directly add hydrogenation catalyst in polymerization liquid.
The suitable condition and range of hydrogenation is also different according to the hydrogenation catalyst system difference used, and temperature of reaction is generally-20 DEG C ~+250 DEG C, is preferably-10 DEG C ~+220 DEG C, is more preferably 0 DEG C ~ 200 DEG C.If hydrogenation temperature is too low, then speed of response became slowly sometimes, if too high, then sometimes caused side reaction.Hydrogen pressure is generally 0.01 ~ 20MPa, is preferably 0.05 ~ 15MPa, is more preferably 0.1 ~ 10MPa.If hydrogen pressure is too low, then hydrogenation rate became slowly sometimes, if too high, then need high pressure-resistant reaction device, device receives restriction in this respect.As long as the reaction times forms the hydrogenation ratio expected and just do not limit, be generally 0.1 ~ 10 hour.
Hydrogenation ratio (ratio of the main chain double bond of hydrogenation) in the hydrogenation of cyclic olefin ring-opening polymerization polymer is not particularly limited, and is preferably more than 70%, is more preferably more than 80%, is particularly preferably more than 90%, most preferably be more than 99%.Hydrogenation ratio becomes higher, and the thermotolerance of crystallizing cyclic alkene ring-opening polymerization polymer hydride becomes better.
As above the crystallizing cyclic alkene ring-opening polymerization polymer hydride obtained has the repeating unit being derived from polycycle Norbornene derivative such shown in formula described as follows (4) or formula (5).
[chemical formula 4]
(in formula, R 1, R 2separately represent hydrogen atom; Halogen atom; The alkyl of substituent carbonatoms 1 ~ 20 can be had; Or the substituting group containing Siliciumatom, Sauerstoffatom or nitrogen-atoms.R 1, R 2can bonding and form ring.R 3for the alkyl of the divalence of substituent carbonatoms 1 ~ 20 can be had.)
[chemical formula 5]
(in formula (4), (5), R 1~ R 7and m represents and above-mentioned R 1~ R 7and the implication that m is identical.)
In addition, in the crystallizing cyclic alkene ring-opening polymerization polymer hydride as above obtained, the syndiotactic regularity that the ring-opening polymerization polymer that is supplied in hydrogenation has can be maintained.Therefore, the cyclic olefin ring-opening polymerization polymer hydride obtained has syndiotactic regularity.As long as its hydride of ratio for the racemize diad in crystallizing cyclic alkene ring-opening polymerization polymer hydride of the present invention has crystallinity and is just not particularly limited, be generally more than 55%, be preferably more than 60%, be more preferably 65 ~ 99%.
Because the three-dimensional regularity of polymkeric substance in hydrogenation can not change, therefore, by there is the cyclic olefin ring-opening polymerization polymer of syndiotactic regularity for hydrogenation, based on having syndiotactic regularity this point, can obtain there is crystallinity and there is the crystallizing cyclic alkene ring-opening polymerization polymer hydride of the repeating unit being derived from polycycle Norbornene derivative.
By using such crystallizing cyclic alkene ring-opening polymerization polymer hydride with syndiotactic regularity, the molding that the resin combination obtained particularly not easily deforms because of the impact of heat can be provided.In addition, the ratio of the racemize diad of crystallizing cyclic alkene ring-opening polymerization polymer hydride depends on the ratio of the racemize diad of the cyclic olefin ring-opening polymerization polymer for hydrogenation.
The ratio of the racemize diad of crystallizing cyclic alkene ring-opening polymerization polymer hydride can by right 13c-NMR wave spectrum measures, then comes quantitatively based on this spectral data.Quantitative method is also different according to polymkeric substance, such as, when the ring-opening polymerization polymer hydride of Dicyclopentadiene (DCPD), using orthodichlorobenzene-d4 as solvent, carries out at 150 DEG C 13c-NMR measures, can by be derived from meso diad 43.35ppm signal and be derived from the ratio of intensity ratio determination racemize diad of signal of 43.43ppm of racemize diad.
As long as have crystallinity for the crystallizing cyclic alkene ring-opening polymerization polymer hydride forming resin combination of the present invention, then its fusing point is not particularly limited, and preferably has the fusing point of more than 200 DEG C, more preferably has the fusing point of 230 ~ 290 DEG C.By using the crystallizing cyclic alkene ring-opening polymerization polymer hydride with such fusing point, the resin combination that the balance of plasticity and thermotolerance is excellent especially can be obtained.The fusing point of crystallizing cyclic alkene ring-opening polymerization polymer hydride can regulate by regulating the kind etc. of advising the degree (ratio of racemize diad) of tacticity or the monomer of choice for use therebetween.
< wax >
The wax being matched with resin combination of the present invention can be natural wax, also can be synthetic wax.The grease-like material that the fusing points such as the ester of the higher alcohols formation of such as higher fatty acid and unitary or binary are high, the neutral fat showing the character closely similar with it and higher fatty acid, hydrocarbon etc.
Wax is usually at the solid that room temperature is soft and smooth, and fusing point is generally 25 ~ 120 DEG C, and gas is easy to burning.Specifically, can enumerate: the wax obtained by animal, plant and mineral, with the hydrocarbon obtained in crude oil distillation process for main component and at normal temperatures for the hydrocarbon of solid and petroleum-type wax (paraffin, Microcrystalline Wax or soft wax), the hydrocarbon wax (Fischer-Tropsch wax), the polyalkylene wax that are synthesized by Fischer-Tropsch method.
Wherein, consider from the height of the transparency of the molding obtained, preferably as petroleum-type wax, Fischer-Tropsch wax or polyalkylene wax and so on C nh 2n+2shown hydrocarbon wax, more preferably Fischer-Tropsch wax.Hydrocarbon wax contains the stable hydrocarbon of the straight or branched of more than 95 % by weight.
The use level of wax is selected in the scope of 1 ~ 4 weight part, preferably 1 ~ 3 weight part relative to crystallizing cyclic alkene ring-opening polymerization polymer hydride 100 weight part.If use level is very few, then the crystallization under low die temperature cannot fully carry out, if use level is too much, then thermotolerance is low, not preferably.
< nucleator >
As the nucleator being matched with resin combination of the present invention, existing known material can be used.Such as can enumerate: the metal-salt of Sorbitol Powder compounds, organic phosphoric acid, the metal-salt of organic carboxyl acid, hindered amine compound, hindered phenol compound, kaolin and talcum etc.
As the concrete example of Sorbitol Powder compounds, can enumerate: dibenzylidene sorbitol, two pairs of methyldibenzylidene sorbitol etc.
As the metal-salt of organic phosphoric acid, can enumerate, phosphoric acid 2,2 '-methylene-bis (4,6-di-tert-butyl-phenyl) sodium, two (2,4,8,10-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1,2,3] dioxy phospha eight ring-6-oxide compound) aluminium hydroxide salt etc.
As the metal-salt of organic carboxyl acid, can enumerate: Sodium Benzoate, caoxalate, Magnesium Stearate, calcium benzoate etc.
As hindered amine compound, can enumerate: two (1,2,2,6,6-pentamethyl--4-piperidyl) [[two (1,1-the dimethyl ethyl)-4-hydroxy phenyl of 3,5-] methyl] butyl malonic acid ester etc.
As hindered phenol compound.Can enumerate: triethylene glycol-bis-[3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester], 1,3,5-tri-[(the 4-tertiary butyl-3-hydroxyl-2,6-xylyl) methyl]-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketone, 1,3,5-trimethylammonium-2,4,6-tri-(3 ', 5 '-di-tert-butyl-4-hydroxyl benzyl) benzene etc.
Wherein, the metal-salt of preferred organic phosphoric acid and talcum.
As the metal-salt of organic phosphoric acid, particularly preferably phosphoric acid 2,2 '-methylene-bis (4,6-di-tert-butyl-phenyl) sodium.
As talcum, can enumerate and generally speaking will be called the powder that the mineral of talcum are pulverized.Material talc is for containing hydrous magnesium silicate (3MgO4SiO 2h 2o) as main component, containing Al 2o 3, Fe 2o 3, CaO, K 2o, Na 2o etc. are as the natural mineral of minor component.
The whiteness of the talcum used in the present invention is generally more than 90%, is preferably 90 ~ 97%, is more preferably 93 ~ 97%.Such talcum can be obtained by Japanese talcum society and Lin Huacheng company.
Whiteness affects by the composition of talcum, if above-mentioned scope, then also can not be painted by melt-shaping, and the molding of excellent heat resistance can be obtained.In addition, whiteness measures according to JIS P8123.
The median size (D50) of talcum, as long as be just not particularly limited in commercially available scope, be preferably less than 25 μm, be more preferably less than 20 μm, be particularly preferably less than 15 μm.In addition, median size (D50) measures by laser diffractometry.
The use level of nucleator is not particularly limited, relative to 100 parts by weight Crystalline cyclic olefin ring-opening polymerization polymer hydride, usually at 0.001 ~ 5 weight part, preferably select in the scope of 0.1 ~ 3 weight part.
When using talcum as nucleator, except coordinating except talcum in crystallizing cyclic alkene ring-opening polymerization polymer hydride, when making the hydrogenation of cyclic olefin ring-opening polymerization polymer with homogeneous catalyst, talcum can be coordinated.
Other composition > of <
Resin combination of the present invention can be only made up of crystallizing cyclic alkene ring-opening polymerization polymer hydride, wax and nucleator, and then other one-tenth also can be coordinated to assign to form.
As other composition, can illustrate: the macromolecular material etc. beyond white pigment, glass fibre, antioxidant, weighting agent, tinting material, fire retardant, flame retardant, antistatic agent, softening agent, UV light absorber, photostabilizer, near infrared ray absorption lubricant and crystallizing cyclic alkene ring-opening polymerization polymer hydride.
Particularly when the manufacture for LED light tamper described later, for the object improving thermotolerance, preferably use white pigment and/or glass fibre.
As white pigment, be not particularly limited, such as, can enumerate: silicon-dioxide, aluminum oxide, titanium oxide, magnesium oxide, magnesiumcarbonate, alkaline magnesium carbonate, calcium oxide, calcium carbonate, calcium sulfate, precipitated chalk, calcium sulfite, potassium titanate, lead titanate, barium sulfate, barium carbonate, barium sulfate, white lead, the flowers of zinc, basic lead sulfates, zinc sulfide white, zinc sulphide, zirconium white, barite, chalk, gypsum, clay, talcum powder, diatomite etc.
These can be used alone a kind, or combinationally use two or more.
The shape of white pigment can be any shapes such as tabular, granular, spherical, fibrous or amorphous.
Wherein, preferably use titanium oxide as white pigment.
The kind of titanium oxide is not particularly limited, and in Titanium Dioxide (Rutile) Top grade, anatase-type titanium oxide, any one all can use, from the viewpoint of thermostability, particularly preferably use Titanium Dioxide (Rutile) Top grade.In addition, the shape of titanium oxide is also not particularly limited, can be spherical, flakey, amorphous etc. in any one.The median size of titanium oxide is generally 0.05 ~ 5 μm, is preferably 0.05 ~ 1 μm, more preferably 0.1 ~ 1 μm.By using the titanium oxide with such median size, can obtain can to the composition of the visible light reflectance especially LED light tamper of excellence.
In addition, the particle diameter of so-called titanium oxide, spherical situation refers to diameter, and other situation refers to the longest go-and-retum distance.In addition, median size is for measuring some single particle sizes and the value being averaged and obtaining with electron microscope (infiltration type (TEM) or sweep type (SEM)).
The use level of white pigment is when shaping LED light tamper, as long as consider the luminous reflectance factor of composition that obtains and thermotolerance, the balance of plasticity carry out determining, be not particularly limited, relative to crystallizing cyclic alkene ring-opening polymerization polymer hydride 100 weight part, usually at 20 ~ 200 weight parts, preferably select in the scope of 25 ~ 100 weight parts.
As glass fibre, such as, can enumerate: glass fibre, sheet glass, granulated glass sphere, Calucium Silicate powder, montmorillonite, wilkinite, graphite, aluminium powder, moly-sulfide etc.These can be used alone a kind, or combinationally use two or more.
When shaping LED light tamper, from the viewpoint of thermotolerance, preferably use glass fibre and/or titanium oxide, particularly preferably use glass fibre and titanium oxide.
Both total use levels when using glass fibre and titanium oxide usually at 21 ~ 200 weight parts, preferably at 45 ~ 190 weight parts, more preferably select in the scope of 50 ~ 180 weight parts.
In addition, when shaping LED light tamper, also preferably antioxidant is added.As antioxidant, be not particularly limited, such as, can use phenol antioxidant, phosphorus antioxidants, sulphur class antioxidant.Wherein, preferably phenol antioxidant is used.
As phenol antioxidant, existing known material can be used, such as can enumerate: the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate, 2, acrylic ester compound described in the Japanese Laid-Open Patent Publication 63-179953 publications such as 4-bis-tert-pentyl-6-(1-(3,5-bis-tert-pentyl-2-hydroxy phenyl) ethyl) phenyl acrylate or Japanese Unexamined Patent Publication 1-168643 publication, octadecyl-3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester, 2, 2 '-methylene radical-bis-(4-methyl-6-tert-butylphenol), 1, 1, 3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, four (methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy-phenylpropionic acid ester) methane is [namely, four (3-(3, 5-di-tert-butyl-hydroxy phenyl propionic acid tetramethylolmethane methyl esters)], the alkyl-substituted phenols compounds such as triethylene glycol two (3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester), the two pungent sulfenyl-1,3 of 6-(4-hydroxyl-3,5-di-tert-butyl amido)-2,4-, the pungent sulfenyl-4,6-two-(3 of the two pungent sulfenyl-1,3,5-triazines of 5-triazine, 4-, 2-, 5-di-t-butyl-4-oxygen base anilino)-1,3,5-triazines etc. is containing triazinyl phenolic compound etc.Wherein, alkyl-substituted phenols class antioxidant can particularly preferably be used.
As phosphorus antioxidants, such as can enumerate: triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diiso decyl phosphorous acid ester, three (nonyl phenyl) phosphorous acid ester, three (dinonylphenyl) phosphorous acid ester, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, 10-(3,5-di-tert-butyl-4-hydroxyl benzyl) single phosphite ester compound such as-9,10-dihydro-9-oxies generation-10-phospho hetero phenanthrene (phosphaphenanthrene)-10-oxide compounds; 4,4 '-butylidene-bis-(3-methyl-6-tert butyl phenyl-two (three decyl phosphorous acid esters)), 4, the diphosphorous acid ester compounds such as 4 '-isopropylidene-bis-(phenyl-dialkyl phosphites) (carbonatoms 12 ~ 15 of moieties).
As sulphur class antioxidant, such as can enumerate: 3,3-Tyox B, 3,3 '-thio-2 acid two myristin, 3,3-distearylthiodi-propionate, 3,3-thio-2 acid lauryl stearyl esters, tetramethylolmethane-four-(β-lauryl-thiopropionate), 3, two (the 2-dodecylthio ethyl)-2 of 9-, 4,8,10-tetra-oxaspiro [5.5] undecane etc.
When using antioxidant, its use level is not particularly limited, relative to 100 parts by weight Crystalline cyclic olefin ring-opening polymerization polymer hydride, usually at 0.001 ~ 5 weight part, preferably select in the scope of 0.1 ~ 3 weight part.
Resin combination of the present invention can according to well-established law by coordinating the preparation and blended wax, nucleator and other the one-tenth according to expectation are assigned in crystallizing cyclic alkene ring-opening polymerization polymer hydride.Blending means is not particularly limited, such as, can carry out melting mixing to carry out by single shaft mixing roll or twin shaft mixing roll etc., mixing machine etc. also can be used to carry out dry type mixing and carry out.
In addition, LED light tamper is shaped and uses, as mentioned above, except crystallinity cyclic olefin ring-opening polymerization polymer hydride, wax, nucleator, preferably by coordinating white pigment and glass fibre, carrying out mixing prepare resin combination according to other the composition (such as antioxidant) expected further.By using such resin combination, even if the LED light tamper that the luminous reflectance factor that can obtain more excellent its excellence under the high temperature conditions of luminous reflectance factor with good plasticity also can maintain for a long time and can not reduce.
The luminous reflectance factor of LED light tamper shaping resin combination (before the spectral reflectance of wavelength 450nm, deterioration) is not particularly limited, and is preferably more than 80%, is more preferably 85 ~ 95%.The luminous reflectance factor of LED light tamper shaping resin combination can regulate according to the kind of white pigment and use level.
The melt flow rate (280 DEG C, 2.16kgf) of LED light tamper shaping resin combination is not particularly limited, and is preferably 5 ~ 150g/10 minute, is more preferably 10 ~ 100g/10 minute.The melt flow rate of LED light tamper shaping resin combination can regulate according to the molecular weight of crystallizing cyclic alkene ring-opening polymerization polymer hydride used or the kind of white pigment and use level.
According to resin combination of the present invention, even if can provide a kind of to carry out injection forming under compared with the die temperature of low temperature, crystallization also fully carries out, not easily because the impact of heat causes the molding of distortion.
2) molding
The feature of molding of the present invention is, obtains by carrying out melt-shaping to resin combination of the present invention.
As the method for melt-shaping, can enumerate: the method such as injection forming, extrusion molding, press forming, blow molding, calendaring molding.As long as melt-shaping method carries out selecting according to target shape etc., because resin combination of the present invention has excellent plasticity (melt-shaping), therefore, the injection molding method of advantageous applications production excellence.
The shape of molding is not particularly limited.
As molding, such as, can enumerate: the electronic component such as junctor, rly., electrical condenser, sensor, antenna, IC pallet, chassis, coil sealing member, motor case, power supply box; LED light tamper; The reverberator of lamps apparatus for vehicle; The auto parts such as electric automotive casing, sensor shell, module part shell; Optical lens lens barrel; Flexible printed board; The stacked mold release film of printing distributing board; Substrate for solar cell; Family's electrical accessories such as microwave oven, electric cooker, electric hot water bottle, drying washing machine, dishwasher, air-conditioning; Packaging, bale packing film; Food sheet material, pallet; LED die material; Pump housing, impeller, pipe-fitting joint, bathroom panel etc. firmly establish part etc.
Wherein, as molding of the present invention, be preferably LED light tamper.
As LED light tamper, such as, can enumerate: the light reflector etc. that can be used as the LED of the light source of the electric light display panel such as the light source of the backlight of the liquid-crystal display of the miniaturized electronicss such as the light source of the backlight of large-scale liquid crystal display device, lighting fixtures, portable phone, road traffic display panel.
As long as the shape of LED light tamper is determined according to its purposes etc. is suitable, also LED light tamper can be formed with other combination of materials as required.
Can by forming LED according to well-established law combined semiconductor chip and sealing material in the LED light tamper obtained.
Embodiment
Below, enumerate embodiment and comparative example to the present invention more Delicatement be described.In addition, the part in each example and % unless otherwise specified, are then weight basis.
In addition, the mensuration in each example and evaluation are undertaken by following method.
(1) molecular weight (weight-average molecular weight and number-average molecular weight) of cyclic olefin ring-opening polymerization polymer
By gel permeation chromatography (GPC) system HLC-8220 (Dong Cao Inc.), use H type post (Dong Cao Inc.), measure at 40 DEG C using tetrahydrofuran (THF) as solvent, obtain with the form of polystyrene conversion value.
(2) hydrogenation ratio in cyclic olefin ring-opening polymerization polymer hydride
Pass through 1h-NMR measures and obtains.
(3) fusing point of cyclic olefin ring-opening polymerization polymer hydride
Use differential scanning calorimeter, at warming temperature: measure under the condition of 10 DEG C/min.
(4) ratio of the racemize diad of cyclic olefin ring-opening polymerization polymer hydride
With orthodichlorobenzene-d 4as solvent, carry out at 150 DEG C 13c-NMR measures, and determines based on the signal of 43.35ppm and the strength ratio of signal of the 43.43ppm that is derived from racemize diad being derived from meso diad (メ ソ ダ イ ア ッ De).
(5)(ΔHm-ΔHc)/ΔHm
Use differential scanning calorimeter, obtain crystallization by Thermogram when being heated up with rate of heating 10 DEG C/min based on JIS K7122 by molding 10mg and melt heat Δ Hm (J/g) and crystallization heat Δ Hc (J/g), and calculate.
The maximum value of this numerical value is 1.0, and numerical value is larger, means that crystallization carries out more abundant, if less than 0.9, then crystallization does not fully carry out, and dimensional stability reduces, or scolding tin thermotolerance is insufficient, therefore not preferred.
At this, being that the average evaluation of more than 0.9 is zero by this numerical value, is △ by more than 0.6 and lower than the average evaluation of 0.9, by the average evaluation less than 0.6 be ×.
(6) heat-resisting long-term stable experiment
About the flat board determining initial stage reflectivity.After using baking box to carry out the thermal treatment of 200 DEG C × 10 hours, confirm the size distortion of molding.
Being zero by undeformed average evaluation, is △ by the average evaluation of the warpage finding more than 0.2mm, by find the average evaluation of the warpage of more than 0.5mm be ×.
[synthesis example 1]
After abundant drying, 75% cyclohexane solution 40 parts (be 30 part with the gauge of Dicyclopentadiene (DCPD)) of Dicyclopentadiene (DCPD) (inner mold content is more than 99%) is loaded in the glass pressure-resistant reaction vessel of nitrogen displacement, add hexanaphthene 738 parts and 1-hexene 3.3 parts again, be heated to 50 DEG C.On the other hand, add the diethylaluminum ethoxide/hexane solution 4.6 parts of 19 % by weight and stir 10 minutes, Kaolinite Preparation of Catalyst solution 1.1 parts, monoethyl imide tungsten (tetrahydrofuran (THF)) complex compound being dissolved in the solution in the toluene of 56 parts.Add this catalyst solution in the reactor, cause ring-opening polymerization.Then, keep 50 DEG C to add 75% Dicyclopentadiene (DCPD)/cyclohexane solution 40 parts every 5 minutes, after adding 9 times altogether, sustained reaction 2 hours.Then, add a small amount of Virahol, polyreaction is stopped, then, polymeric reaction solution being injected in a large amount of Virahols, ring-opening polymerization polymer is solidified.
Polymkeric substance after being solidified by filtered and recycled.By the ring-opening polymerization polymer that obtains under reduced pressure at 40 DEG C dry 20 hours.The receipts amount of polymkeric substance is 296 parts (yield=99%).In addition, number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of this polymkeric substance are respectively 10,100 and 17,200, and the molecular weight distribution (Mw/Mn) obtained thus is 1.70.
Next, in pressure-resistant reaction vessel, add the ring-opening polymerization polymer 60 parts that obtains and hexanaphthene 261 parts and stir, make polymer dissolution after hexanaphthene, add and chlorine hydrogen carbonyl three (triphenylphosphine) ruthenium 0.039 is dissolved in toluene 40 parts of hydrogenation catalyst solutions obtained, carry out 5 hours hydrogenations at hydrogen pressure 4MPa, at 160 DEG C.Being injected in a large amount of isopropyl alcohol by the hydrogenation liquid obtained makes polymkeric substance separate out completely, and after filtering cleaning, drying under reduced pressure 24 hours at 60 DEG C, obtains crystallizing cyclic alkene ring-opening polymerization polymer hydride A.
The hydrogenation ratio of crystallizing cyclic alkene ring-opening polymerization polymer hydride A is more than 99%, and the ratio of racemize diad is 79%, and fusing point is 260 DEG C.The amount of the 1-hexene used in polyreaction, the number-average molecular weight (Mn) of ring-opening polymerization polymer obtained, weight-average molecular weight (Mw) and molecular weight distribution (Mw/Mn) and the hydrogenation ratio of ring-opening polymerization polymer hydride obtained and fusing point are gathered and is shown in following table 1.
[synthesis example 2,3]
In synthesis example 1, the amount of 1-hexene is changed as described in Table 1, in addition, obtain crystallizing cyclic alkene ring-opening polymerization polymer hydride B, C in the same manner as synthesis example 1.The number-average molecular weight (Mn) of the ring-opening polymerization polymer obtained, weight-average molecular weight (Mw) and molecular weight distribution (Mw/Mn) and the hydrogenation ratio of ring-opening polymerization polymer hydride obtained, the ratio of racemize diad and fusing point are gathered and is shown in following table 1.
[table 1]
[embodiment 1]
By crystallizing cyclic alkene ring-opening polymerization polymer hydride A100 part, wax (fusing point 69 DEG C, trade(brand)name " LUVAX1266 ", Jing La Inc. of Japan) 2 parts, antioxidant (four [methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester] methane, trade(brand)name " Irganox (registered trademark) 1010 ", BASF Japanese firm system) 0.8 part, and nucleator (phosphoric acid 2, 2 '-methylene-bis (4, 6-di-tert-butyl-phenyl) sodium, trade(brand)name " Adecastab (registered trademark) NA-11 ", ADEKA Inc.) after 0.8 part of mixing, use small-sized mixing roll (Micro15Compounder, DSM Xplore system) at 290 DEG C, under the condition of 100rpm mixing 2 minutes, by the mixing composition granule obtained.Then, be the flat board of long 70mm, wide 30mm, thickness 3mm of being shaped under the condition of 100 DEG C, 120 DEG C, 150 DEG C by small injection forming mill (Micro InjectionMoulding Machine10cc, DSM Xplore company manufacture) 10 seconds hold-times, respective die temperature in forming temperature 290 DEG C, injection pressure 0.7MPa, mould.Use differential scanning calorimeter to obtain (Δ Hm-Δ Hc)/Δ Hm the fragment of respective forming board, heat-resisting long-term stable experiment is carried out to the flat board be shaped at 100 DEG C, mould, confirm not distortion.The composition of composition and respective evaluation result are gathered and is shown in following table 2.
[embodiment 2 ~ 5 and comparative example 1 ~ 5]
Composition use level (weight part) in embodiment 1 is changed to as described in Table 2, in addition, obtains molding similarly to Example 1, carry out it and evaluate.Respective evaluation result gathers and is shown in table 2.In addition, in table 2, the talcum used as nucleator is trade(brand)name " MS " (whiteness 93%, median size (D50) 14 μm, Japanese talcum company manufacture), and the glass fibre of inorganic filler is trade(brand)name " CSG3PA-830 " (Dong Fang Inc.), titanium oxide is trade(brand)name " FTR-700 " (Titanium Dioxide (Rutile) Top grade that median size is 0.2 μm, Sakai chemical industrial company system).The adipic acid ester used as softening agent uses hexanodioic acid two 2-ethylhexyl (DOA), phthalic ester to use phthalic acid two 2-ethylhexyl (DOP).
[table 2]
As shown in Table 2, resin combination of the present invention (embodiment 1 ~ 5) possesses good plasticity, even if under lower die temperature, also can carry out crystallization, can obtain the molding of excellent heat resistance.On the other hand, if wax amount is few, then not easily crystallization occurs, the long-term heat resistance of the molding obtained is insufficient (comparative example 1,2).In addition, if wax amount is many, although then crystallization carries out, because the thermotolerance of wax is low, therefore, the long-term heat resistance difference (comparative example 3) of molding.In addition, when using softening agent to replace wax, the crystallization under low temperature is insufficient, and the distortion after the heat-resisting long-term stable experiment of the molding obtained is large, thermotolerance insufficient (comparative example 4,5).

Claims (7)

1. a resin combination, it contains: crystallizing cyclic alkene ring-opening polymerization polymer hydride, be wax and the nucleator of 1 ~ 4 weight part relative to this hydride of 100 weight parts, described cyclic olefin ring-opening polymerization polymer hydride have relative to the total amount of monomer whose unit be more than 80 % by weight the repeating unit being derived from polycycle Norbornene derivative.
2. resin combination according to claim 1, wherein, described cyclic olefin ring-opening polymerization polymer hydride is the cyclic olefin ring-opening polymerization polymer hydride with syndiotactic regularity.
3. resin combination according to claim 1, wherein, described wax is hydrocarbon wax.
4. resin combination according to claim 1, wherein, described nucleator is the metal-salt of talcum or organic phosphoric acid.
5. resin combination according to claim 1, wherein, relative to cyclic olefin ring-opening polymerization polymer hydride described in 100 weight parts, the content of described nucleator is 0.001 ~ 5 weight part.
6. a molding, it obtains by carrying out melt-shaping to the resin combination according to any one of Claims 1 to 5.
7. molding according to claim 6, it is LED light tamper.
CN201180053111.3A 2010-09-07 2011-09-06 Resin combination and molding thereof Expired - Fee Related CN103237843B (en)

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