CN103391835A - Process of producing molding, and molding - Google Patents
Process of producing molding, and molding Download PDFInfo
- Publication number
- CN103391835A CN103391835A CN2011800681680A CN201180068168A CN103391835A CN 103391835 A CN103391835 A CN 103391835A CN 2011800681680 A CN2011800681680 A CN 2011800681680A CN 201180068168 A CN201180068168 A CN 201180068168A CN 103391835 A CN103391835 A CN 103391835A
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- CN
- China
- Prior art keywords
- cyclic olefin
- olefin resin
- products formed
- thermoplastic elastomer
- tpe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/76—Measuring, controlling or regulating
- B29C45/78—Measuring, controlling or regulating of temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
Abstract
Provided is a process of producing a molding which contains a cyclic olefin resin and exhibits an extremely small degree of deterioration in transparency even when exposed to high-temperature/high-humidity environments. A cyclic olefin resin composition comprising a cyclic olefin resin and a thermoplastic elastomer, wherein the content of the thermoplastic elastomer is 0.1 to 2 mass% inclusive, is molded under the conditions in which the cylinder temperature is equal to or lower than a temperature that is higher by 170 DEG C than the glass transition temperature (Tg) of the cyclic olefin resin. With regard to the requirement for the cylinder temperature, it is preferred that the cylinder temperature falls within the range from 250 to 300 DEG C inclusive.
Description
Technical field
The present invention relates to manufacture method and the products formed of products formed.
Background technology
Cyclic olefin resin is to have the resin of cyclic olefin skeleton in main chain, for having high transparent, low-birefringence, high heat distortion temperature, light weight, dimensional stability, low water absorbable, hydrolytic resistance, chemical reagent resistance, low-k, low-dielectric loss, do not contain the resin of many features such as environmentally harmful material.Therefore, cyclic olefin resin need to be used to the diversified field of these features.
Cyclic olefin resin as mentioned above, has the feature of many excellences, but has the situation that requires to improve physical property.A problem as requiring to improve can list: the products formed that will comprise cyclic olefin resin is exposed to the hot and humid transparency reduction of lower time.Particularly as described below.
The container of food, pharmaceuticals etc. utilizes hot water, steam etc. to carry out cleaning treatment for sterilization.Especially, in the container of pharmaceuticals etc., usually implement wet sterilization.For cyclic olefin resin, because heat resistance, rigidity, moisture resistance are excellent, therefore the raw material as the container of pharmaceuticals etc. is preferred, but the problem that has the transparency that is exposed to hot and humid lower time to reduce.
In addition, the optical goods such as the lens that optical device is used, optical record medium, food, pharmaceuticals are packed the goods of purposes in conveyance process etc., are placed on sometimes under the severe rugged environment of high temperature, high humility.The problem that the transparency reduction of the products formed that is exposed to hot and humid lower time is also arranged under these circumstances.
As mentioned above, comprising products formed that the material forming of cyclic olefin resin forms is exposed to the transparency reduction in hot and humid lower time and can affects various purposes.So, disclose with comprising the resin combination that specific cyclic olefin resin and specific D-sorbite are derivative and suppressed the technology (for example with reference to patent documentation 1) that the above-mentioned transparency reduces.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2001-26682 communique
Summary of the invention
The problem that invention will solve
, according to the invention of patent documentation 1 record, can suppress to comprise products formed that the material forming of cyclic olefin resin forms and be exposed to the transparency in hot and humid lower time and reduce.Yet, in recent years in various purposes, require the further raising of the transparency, require further to suppress to be exposed to the technology of reduction of the transparency of the products formed under hot and humid.
The present invention makes in order to overcome the above problems, even if its purpose is to provide the products formed that will comprise cyclic olefin resin to be exposed to hot and humid lower time, the reduction of the transparency is the manufacture method of very little products formed also.
Be used for the scheme of dealing with problems
The inventor etc. have carried out repeatedly deep research in order to address the above problem.Found that, be more than 0.1 quality % and the cyclic olefin resin composition below 2 quality % is that condition compacted under below the glass transition temperature (Tg)+170 ℃ of above-mentioned cyclic olefin resin can address the above problem at barrel zone temperature by the content that will comprise cyclic olefin resin and thermoplastic elastomer (TPE) and thermoplastic elastomer (TPE), thereby completed the present invention.More specifically, the invention provides following scheme.
(1) a kind of manufacture method of products formed, the content that wherein, will comprise cyclic olefin resin and thermoplastic elastomer (TPE) and aforementioned hot thermoplastic elastic is 0.1 quality % is above and 2 quality % are following cyclic olefin resin composition is condition compacted under below the glass transition temperature (Tg)+170 ℃ of aforementioned cyclic olefin resin at barrel zone temperature.
(2) according to the manufacture method of (1) described products formed, wherein, the condition of aforementioned barrel zone temperature is more than 250 ℃ and below 300 ℃.
(3) according to the manufacture method of (1) or (2) described products formed, wherein, aforementioned cyclic olefin resin is the copolymer of ENB and ethene.
(4) a kind of products formed, wherein, contain the cyclic olefin resin that 95.0 quality % are above and 99.9 quality % are following, the thermoplastic elastomer (TPE) that 0.1 quality % is above and 2.0 quality % are following in cyclic olefin resin composition, described products formed to measure based on the JIS-K7136 test film that is 2mm to thickness the haze value that obtains be below 0.6%.
(5) products formed described according to (4), wherein,, through the afore-mentioned test sheet being exposed in the environment of 85 ℃ of temperature, humidity 85% front 240 hours, be below 0.4% with the haze value of this test film this test film after the processing of cooling 1.5 hours in the environment of 23 ℃ of temperature, humidity 50% and the difference of aforementioned haze value thereafter.
(6) according to (4) or (5) described products formed, wherein, aforementioned products formed is optics.
(7) manufacture method of the described products formed of basis (1)～(3) any one, wherein, aforementioned cyclic olefin resin composition is made by the following method: add thermoplastic elastomer (TPE) in the monomer composition that comprises the cycloolefin monomer carries out the polymeric solution that contains cyclic olefin resin that polymerisation in solution forms or remove the polymer of the molten condition that polymer solvent forms from polymeric solution.
The effect of invention
According to the present invention, even if also very little products formed of the reduction that can obtain being exposed to hot and humid lower time transparency.
The specific embodiment
Below, embodiments of the present invention are described.Need to prove, the present invention is not limited to following embodiment.
The manufacture method of＜products formed 〉
The manufacture method of products formed of the present invention refers to that the content that will comprise cyclic olefin resin and thermoplastic elastomer (TPE) and thermoplastic elastomer (TPE) is more than 0.1 quality % and the cyclic olefin resin composition below 2 quality % is the method for the condition compacted under below the glass transition temperature (Tg)+170 ℃ of above-mentioned cyclic olefin resin at barrel zone temperature.
[cyclic olefin resin composition]
Cyclic olefin resin composition comprises cyclic olefin resin and thermoplastic elastomer (TPE).Below, cyclic olefin resin, thermoplastic elastomer (TPE), other compositions are described.
Cyclic olefin resin is to comprise the resin of cyclic olefin composition as copolymer composition, so long as comprise the polyolefin-based resins of cyclic olefin composition in main chain, just has no particular limits.Such as listing: the addition copolymer of the addition polymer of cyclic olefin or its hydrogenation products, cyclic olefin and alpha-olefin or its hydrogenation products etc.
In addition,, as cyclic olefin resin, also be included on above-mentioned polymer the material that unsaturated compound that further grafting and/or copolymerization have polar group forms.
As polar group, such as listing: carboxyl, anhydride group, epoxy radicals, amide groups, ester group, hydroxyl etc.,, as the unsaturated compound with polar group, can list (methyl) acrylic acid, maleic acid, maleic anhydride, itaconic anhydride, (methyl) glycidyl acrylate, (methyl) acrylic acid alkyl (carbon number 1～10) ester, maleic acid alkyl (carbon number 1～10) ester, (methyl) acrylamide, (methyl) 2-Hydroxy ethyl acrylate etc.
As cyclic olefin resin, addition copolymer or its hydrogenation products of preferred cyclic olefin and alpha-olefin.
In addition, as what use in the present invention, comprise the cyclic olefin resin of cyclic olefin composition as copolymer composition, also can use commercially available resin.As commercially available cyclic olefin resin, such as listing: the TOPAS(registration mark) (manufacturing of Topas Advanced Polymers company), APEL(registration mark) (Mitsui Chemicals, Inc. manufacturing), ZEONEX(registration mark) (ZEON CORPORATION manufacturing), ZEONOR(registration mark) (ZEON CORPORATION manufacturing), ARTON(registration mark) (manufacturing of JSR company) etc.
, as the addition copolymer of cyclic olefin and alpha-olefin,, as more preferred example, can list: comprise the alpha-olefin composition of [1] carbon number 2～20 and the copolymer of the cyclic olefin composition shown in [2] following general formula (I).
[Chemical formula 1]
(in formula, R
1～R
12Can be same to each other or different to each other, be the group that selects in the group that free hydrogen atom, halogen atom and alkyl form,
R
9With R
10, R
11With R
12Can be integrated and form the alkyl of divalence,
R
9Or R
10, and R
11Or R
12Can mutually form ring.
In addition, n represents 0 or positive integer,
N is 2 when above, in each repetitive, and R
5～R
8Can be same to each other or different to each other.）
[the alpha-olefin composition of [1] carbon number 2～20]
Alpha-olefin to carbon number 2～20 has no particular limits.For example can list the material same with TOHKEMY 2007-302722.In addition, these alpha-olefin compositions can be used alone, and also can use simultaneously two or more.Wherein, most preferably use separately ethene.
[[2] are by the cyclic olefin composition of general formula (I) expression]
R in general formula (I)
1～R
12Can be same to each other or different to each other, be the group that selects in the group that free hydrogen atom, halogen atom and alkyl form.
As R
1～R
8Concrete example, for example can list: hydrogen atom, the halogen atoms such as fluorine, chlorine, bromine, the low alkyl groups such as methyl, ethyl, propyl group, butyl etc., they can differ from one another, and are also can part different, can also be all identical.
In addition, as R
9～R
12Concrete example, for example can list: hydrogen atom, the halogen atoms such as fluorine, chlorine, bromine, the alkyl such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, hexyl, stearyl, the cycloalkyl such as cyclohexyl, phenyl, tolyl, ethylbenzene, cumenyl, naphthyl, anthryl etc. replace or without the aromatic hydrocarbyl that replaces, benzyl, phenethyl etc. replace aralkyl that aryl is arranged etc. on alkyl, they can differ from one another, also can be partly different, and can also be all identical.
As R
9With R
10, or R
11With R
12Integrated and concrete example while forming the alkyl of divalence, such as listing: the alkylidene radicals such as ethidine, propylidene base, isopropylidene etc.
R
9Or R
10, and R
11Or R
12While mutually forming ring, the ring of formation can be monocycle, can be also many rings, can be also the many rings with bridge, can be also the ring with two keys, can also be the ring that is combined by these rings.In addition, these rings can have the substituting groups such as methyl.
Concrete example as the cyclic olefin composition by general formula (I) expression, can list the material same with TOHKEMY 2007-302722.
These cyclic olefin compositions can be used alone, and also can be used in combination two or more.Wherein, preferred dicyclo [2.2.1] hept-2-ene" (common first names: ENB) of using separately.
Particularly, for the copolymer that comprises ENB and ethene during as the products formed of cyclic olefin resin, there is the tendency of the problem that the transparency that hot and humid lower time easily occurs being exposed to reduces., according to the present invention,, even if use the cyclic olefin resin that like this easily goes wrong, also can suppress fully the reduction of the transparency.
[other copolymer composition]
For cyclic olefin resin, except the alpha-olefin composition and [2] cyclic olefin composition by general formula (I) expression of above-mentioned [1] carbon number 2～20, in the scope of not damaging purpose of the present invention, but also can contain as required the unsaturated monomer composition of other copolymerization.
Content to cyclic olefin resin has no particular limits, be more than 95.0 quality % and below 99.9 quality % in cyclic olefin resin composition, more than being preferably 97.0 quality % and below 99.9 quality %, more preferably more than 98.0 quality % and below 99.9 quality %.Products formed by method manufacturing of the present invention is characterised in that the transparency is high,, in order to give full play to the high transparent as the feature of cyclic olefin resin, preferably the content of cyclic olefin resin is adjusted into above-mentioned content.
For the alpha-olefin composition of [1] carbon number 2～20 and [2] method of hydrotreating by the polymerization of the cyclic olefin composition of general formula (I) expression and the polymer that obtains, have no particular limits, can carry out according to known method.In addition, can be random copolymerization, also can be block copolymerization, be preferably random copolymerization.Need to prove,, as concrete polymerization methods, can adopt any polymerization methods of polymerisation in solution, polymerisation in bulk and slurry polymerization, can also be any polymerization methods of continuous polymerization and batch polymerization.
An example to the manufacture method of cyclic olefin resin describes.Can make by the following method: the monomer composition that will comprise cyclic olefin composition and alpha-olefin composition imports in reactor, add therein polymerization catalyst, polymer solvent, be set as reaction temperature, the reaction pressure of regulation, thereby make cyclic olefin resin.Cyclic olefin resin obtains to be contained in the state in polymer solvent.Then, remove desolventizing under the conditions such as high temperature, decompression, thereby obtain cyclic olefin resin.
Need to prove, reaction temperature, reaction pressure can be so that cyclic olefin composition and alpha-olefin composition contain the suitable setting of mode in the scope that ratio is in expectation in resin.In addition,, for reaction pressure, when the alpha-olefin composition is gas,, as long as determined the concentration (mol/L) of the gas of alpha-olefin composition, just can directly determine.
Polymerization catalyst for the manufacturing that can be used for cyclic olefin resin, have no particular limits, and can use that Z-N system, double decomposition (metathesis) are, the known catalyst in the past such as metallocene series catalysts.These catalyst can be made by known method in the past, also can use commercially available product., for addition copolymer or its hydrogenation products of cyclic olefin composition and alpha-olefin composition, preferably with the metallocene series catalysts, make.
As polymer solvent, such as exemplifying: the aliphatic hydrocarbons such as hexane, heptane, octane, kerosene, the clicyclic hydrocarbons such as cyclohexane, hexahydrotoluene, decahydronaphthalene, the aromatic hydrocarbons such as benzene,toluene,xylene etc.These hydrocarbon system solvents can be used alone or be used in combination two or more.
For thermoplastic elastomer (TPE), have no particular limits, can use known thermoplastic elastomer (TPE) in the past according to purposes etc.As known thermoplastic elastomer resin in the past, such as listing: olefin-based elastomer resin, styrene series elastomer resin, polyamide-based elastomer resin, polyester based elastomers resin, polyurethane series elastomer resin etc.More specifically, can use the elastomer resin of record in TOHKEMY 2006-291100, TOHKEMY 2004-156048, TOHKEMY 2008-006829, Japanese kokai publication hei 09-48902, Japanese kokai publication hei 10-158487 etc.
Be used as raw material by the cyclic olefin resin composition that will include thermoplastic elastomer resin, become and be not easy to occur that products formed is exposed to the problem of the transparency reduction of hot and humid generation of lower time.
, for the kind of thermoplastic elastomer resin, can carry out the preferred thermoplastic elastomer resin of suitable selection according to the kind of the cyclic olefin resin of use.In the present invention,, in order to realize high transparent, need that thermoplastic elastomer (TPE) is little to be scattered in cyclic olefin resin., in order to make its differential loose, need to easily with cyclic olefin resin, mix by thermoplastic elastomer (TPE) in the condition of barrel zone temperature described later.After being chosen in of concrete thermoplastic elastomer (TPE) determined the cyclic olefin resin of expectation, the viscosity of the cyclic olefin resin under the barrel zone temperature during take the moulding of products formed and the viscosity of the thermoplastic elastomer (TPE) under above-mentioned barrel zone temperature were carried out as the mode of close value.Usually select the elastomer higher than the melt viscosity of cyclic olefin resin.At this moment, in order to carry out for elastomer is little decentralized and the viscosity coupling implemented reduces barrel zone temperature, reduces resin temperature when injection mo(u)lding.That is to say, need to improve the viscosity of cyclic olefin resin, make the viscosity of cyclic olefin resin relatively approach and have more full-bodied elastomer.
, for the content of thermoplastic elastomer (TPE), be more than 0.1 quality % and below 2 quality % in cyclic olefin resin composition.The content of thermoplastic elastomer (TPE) is 0.1 quality % when above, can fully realize suppressing the effect that the transparency that products formed is exposed to hot and humid lower time reduces.In addition, be 2 quality % when following, the transparency almost not impact of the interpolation of thermoplastic elastomer (TPE) on products formed, products formed has high transparent.
Method for producing thermoplastic elastomer is had no particular limits, can adopt known method in the past.In addition, also can use commercially available product as thermoplastic elastomer (TPE).concrete example as commercially available product, can list: " HYTREL " (DU PONT-TORAY CO., LTD. the trade name of making), " PELPRENE S ", " PELPRENE P " (trade name that Japan's textile company is made), " GRILUX E " (trade name that large Japanese ink chemical industrial company makes), the commercially available polyester based elastomers resins such as " NOUVELAN " (trade name that TEIJIN LIMITED. makes), " KRATON G " (trade name that KRATON PERFORMANCE POLYMERS INC. makes), " TUFTEC " (trade name that Asahi Kasei Corporation is made), " SEPTON ", " HYBRAR " (both are the trade name that Kuraray company makes), " KRATON G COMPOUND " (trade name that KRATON PERFORMANCE POLYMERS INC. makes), " TUFTEC COMPOUND " (trade name that Asahi Kasei Corporation is made), " RABALON " (trade name that Mitsubishi Chemical Ind makes), " Sumitomo TPE(SB series) " commercially available styrene series elastomer resins such as (trade names that Sumitomo Chemical Co. Ltd. makes), " MILASTOMER " (trade name that Mitsui Chemicals, Inc. is made), " THERMORUN " (trade name that Mitsubishi Chemical Ind makes), the commercially available olefin-based elastomer resins such as " Sumitomo TPE " (trade name that Sumitomo Chemical Co. Ltd. makes).
, for cyclic olefin resin composition, in the scope of not damaging effect of the present invention, also can contain the known additive in the past such as other resin, colouring agent, antioxidant, stabilizing agent, plasticizer, lubricant, releasing agent and fire retardant.
[manufacture method of cyclic olefin resin composition]
Manufacture method to cyclic olefin resin composition has no particular limits, can be by cyclic olefin resin and thermoplastic elastomer (TPE) are mixed to make.The method of mixing is had no particular limits, for example by following method, can make the cyclic olefin resin composition pellet.
for example, as first example, add thermoplastic elastomer (TPE) in polymeric solution after polymerisation in solution (solution that contains cyclic olefin resin in polymer solvent), obtain comprising the polymeric solution of cyclic olefin resin and thermoplastic elastomer (TPE), then, at high temperature, remove polymer solvent under the condition of decompression from this polymeric solution, obtain the mixture that comprises cyclic olefin resin and thermoplastic elastomer (TPE) of molten condition, then, this mixture is extruded as line material (strand) shape, with known method was cooling with the mixture of line material shape in the past, use the cut-out line material shape things such as comminutor, thereby make the cyclic olefin resin composition pellet.
As second example, can also be for adding the method for thermoplastic elastomer (TPE) in the cyclic olefin resin of the molten condition remove polymer solvent from polymeric solution after.For the method, except the interpolation difference on opportunity of thermoplastic elastomer (TPE), identical with the manufacture method of the cyclic olefin resin composition pellet of above-mentioned first example.
, as the 3rd example, can also add by the melting mixing thermoplastic elastomer (TPE) in cyclic olefin resin.Particularly,, for cyclic olefin resin, thermoplastic elastomer (TPE) melting mixing together or in turn, make in the same manner method of cyclic olefin resin composition pellet etc. with said method.Need to prove, as the method for melting mixing, such as listing: the screw extruder of use single shaft or twin shaft, Banbury mixer, roller, various kneaders etc. carry out the method for melting mixing etc.
In the manufacture method of cyclic olefin resin composition pellet as above, the temperature in melting mixing is had no particular limits.The temperature that is the raw materials melt of the inputs such as cyclic olefin resin, thermoplastic elastomer (TPE) gets final product.Usually, more than 200 ℃ and below 350 ℃, preferably implementing more than 180 ℃ and in the temperature range below 300 ℃.
Manufacture method as the cyclic olefin resin composition pellet, the preferred middle method of thermoplastic elastomer (TPE) or the method for adding thermoplastic elastomer (TPE) in the cyclic olefin resin of removing polymer solvent molten condition afterwards from polymeric solution of second example (that is to say, preferably the method for interpolation thermoplastic elastomer (TPE) when making cyclic olefin resin) of adding of the polymeric solution after polymerisation in solution (solution that comprises cyclic olefin resin in polymer solvent) that adopts first example.When cyclic olefin resin and thermoplastic elastomer (TPE) are dropped into the method for making the cyclic olefin resin composition pellet in extruder when the 3rd example (for example), can experience extraly 1 time thermal history before becoming the cyclic olefin resin composition pellet.This extra thermal history becomes the reason of variable color etc., therefore,, in order to obtain the cyclic olefin resin pellet for the manufacture of the higher products formed of the transparency, preferably by first example or second example, makes the cyclic olefin resin composition pellet.
Need to prove, while adding other composition in cyclic olefin resin composition, the adding method of other composition is had no particular limits.Can be according to known method interpolation in the past.
It is the transparency more than 90% that the cyclic olefin resin pellet that obtains by method as above has total light transmittance.Have as the transparency of the cyclic olefin resin composition pellet of the raw material of products formed highlyer, the transparency of the products formed that obtains is higher tendency also.So, use the transparency of the products formed of above-mentioned cyclic olefin resin composition pellet manufacturing to uprise.At this, total light transmittance refers to, while measuring in light path 2mm, no matter directly advance the ratio of the light quantity that sees through with the visible light quantity that is incident to sample of still scattering.Need to prove, for the transparency of cyclic olefin resin composition pellet, the total light transmittance while preferably measuring in light path 2mm is more than 80%.
During for the cyclic olefin resin pellet of total light transmittance as above, can think that each composition differential such as thermoplastic elastomer (TPE) are dispersed in cyclic olefin resin.
[manufacture method of products formed]
The manufacture method of products formed of the present invention is at specific barrel zone temperature compacted under with cyclic olefin resin composition.Forming method is had no particular limits, can adopt the general forming methods such as injection mo(u)lding, extrusion molding.Specific barrel zone temperature refers to, below the glass transition temperature (Tg)+170 of the contained cyclic olefin resin of cyclic olefin resin composition ℃, is preferably below (Tg)+150 ℃, more preferably below (Tg)+120 ℃.Be adjusted to specific scope by the condition with barrel zone temperature, even if products formed is exposed to high humidity high temperature lower time, the transparency also reduces hardly.In addition, can fully improve and be exposed to the transparency before under high humidity high temperature, products formed just moulding.
In the manufacture method of products formed of the present invention, barrel zone temperature preferably is adjusted to more than 250 ℃ and below 300 ℃.Barrel zone temperature is below Tg+170 ℃ the time, can reach effect of the present invention,, by barrel zone temperature being adjusted to more than 250 ℃ and the scope below 300 ℃, can fully suppress deteriorated, other composition deteriorated of deteriorated, the thermoplastic elastomer (TPE) of the cyclic olefin resin that causes because of thermal conductance.Deteriorated by suppressing these, can suppress the reduction of the transparency of products formed, can suppress the reduction of other physical property.
Condition of molding beyond suitable setting barrel zone temperature.Particularly, be careful following aspect and determine other condition of molding., for other compositions such as thermoplastic elastomer (TPE)s,, in order to reduce not significantly the transparency of products formed, need to make their little being scattered in cyclic olefin resin.For the composition of melting as thermoplastic elastomer (TPE) etc., also melting of these compositions during with the cyclic olefin resin melting mixing, adjust condition of molding in the close mode of viscosity of these compositions of the viscosity of the cyclic olefin resin of molten condition and molten condition and get final product.In addition, while containing not molten component, with the conditions such as the suitable setting screw speed of mode of not assembling, get final product.While comprising the composition of two types, above-mentioned condition is all taken the condition of molding that decides other into account.Need to prove, be technology general knowledge for the manufacture of the condition of molding of transparent products formed, the determining method of this condition of molding, determines that according to these technology in the past other condition of molding is in most of the cases no problem.
Need to prove, the glass transition temperature of cyclic olefin resin adopts the value of measuring under the condition of 10 ℃/minute of programming rates by DSC method (the described method of JIS K7121).In addition, while comprising multiple cyclic olefin resin in cyclic olefin resin composition, use the glass transition temperature of main cyclic olefin resin while determining the barrel zone temperature condition.
＜products formed 〉
The products formed of products formed of the present invention for by manufacture method of the present invention, making, comprise the cyclic olefin resin that 95.0 quality % are above and 99.9 quality % are following, comprises the thermoplastic elastomer (TPE) that 0.1 quality % is above and 2.0 quality % are following.As mentioned above, therefore description thereof is omitted for cyclic olefin resin, thermoplastic elastomer (TPE).In addition, products formed of the present invention also can contain other composition.For other composition, also identical with other composition that can contain in above-mentioned cyclic olefin resin composition, therefore description thereof is omitted.
Products formed of the present invention to measure based on the JIS-K7136 test film that is 2mm to thickness the haze value that obtains be below 0.6%.As mentioned above, products formed of the present invention, take cyclic olefin resin as main component, is therefore the very high products formed of the transparency.
In addition, about products formed of the present invention, the value of the haze value before the haze value after following processing-processing is 0.4% when following, can think that products formed is exposed to the reduction of the hot and humid lower transparency afterwards very little.Especially,, according to the manufacture method of products formed of the present invention, can easily make the extremely excellent products formed of such transparency.
Need to prove, low initial haze value as above shows that in cyclic olefin resin composition the composition such as thermoplastic elastomer (TPE) is that differential is loose, and these compositions can bring harmful effect to the transparency of products formed hardly.
As mentioned above, the products formed of the present invention with very high transparency has the various characteristics that cyclic olefin resin brings, and can keep high transparent.Therefore, products formed of the present invention for example can be preferred for: optical applications, medical application, packing purposes, electrical and electronic parts purposes, industrial sector parts purposes.Especially can be preferred for the optical applications that is maintained important necessary condition of the transparency, such as being used as: f-θ lens, shooting are optical lens, LGP, the diffraction grating such as lens, optical pick-up device lens.
Embodiment
Below enumerate embodiment the present invention is described in further detail, but the present invention is not limited to these embodiment.
＜cyclic olefin resin composition pellet 1～4(pellet 1～4) manufacturing 〉
As cyclic olefin resin, the TOPAS6013(glass transition temperature (Tg) that uses TOPAS Advanced Polymers company to make is 138 ℃), with respect to cyclic olefin resin with the formula shown in table 1 add material that thermoplastic elastomer (TPE) (SEPTON2104 that Kuraray company makes) forms being set as 260 ℃ of barrel zone temperatures, extrusion capacity 15kg/hr(uses constant feeder), melt extrude in the 30mm Φ biaxial extruder of screw speed 200rpm, pellet.
＜cyclic olefin resin composition pellet 5(pellet 5) manufacturing 〉
Supply with ENB, hydrocarbon system solvent (polymer solvent), ethene and hydrogen in continuous polymerization unit, the quantity delivered of ENB is that the quantity delivered of 10kg/h, polymer solvent is that the quantity delivered of 40kg/hr, ethene is that the quantity delivered of 2.2kg/hr, hydrogen is 10kg/hr.To be supplied in reaction unit by the racemic-isopropylidene as catalyst (polymerization catalyst)-two (tetrahydro indenyl) zirconium chloride, the catalyst system that forms as the MAO (10% toluene solution) of co-catalyst simultaneously.The temperature of reaction unit is remained 90 ℃, add in the tank diameter of ensuing operation with respect to cyclic olefin resin is the antioxidant (trade name: IRGANOX1010 of SEPTON2104 and the 0.4 quality % of 0.9 quality %, BASF AG makes), in the desolventizing operation of following, remove desolventizing under high-temperature pressure-reduction.The copolymer that will be in molten condition is extruded as line material shape,, with its cut-out, makes pellet.The glass transition temperature of this cyclic olefin resin composition is 137 ℃.
The evaluation of＜cyclic olefin resin composition pellet 〉
For above-mentioned cyclic olefin resin pellet 1～5, (Sumitomo hoisting machinery company makes to use injection moulding machine, trade name: SE75D), at the condition compacted under of 280 ℃ of barrel zone temperatures, 110 ℃ of mold temperatures, be the flat board of 70mm * 70mm * 2mm, obtain test film.This test film is carried out the evaluation of yellow chromaticity (YI value), total light transmittance.
[yellow chromaticity (YI value)]
Colour difference meter color-sphere with YKB-Gardnar GmbH makes, measure yellow chromaticity (DIN6167).In measurement result shown in table 1.
[total light transmittance]
(Japan's essence mechanism is done manufacturing, trade name: HAZE GARD II), according to the method for JIS K7136, measure total light transmittance to use mist degree instrument (haze meter).In measurement result shown in table 1.
[table 1]
| ? | Pellet 1 | Pellet 2 | Pellet 3 | Pellet 4 | Pellet 5 |
| Cyclic olefin resin (quality %) | 99.2 | 98.2 | 97.0 | 100.0 | 99.1 |
| Thermoplastic elastomer (TPE) (quality %) | 0.8 | 1.2 | 3.0 | 0.0 | 0.9 |
| The YI value | 2.71 | 2.93 | 12.74 | 1.05 | 1.96 |
| Total light transmittance (%) | 90.8 | 90.6 | 85.2 | 91.4 | 91.1 |
With the result of the result of pellet 1～3 and pellet 5 relatively, pellet 5 is less than the YI value of pellet 1～3, total light transmittance is high.Thereby confirmed:, according to add the method for thermoplastic elastomer (TPE) when making cyclic olefin resin, obtain the higher raw material of the transparency.
＜embodiment 1～7, comparative example 1～6 〉
The pellet 1～5 that use obtains in above-mentioned Production Example, (Sumitomo hoisting machinery company makes to use injection moulding machine, trade name: SE75D), condition compacted under 110 ℃ of barrel zone temperature (Table 2,3), the mold temperatures stipulated is the flat board of 70mm * 70mm * 2mm, thereby obtains test film.
[evaluation of haze value]
The test film that obtains is carried out the mensuration of the haze value (initial haze value) after moulding.Particularly, (Japan's essence mechanism is done manufacturing, trade name: HAZE GARD II), carry out the mensuration of haze value according to the method for JIS K7136 to use mist degree instrument (haze meter).
Then, test film was exposed in 85 ℃ of temperature, humidity 85% environment after 240 hours, in the environment of 23 ℃ of temperature, humidity 50% cooling 1.5 hours, again measure haze value (haze value after damp heat test), calculate haze value recruitment (haze value after damp heat test-initial haze value).In result shown in table 2,3.
[table 2]
[table 3]
The comparison of the result by embodiment 1 and 2 and the result of comparative example 1, the comparison of the result of embodiment 3 and 4 result and comparative example 2, the result of the result of embodiment 5～8 and comparative example 5 and 6 relatively can be clear and definite, by barrel zone temperature being set as the condition below Tg+170 ℃, the products formed that obtains transparent high, even and if then be exposed to hot and humid lower its transparency and also reduce hardly.
Relatively can confirming of result by embodiment 1, embodiment 3 and embodiment 5 and the result of comparative example 3: thermoplastic elastomer (TPE) contain quantitative change when many, also the become recruitment of not high enough and haze value of the transparency of products formed self is also large, and the reduction of the transparency under hygrothermal environment is large.
Relatively can confirming of result by embodiment 1, embodiment 3 and embodiment 5 and the result of comparative example 4: while not containing thermoplastic elastomer (TPE), the reduction of the transparency of products formed that products formed is exposed to hot and humid lower time is large.
In addition, in the result of result, embodiment 3, embodiment 4 and the comparative example 2 by embodiment 1, embodiment 2 and comparative example 1, table 3, the result of record can be confirmed: within the scope of the invention, the difference of barrel zone temperature and Tg is less, the transparency is higher.
Claims (7)
1. the manufacture method of a products formed, the content that wherein, will comprise cyclic olefin resin and thermoplastic elastomer (TPE) and described thermoplastic elastomer (TPE) is 0.1 quality % is above and 2 quality % are following cyclic olefin resin composition is condition compacted under below the glass transition temperature (Tg)+170 ℃ of described cyclic olefin resin at barrel zone temperature.
2. the manufacture method of products formed according to claim 1, wherein, the condition of described barrel zone temperature is more than 250 ℃ and below 300 ℃.
3. the manufacture method of products formed according to claim 1 and 2, wherein, described cyclic olefin resin is the copolymer of ENB and ethene.
4. products formed, wherein, contain in cyclic olefin resin composition 95.0 quality % are above and 99.9 quality % are following cyclic olefin resin,
The thermoplastic elastomer (TPE) that 0.1 quality % is above and 2.0 quality % are following,
Described products formed to measure based on the JIS-K7136 test film that is 2mm to thickness the haze value that obtains be below 0.6%.
5. products formed according to claim 4, wherein,, through described test film being exposed in the environment of 85 ℃ of temperature, humidity 85% 240 hours, be below 0.4% with the haze value of this test film this test film after the processing of cooling 1.5 hours in the environment of 23 ℃ of temperature, humidity 50% and the difference of aforementioned haze value thereafter.
6. according to claim 4 or 5 described products formeds, wherein, described products formed is optics.
7. the manufacture method of according to claim 1～3 described products formeds of any one, wherein, described cyclic olefin resin composition is made by the following method:
In carrying out the polymeric solution that contains cyclic olefin resin that polymerisation in solution forms or remove the polymer of the molten condition that polymer solvent forms from polymeric solution, the monomer composition that comprises the cycloolefin monomer adds thermoplastic elastomer (TPE).
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| CN104999635A (en) * | 2015-06-18 | 2015-10-28 | 北京汽车股份有限公司 | Automotive glass manufacturing method and automotive glass |
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| JP2014172390A (en) * | 2013-03-13 | 2014-09-22 | Nippon Zeon Co Ltd | Method of molding optical member |
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| EP0559146A1 (en) * | 1992-03-03 | 1993-09-08 | Nippon Zeon Co., Ltd. | Medical implement, polymer composition and optical material |
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| KR20130117829A (en) | 2013-10-28 |
| TW201302900A (en) | 2013-01-16 |
| TWI580723B (en) | 2017-05-01 |
| KR101497637B1 (en) | 2015-03-02 |
| WO2012114608A1 (en) | 2012-08-30 |
| JPWO2012114608A1 (en) | 2014-07-07 |
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