TW200932476A - Process for producing injection-molded article and masterbatch for use in the same - Google Patents

Abstract

A process for producing an injection-molded article. The process facilitates injection molding while taking advantage of the features of a low-molecular cycloolefin resin. Also provided is a masterbatch for use in the process. A masterbatch comprising a cycloolefin resin and a low-molecular cycloolefin resin having a number-average molecular weight of 10,000 or lower and a cycloolefin resin are dry-blended and then injection-molded. The masterbatch preferably comprises 20-95 mass% the cycloolefin resin and 5-80 mass% the low-molecular cycloolefin resin.

Description

In the present invention, the present invention relates to a method for producing an injection molded article using a low molecular weight cyclic olefin resin and a high concentration dyeing of the low molecular weight cyclic rare hydrocarbon resin used therefor. Ingredients. [Prior Art] The cyclic olefin resin is excellent in transparency, chemical properties, moisture resistance, and mechanical properties, and is used as a material for optical applications, medical applications, medical applications, and the like. Further, the cyclic olefin resin is excellent in melt processability and fluidity, and is also used in a film-like or sheet-like molded article and a packaging material. Further, the cyclic olefin resin is excellent in heat shrinkability and printing properties. As described above, the cyclic olefin resin is used in various fields. Further, the cyclic olefin-based resin has a gel-like substance formed during melt molding, and the surface of the cyclic olefin-based resin is roughened to lower the appearance of the surface. This decrease in the appearance characteristics is particularly affected by the use of a cyclic olefin-based resin as a transparent (four), a prior learning application, and a packaging material. In order to solve the above-described deterioration in the appearance characteristics, it is disclosed in the patent document that the surface of the molded article can be smoothed by blending a high molecular weight cyclic olefin resin and a low molecular weight cyclic rare hydrocarbon tree. Technology. [Patent Document 1] International Publication WO2007/132641 Booklet. [Summary of the Invention]

2254-1 〇 158-PF 5 200932476 [Problems to be Solved by the Invention] Ingeniously:: Degrees of resin molding 'usually can be used in a step-by-step process that can be complicated and refined into J. The injection molding method can be completed in a short time. . In the injection molding method, it is possible to process a variety of materials such as parts for enamel products, bones, _% 々 轧 轧, and parts for automobiles. In addition, the complexity of the mold structure, the intensiveness of the parts, and the intensification of the parts have recently been carried out, so that the parts that are not formed by injection molding are increased. = Yes, according to the patent literature! According to the invention, the low molecular weight cyclic smoky tree sap and the cyclic olefin saponin are used as the molding material for injection molding, and the resin = poor input property, and the measurement time becomes long. Therefore, in the patent document i method, the forming material takes time for each forming of the forming material, and the productivity is lowered. Further, the melting of the low-molecular-weight cyclic flue-cured wax and the cyclic dilute-based resin is discrete in the supply amount and the measurement time of each molding, and the quality of the product is not determined. Therefore, it is required to be able to effectively utilize low molecular weight cyclic dilute (tetra) resin characteristics and to easily form a technique for formation. The present invention has been made to solve the above problems, and an object of the present invention is to provide a technique capable of effectively utilizing a low molecular weight cyclic olefin-based resin and easily ejecting and molding. [Means to solve the problem] This month's people 4 solve the above problems and concentrate on repeated research. As a result, the inventors have found that a high-concentration dyeing ingredient containing a cyclic olefin-based resin and a low-molecular-weight cyclic olefin-based resin having a number average component of 100,000 or less and a cyclic olefin-based resin are dried and mixed. After the injection molding, the injection molding can be easily performed. π Completion of the present invention is more specific, and the present invention is provided by the following 2254-1〇158 Section 200932476. (1) A method for producing an injection molded article, which comprises using a cyclic olefin resin; and a method for producing an injection molded article of a low molecular weight cyclic thinning resin having a number average molecular weight of 1 () or less, which is The high-concentration dyeing ingredient comprises a cyclic olefinic resin and a low molecular weight cyclic vodonic resin; and the cyclic olefin resin is dried and mixed, and then injection molded. ❹ ❹ According to the invention of (1), a high-quality injection molded article can be easily obtained. As in the past, when the low-molecular-weight cyclic terpene hydrocarbon tree is not used for the high-concentration dyeing, the glass transition temperature is low, and the granules are very brittle due to the low molecular weight, which is caused by compression or friction during plasticization. It is easy to pulverize into powder and adhere to the surface of the rubber particles of the substrate. Due to the influence of the powder, the friction of the first half of the plasticizable body with the material tube during transportation becomes small and the biting quality is deteriorated. Further, the low molecular weight cyclic olefin resin rapidly melts and exhibits a low viscosity state. Resin and screw, the coefficient of friction, as the coefficient of friction between the resin and the tube is close to the resin, the resin is not transported to the front, and if the coefficient of friction between the resin and the screw exceeds the coefficient of friction between the resin and the tube, The resin will not be transported to the front. Therefore, if the high-density dyeing of the molecular weight cyclic olefin-based resin is not used for dyeing, there is a problem in the biting property of the resin to the screw. In the present invention, by using a low-molecular-weight cyclic olefin-based resin for high-concentration dyeing and dosing, the use of a low-molecular-weight cyclic olefin-based resin glass transition temperature of a low-molecular-weight dyeing ingredient is low, and It improves the toughness of the rubber pellets, and it is easy to lose even if it is plasticized. ^ B ^ Machimachi shrinks and rubs, and it is not easy to form powder, so it can suppress rapid melting and improve the biting property of the resin. (2) The method for producing an injection-molded article according to (1), wherein the above-mentioned high concentration

2254-1015S-PF 200932476 degree dyeing ingredients are from the ring can, the law, ηγ < ^ . m habitat eight; the amount is 20% by mass to 95 mass 〇 / έή ^ ^ ^, the secluded weight system is 5% by mass to 80 mass of dyeing ingredients 'in the above-mentioned dry mixing step, the above cyclic olefin resin 100 mass adjacent, # μ, +, ^_ β 奵 the above-mentioned cyclic load 邛, so that the above high concentration dyeing to 100 mass parts mixture. According to the invention of (2), the needle is contained in the above range, and as long as it is a low-grade dyeing ingredient, the amount of the cyclic olefin-like olefin resin is required to be reduced by the same amount: + The amount of rushing and the ring is ~"" sorghum dyeing ingredients will be sex" and the amount of powder produced is small and it is not easy to cause the measurement problem item to be high: the dyeing ingredient 'is used for (1) or (2) Any of the high-concentration dyeing ingredients of the manufacturing method of the ji-shaped product, the content of the cyclic olefin resin is 20% by mass to 5% by mass. The above-mentioned low molecular weight Jinhua station olefin resin content is 5% by mass to 8 The mass-knife amount ring (4) (3) The high-concentration dyeing and the olefin-like resin content is from 1% by mass to 70% by mass. The above-mentioned low molecular weight ring is in accordance with the inventions of (3) and (4). In the above range, the fat content can be changed from the low molecular weight cyclic terpene hydrocarbon tree to control the occurrence of the gel. Therefore, the injection molded product of the filling quality is produced. The production is advanced with high productivity. High (5) (3) or (4) high road; nine degrees below 100 ° C. 'The glass transfer temperature according to the invention of (5), because of the words, the electricity of A 1 Π Π °r T m , and the glass transition temperature of the music color ingredients is below 100C, so the melt forming degree, the temperature of the dyeing The ingredients are more than the ring.

2254-10158-PF 200932476 The olefin-based resin is first melted, and the cyclic olefin resin can be subjected to a small shear force. Therefore, the generation of the gel can be suppressed more effectively. [Effect of the Invention] According to the present invention, a high-concentration dyeing ingredient is a low-molecular-weight cyclic olefin resin having a number average molecular weight of 1,000,000 or less and a cyclic olefin resin, and a cyclic olefin resin. After the drying and mixing step, the injection molding can effectively utilize the characteristics of the low molecular weight cyclic olefin resin, and a high-quality injection molded article can be easily obtained.实施 Embodiments Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be appropriately modified and implemented within the scope of the object of the present invention. In addition, in the case where the explanation is repeated, it is appropriate to omit the description, and it is not intended to limit the gist of the invention. The present invention relates to a high-concentration dyeing ingredient comprising a cyclic olefin-based resin and a low-molecular-weight cyclic olefin-based resin having a number average molecular weight of 1,000,000 or less; and a cyclic olefin-based resin, which are injection-molded by injection molding after drying and mixing steps. The manufacturing method and the high concentration dyeing ingredients used therefor. The present invention is characterized in that a high-concentration dyeing ingredient comprising a cyclic olefin-based resin and a low molecular weight cyclic olefin-based resin having a number average molecular weight of 1,000,000 or less is used. The south concentration dyeing ingredient used in the present invention comprises a cyclic dilute resin and a low molecular weight cyclic olefin resin having a number average molecular weight of 1,000,000 or less. * "Cyclic olefin-based resin" 2254-1015B-PF 9 200932476 Hereinafter, a cyclic olefin-based resin which is an essential component of the injection-molded article produced by the present invention and the enamel-tune wood-colored component of the present invention will be described. The cyclic thin-type resin to be used in the present invention is a polyolefin-based resin containing a cyclic olefin component as a copolymer component, and is not particularly limited as long as it is a polyolefin-based resin containing a cyclic olefin component in the main chain. For example, an addition polymer of (al) a cyclic olefin or a hydrogenated product thereof can be mentioned. (a2) a cyclic olefin and an α-olefin addition copolymer or a hydrogenated product thereof.

❹ U3) a cyclic olefin ring-opening (co)polymer or a hydrogenated product thereof. Further, the cyclic olefin resin containing the cyclic olefin component of the present invention as a copolymerization component has U4) a resin having the polar group in the above (al) to (a3) resins, and grafting and/or copolymerization. Saturated compound. Examples of the polar group include, for example, a slow group, an acid group, an epoxy group, an amine group, a S-mercapto group, and the like, and a polar group-containing unsaturated compound, and examples thereof include (meth)acrylic acid, maleic acid, and horse. Anhydride, Yi Kang liver, glycidyl (meth) acrylate vinegar, (meth) acrylic acid hospital base (carbon number (9) vinegar, maleic acid sulfhydryl (carbon number 1 ~ 10) vinegar, (曱 ) 醯 醯 ) 醯 、 醯 醯 醯 醯 醯 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 环状 环状 环状 环状 环状 环状 环状 环状 环状 环状 环状 环状 环状 环状 环状 环状 环状 环状 环状In the case of the cyclic olefin resin which is used as the copolymer component in the cyclic olefin component of the present invention, a commercially available resin may be used. A commercially available cyclic olefinic resin may be used. For example, Cong S (registered trademark) (Cong Seng listens to POLYMER company), ship (registered trademark) (Mitsui Chemical Co., Ltd.)

2254-10158-PF 200932476 ΖΕ0ΝΕΧ (registered trademark) (manufactured by Nippon Co., Ltd.), ZE0N0R (registered trademark) (manufactured by Nippon Co., Ltd.) ' ART0N (registered trademark) (manufactured by JsR Co., Ltd.). The (a2) cyclic olefin and the a-olefin addition copolymer which can be suitably used in the composition of the present invention are not particularly limited. Particularly preferred examples thereof include a copolymer of a cyclic olefin component represented by the following formula (I): [1] an α-ene fe component having 2 to 20 carbon atoms; and [2].

❺ ❹ * * * (I ) (wherein m may be the same or different, selected from the group consisting of a dentate atom and a hydrocarbon group, or aRie, R - may be formed to form a divalent hydrocarbon group'" ^" and ~ mutually, η means 0 or a positive integer, 瞒2 or more, into a ring. The units can be the same or different.) Repeat [[1] carbon number 2~20 α -Olefin component] It can be suitably used for the addition of other *polymerizable components such as dilute in the present invention:: two components and an olefin which can be 2 to 20, and the helmet "the carbon number of the polymerization component I is limited." It can be mentioned that your butene ' 1-pentene, 1-hexene, 3, ene, Bu 1 Τ 一 I I - Ding entropy, q field basin, 3-ethyl-1-pentene, 4_ methyl group - 1 pentene, 44 τ 1-1-pentene, 4 dimethyl-1-hexene, 4,4-methyl, a olefin, 4,4~, a-methyl-p-pentene, 4 ethyl-b-hexane, b-octene, diterpenoid, 3~undecene, tetradecene,

2254-10158-PF 200932476 hexadecene, 1-octadecene, and eicosene. Further, these α-olefin components may be used alone or in combination of two or more. It is best to use ethylene alone. [[2] a cyclic olefin component represented by the formula (I)] is an additive polymer which can be suitably used in the cyclic olefin component of the present invention and another copolymer component such as ethylene, and is a copolymerization component. A cyclic olefin component represented by the formula (I). ❹ 在于 In the formula (I), R1 to R12, respectively, may be the same or different and are selected from the group consisting of a gas atom, a dentate atom, and a hydrocarbon group. Specific examples thereof include a hydrogen atom, fluorine, chlorine, and a dentate atom; a lower alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group; and the like may be different or partially different. And, they can all be the same. Specific examples of the second element include, for example, a hydrogen atom; an alkyl group such as fluorine, gas, or a dentate atom such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, or a hard wax group; Hexyl and other cycloalkylethylphenyl, isopropylphenyl, benzylidene, aromatic hydrocarbon; substituted or unsubstituted aryl group 箄H, fluorenyl, etc. substituted by other morphologies The aryl group says base and so on. The materials may be different, or may be partially the same or may be all R and R or R, R12 integrated to form a divalent nicotine. For example, an ethylene group, a propylene group, or an iso-form may be added. , or add a ring to each other: a sub-base or the like. It can also be a multi-ring, which can be a multi-ring with a bridge, or == can be a single ring or a ring combined with the rings. ~ Double-bonded ring, and the rings can also have a methyl group, etc.

2254-10158-PF 12 200932476 Substituent. Specific examples of the cyclic olefin component represented by the formula (I) include bicyclo[2.2.1]hept-2-ene (common name: norbornene), 5-methyl-bicyclo[2] 2. 1] Geng_2-diluted, 5,5-dimethyl-bicyclo[2.2.1]heptane-2~~diluted, 5-ethyl-~~bicyclo[2. 2·1]heptane- 2-distilled, 5-butyl-bicyclo[2·2·1]hept-2-diene, 5-ethylidene-bicyclo[2·2·1]hept-2-ene, 5-hexyl-di Ring [2· 2. 1 ]hept-2-ene, 5-octyl-bicyclo[2·2.1]hept-2-ene, 5-h-octyl-bicyclo[2.2.1]hept-2- Alkene, 5-indenyl-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, 5-propenyl-di a 2-ring cyclic olefin such as a ring [2.2.1]hept-2-ene; a tricyclo[4.3.0.12'5]indole-3,7-diene (common name: dicyclopentadiene), a tricyclic ring [4. 3. 0· I2'5] indole-3-ene; tricyclo[4. 4· 0· I2'5] undecen-3, 7-diene or tricyclo[4. 4. 0. I2'5] undecane-3, 8-diene or a partial hydrogenation (or an adduct of cyclopentadiene and cyclohexene) of the tricyclic ring [4.4.0.I2'5] Monocarb-3-ene; 5-cyclopentyl-bicyclo[2.2.1]hept-2-diene, 5-cyclohexyl-bicyclo[2.2.1]heptane-2-dilute, 5-cyclohexyl - Second ring w [2. 2. 1] a 3-ring cyclic olefin such as hept-2-ene, 5-phenylbicyclo[2. 2·1]hept-2-ene; tetracyclic [4. 4· 0. I2'5. Γ1 . ]Dodeca-3-ene (also referred to simply as tetracyclododecarbene), 8-mercaptotetracyclo[4. 4. 0. I2, 5. I7'1. ]Dodeca-3-ene, 8-ethyltetracycline [4. 4. 0. I2'5. Plant '10] dodeca-3-ene, 8-methylenetetracycline [4_4.0· 12'5.Γ'1()]dodec-3-ene, 8-ethylenetetracyclo[4.4.0.12'5.17'1D]dodec-3-ene, 8-vinyltetracycline [4_ 4. 0. I2'5. Γ'111] Twelve, carbon-3-ene, 8-propenyl-tetracyclic 2254-10158-PF = 13 200932476 [4.4.0.iu.r'u] twelve carbon a 4-ring cyclic dilute hydrocarbon such as _3_ene; a group of cyclopentyl-tetracyclo[". Ο.12, 5.17'1.] twelve carbon 1 埽, 8-cyclohexyl-tetracyclo[U. 0.125·17,1.]12-carbon-3~dilute, 8-cyclohexenyl-tetracyclo[4'4'i1 22 55 'l71°] ten m 8' stupyl-cyclopentyl-tetracyclic four Carbon-U, u, 13-tetraene (also known as ❹ ❹ ❹; four rings [8.4.l4,7.〇1,u.〇3.8] fifteen carbon-5,10,12,14-four Rare (also known as w'Mfm4a'5,1Q,1Ga_A^i);^ (6.6.1.m,14]-4-hexadecene, pentacyclic [6.5.1.1-.〇-.〇9,13 ]_4_ fifteen rings ^ Qiu, Wuhuan [7.4. 〇, 〇ul3'6.lle, 13]_4_ fifteen carbon 埽 seven rings [8*7.0.12.9.14, 7.lu'm-5- twenty a polycyclic cyclic olefin such as a carbonium, seven, or twelve, a tetracene-ene tetramer, etc. A - ^ The cyclic dilute hydrocarbon component may be used alone or in combination with 2_0 [1] as a carbon number 2 to _α_dilute hydrocarbon component and [2] formula (method of polymerization of the olefin component and oxygenation method of the obtained polymer, ring-shaped ' can be carried out according to a conventional method. It can be a random copolymerization, : = a later stage copolymerization. It can also be a 'Zigler Nata system for the use of the polymerization catalyst, and there is no particular limitation on the former. Open-ring system, metallocene catalyst = first catalyst obtained by a known method. It can be suitably used in the present invention, hydrocarbon and α-olefin addition copolymer or hydrogenated product thereof, preferably using gold Alkene

2254-10158-PF 14 200932476 Media or Ziegler Natta is a catalyst manufacturer. For the reopening of the ring catalyst, it is known to use a molybdenum or tungsten-based reopening ring catalyst as a catalyst for ring-opening polymerization of a cyclic olefin (for example, JP-A-58-127728, JP-A-58-129013) Etc.). Further, the polymer obtained by using the reopening ring catalyst is an inorganic carrier-supported transition metal catalyst, and more than 90% of the double bond of the main chain is bonded, and the carbon-carbon double bond in the aromatic ring of the side chain is bonded. More than 98% hydrogenation is preferred. [other copolymerization ingredients]

The (a2) cyclic olefin = α-olefin addition copolymer which can be particularly preferably used in the composition of the present invention, the olefin component having a carbon number of 2 to 2 Å in the above [], and the formula (2) In addition to the cyclic olefin component shown, other copolymerizable unsaturated monomer components may be contained as needed in the range which does not impair the object of the present invention. The unsaturated monomer which can be arbitrarily copolymerized is not particularly limited, and for example, a hydrocarbon-based monomer having two or more carbon-carbon double bonds in the i molecule is equivalent to one or more carbons in one knives. - Specific examples of the carbon double bond-bonded flue monomer may be 1 4-p-, knee 1 β ^ β 竿 U hexene, υ-octadiene, 2-methyl-di-hexanene 4 -Methyl-hexamethylene dichloride, 5-methylexene dichloride, 6m heptane dilute, 7-methyl-U-octadiene, etc. Cyclopentanediolate 'methyl read base section, vinyl-2-original borneol, 5-ethylidene-2-original borneol, 5_methylene 2, raw ice-original borneol, 6-chloroform ...C...-original borneol propyl 4' 9, 5, 8-_ methylene _3a, 4, 4a, 5, 8, 8a, 9, 9a octa hydroxy, fluorene, etc. ; 2, 3 - diiso. propylene ~ 5 - raw ice, ene; 2_

2254-10168-PF 15 200932476 Ethylene 3-isopropylidene-5-norbornene; 2-propenyl-2,2-dicycloheptadiene. Among these, i'4-hexadiene, octadiene, and cyclic non-conjugated dienes, especially dicyclopentadiene, 5-ethylidene-2-formerene, and vinyl -2-Ornirolene, 5-methylene-2-norbornene, 1,4-hexadiene, 1,6-octane dilute is preferred. ❹ 玻璃 The glass transition temperature of the cyclic olefin resin may be 801 or more, for example, 8 (TC to 180 ° C, preferably 10 (TC to 170 ° C, more preferably 〇 :: 〜16 〇 C Further, the glass transition temperature can be controlled by adjusting the ratio of the copolymerization component, the molecular weight, etc. The glass transition temperature (Tg) of the cyclic olefin resin used in the present invention is based on the method described in JIS K7121. The cyclic olefin resin is preferably a cyclic olefin resin having a number average molecular weight of more than 1 Å. More specifically, a cyclic olefin resin is used. The number average molecular weight is preferably 15_~che_, and 2_(M〇〇_ is more preferable, and further preferably 30,000 to 80,000. <Low molecular weight cyclic olefin resin> Low-knife amount of cyclic hydrocarbon resin, The cyclic rare hydrocarbon resin exemplified in the above-mentioned ring-shaped thin-smoke resin is used. The same is true from the viewpoint of compatibility and the like. Or the same kind of resin is preferred. The low knife amount of cyclic polyolefin resin is The ratio of the copolymer (for example, a class such as a woman) can be selected by the whole single ====, but in terms of appearance characteristics and the like, it can be, for example, = 耳耳/55 to 95 mol% left, It’s better. Know, don’t, the copolymerizable monomer is

2254-10158-PF 16 200932476 When ethylene is thin, [thin ratio, depending on the appearance characteristics, etc., may be, for example, 6 (four) mole %, preferably about 70 to 85 mole %. The glass transition temperature of the low-knife amount cyclic olefin resin is preferably 7 Å or less, more preferably 40 t to 70 t. If the glass transition temperature is below 7〇1, it will be a sub-quantity ring-shaped thin-smoke resin, which will be more common than the normal ring-shaped flue-cured tree wax. Therefore, in the case of (4), the (four) rod can be applied to the ring. Shear force of dilute resin. Therefore, the generation of the gel can be suppressed, and only

It is easy to handle at a high concentration of 40 C or more. The glass transition temperature of the low-quantity cyclic olefin resin is preferably lower than the glass transition temperature of the above cyclic olefin resin. The difference is preferably in the order of ~100 °c, more preferably in the range of 20 ° c to 1001. The number average molecular weight of the low molecular weight cyclic terpene hydrocarbon resin is 1 Å or less. The number average molecular weight is preferably 5 〇〇 to _ ,, more preferably 1 〇〇〇 to 7 ,, and further preferably 1500 to 6,000. The difference between the number of the olefin-like olefin resin and the low-molecular-weight cyclic olefin resin is not particularly limited, and it is preferably W 〇 10000 〜 15 〇〇〇〇 f4, A t υ is further improved. 200 〇 (Μ〇〇〇〇〇 is better, 30,000~80000 祛. μ.+, „ __ The number of olefin-based resin and low-molecular-weight ring-shaped sleek resin is equal to eight « The difference in the amount of the knife is only 1 000 or more, because

The effect of producing a gel will be improved, and the M double fruit will become better. As long as it is below 200000, the processing temperature difference A will be -Wr.»*· ρτι in the valley, it will not It is preferable to have an adverse effect on the workability at the time of molding. [High concentration dyeing ingredients]

2254-10158-PF 17·

❹ 200932476 The present invention is characterized in that a low molecular weight cyclic olefin resin and a cyclic olefin resin are dyed and mixed at a high concentration. By the high concentration dyeing, it is possible to prevent the low molecular weight cyclic olefin resin from being rapidly melted during injection molding. Therefore, the resin biteability can be improved, and the molding material can be moved smoothly. As a result, the measurement time per injection is shortened, and the productivity of the injection molded article can be improved. The cyclic olefin resin in the intermediate concentration dyeing composition is preferably 丨〇 mass% by mass. It is more preferably 2% by mass to 9% by mass. When the content of the cyclic olefin resin in the high-concentration dyeing ingredient is within the above range, and the amount of the low molecular weight cyclic olefin resin is equal to or less than the amount of the cyclic olefin resin, the high-concentration dyeing rubber particles can have sufficient toughness. The small amount of production is not easy to cause the problem of measurement. The low-knife amount cyclic olefin-based resin is preferably 5% by mass to 5% by mass, more preferably 10% by mass to 80% by mass: f%. When the amount is 5% by mass or more, the effect of reducing the gel is good, and if it is 9% by mass or less, the amount of the low molecular weight cyclic ring-based resin is equal to the amount of the cyclic thin-smoke resin, that is, It can make the high-concentration dyeing rubber particles have sufficient (4), and the amount of powder generated is small: it is better to cause the measurement problem. It is preferable to produce a high-concentration dyeing compound by using a cyclic olefin-based resin and a low-molecular-weight ring-shaped tobacco tree to be extruded into a machine. The type of the extruder is not particularly limited. Due to the rapid melting of the low molecular weight cyclic thin-smoke resin, it is difficult to produce high-concentration dyeing by injection molding. • Preparation of dyeing ingredients in the south concentration requires the formation of a cyclic olefin resin and

2254-10158-PF 18 200932476 The low molecular weight cyclic olefin resin is uniformly kneaded in the extruder in the present invention. Since the low molecular weight cyclic (tetra) (tetra) grease is rapidly melted, the temperature of the tube is from 18 to 340. It is better. It is better to use 2〇〇t~32(rc. Also 'the number of rotations of the screw is 5G per minute~ every minute is better, and it is better to turn 100 rpm to 25 〇Γριη per minute. 5kg / h Bu 200kg / hr is better. 1 〇 kg / h 〗 〖 kg / hr better. The high concentration of dyeing ingredients obtained by the glass transfer temperature to 〗 〖t below "... (^, .... When the glass transition temperature is within the above range, the high-density dyeing ingredients can be rapidly melted, and the low-molecular-weight cyclic hydrocarbons which are required for easy injection molding can be smoothly transferred during injection molding. Preferably, the [cyclic olefin resin] is a cyclic olefin which is dry-mixed with the agricultural dyeing ingredient, and can be exemplified by the above-mentioned cyclic olefin resin which is not contained in the high-concentration dyeing ingredient. The cyclic olefin-based resin which is dried and mixed with a high-concentration dyeing ingredient may be a resin different from the cyclic rare-earth resin containing a high-concentration dyeing ingredient, and it is preferable to use the same resin from the viewpoint of compatibility and the like. [Injection Forming] The present invention is characterized in that injection molding is performed. Injection into several steps, using the above-described reasons of high waves dyeing ingredients preferably two injection molding, the material can be divided into steps, holding pressure cooling step. 'Step emitted.

&lt;Material input step&gt; 2254-] 〇l5S^PF 19 200932476 The injection molding of the present invention is characterized by dry mixing. If it is not: dry mixing, the generation of the gelatinous substance cannot be effectively suppressed due to the low molecular weight cyclic olefin wax which appears on the surface. The use of a cyclic olefin-based resin colloid having a high content of a low molecular weight cyclic olefin resin as a molding material can facilitate the formation of an injection. However, when the content of the low molecular weight cyclic olefin resin in the injection molded article is increased, the mechanical strength such as tensile elongation at break is lowered, which is not preferable.

This is effective in suppressing the generation of a gel and obtaining a high-quality injection molded article, which requires dry mixing. The shape of the cyclic olefin resin which is dry-mixed with the high-concentration dyeing ingredient is not particularly limited, and may be a powder, but it is preferably a rubber particle. <Plasticizing Step> In the plasticizing step, a cyclic olefin resin, a high-concentration dyeing ingredient, and the like (molding material) supplied from the hopper are conveyed and melted to form a homogeneous melt. The formation of the cyclic olefin resin and the high-concentration dyeing ingredients, etc., which are fed from the hopper, is transferred from the hopper side to the nozzle direction side by the rotation of the screw. The screw is composed of a supply zone (supply portion), a compression zone (compression section), and a metering zone (metering section) on the side of the hopper. The supply unit generally serves to transport the resin micelles from the hopper to the nozzle in a temperature setting in which the resin micelles are not melted. Although it is taken at a low temperature, it is preheated by an external heater as a preparation stage for melting. In addition, the tree scorpion kicking is sandwiched between the rotating screw and the material tube, and friction is added to the resin granules to generate frictional heat. The low molecular weight of the glass transition temperature is low.

W2254-10158-PF 20 200932476 Cyclic olefin oxime resin generally has a melting point, multi-handle θ s 孜 右 low, using a fine moxibustion rubber particle containing a large amount of such a low-knife-set cyclic olefin resin as a molding material, Preheating and frictional heat and melting. When the forming material is melted at this stage, it is co-rotated with the screw to efficiently transport the forming material. Moreover, even if &amp; ..., evening "contains a lot of low-molecular-weight cyclic olefin tree, the rubber particles are not completely refining and become a large clump together with the ring-shaped thin resin." The block is shallower than the groove of the screw

The shaped material cannot be efficiently transported. Since the conveyance cannot be smoothly performed, the amount of time per time is increased, and the productivity of the injection molded article is lowered. In addition, because the transport benefit method is swung from the side 疋..., the second time is smooth, so the difference between each time becomes larger. Because the discrete (4) measurement time affects the shape of the radiation. However, in order to suppress the generation of gelatinous substances, it is necessary to melt the south concentration dyeing ingredients earlier than the ring (tetra) hydrocarbon resin to reduce the shearing force of the olefin-based resin. Low molecular weight cyclic olefinic taro is required for this purpose. Therefore, according to the present invention, a high-intensity dyeing formulation comprising a cyclic olefinic wax and a low molecular weight cyclic olefin resin is used as a forming material: The glass transition temperature and melting point of the dyeing ingredients will increase without melting in the supply part. Therefore, as long as the low molecular weight cyclic smog = high concentration dyeing of the cyclic olefin (tetra) is used, the low molecular weight can be smoothly sent. A cyclic olefin resin. 3 In order to smooth the conveyance of the molding material, the hydrocarbon resin of the high-concentration dyeing ingredient is 50% by mass to 95% by mass, more preferably 2% by mass to 95% by mass. Moreover, in order to smooth the transport, the content of the low molecular weight cyclic olefin resin is relatively

2254-10158-PF 21 200932476 It is preferable that it is a low molecular weight cyclic olefin resin containing 5 mass% to 80 mass%. With 10 quality and 60 quality! Better. The glass transition temperature of the high-concentration dyeing ingredient is preferably less than 10 °C. As long as the glass transition temperature is below i 00 〇C, high-concentration dyeing ingredients can be prevented from melting at the supply. Therefore, the high-concentration dyeing ingredient containing the low molecular weight cyclic olefin-based resin can be smoothly delivered to the compression zone. High-concentration dyeing ingredients have better glass transition temperature of 5〇〇c~1〇(rc, further 6〇()(::~1〇〇 it is better. *&quot;, 0 compression. Tethered with screw Since the depth of the groove is gradually shallower, pressure is applied to the resin colloid in the compression portion. Therefore, the resin colloid is melted in the compression portion and is conveyed forward (in the direction from the hopper to the nozzle). The reason for the gel is the shearing force at the time of melting. The high-concentration dyeing ingredient containing the low molecular weight cyclic olefin resin is melted first than the cyclic olefin resin, and the shearing force of the cyclic olefin resin can be alleviated. In the present invention, in order to smooth the transportation in the supply portion, a high-concentration dyeing ingredient containing a cyclic olefin resin and a low molecular weight cyclic olefin resin is used. The high-concentration dyeing ingredient is only a low molecular weight cyclic olefin resin. The formed colloidal particles are difficult to be melted, but it is required to be melted to form a high-concentration dyeing ingredient which is melted by the ring-shaped thin-smoke resin pellets to alleviate the shearing force of the ring (tetra) hydrocarbon-based resin. Make a low score The high-concentration dyeing ingredient of the ring-shaped thin-smoke resin is firstly refined than the cyclic olefin-based resin, and it is preferably contained in an amount of 5% by mass to 8% by mass of the extremely octa-β 贞 low knife I olefin-like resin. The mass % to 60% by mass is more preferable. 2254-10158-PF - 22 200932476 Here, the 'high-concentration dyeing ingredients will melt first because of the presence of a predetermined low molecular weight cyclic olefin resin on the surface of the high-concentration dyeing ingredient. When the content of the low molecular weight cyclic olefin resin is within the above range, the low molecular weight cyclic olefin resin which is first melted can alleviate the shearing force of the cyclic olefin resin.

Further, since the low molecular weight cyclic olefin resin is also a cyclic olefin resin, if the low molecular weight cyclic baking hydrocarbon resin is too large, there is a risk that a gelling property will be generated due to shearing force. Therefore, the content of the low-knife amount of the olefin-based resin contained in the high-concentration dyeing composition is preferably in the above range. In order to reduce the content of the low molecular weight ring (tetra) hydrocarbon resin, the size of the resin (4) is as wide as 4 ug, the length 5 is ~lmffi, and the thickness 4 is preferably as follows. As long as the size of the colloidal particles is in the above range, even if a small amount of low molecular weight cyclic (four) tree bet is used, the probability of the low molecular weight cyclic olefin resin appearing on the surface of the knee surface can be improved. In order to generally alleviate the shearing force of the cyclic olefin-based resin, the sulphate = compounding, and the ring-shaped dilute tree 曰 10 which is dry-mixed with the high-concentration dyeing ingredients. The quality department 'uses 5 mass parts, and the mass part is preferable. To! Part ~ 100 quality parts is better. In the metering part, the molding material is completely melted, and the figure can be plasticized, and the money is transferred to the front. For high-quality injection molding, it is not enough. The plasticity becomes uneven and the original temperature is different from the starting point (4). In the present invention, the ingredient is injected: the ruthenium molecular weight cyclic olefin resin is dyed at a high concentration. Therefore, it is necessary to choose a plasticized one that can achieve a uniform sentence.

2254-10158-PF 23 200932476 Forming material. In order to make the plasticization uniform, the content of the olefin-based resin is dyed at a high concentration of 9 and a high concentration, and the content of the ring-based resin is 5% by mass φ θ, and the amount of the cyclic olefin is adjusted to a high concentration. For the inter-concentration dyeing quality portion, it is preferable to use a mass of 5 parts 呷5〇, and the amount of the cyclic olefin-based resin 100 is more preferable. ° Quality is preferred. Take 丨. Quality part quality To achieve uniform plasticization ❹ (5) High-concentration dyeing ingredients and * (4) Sound:: Sub-quantity cyclic olefin resin Resin-based resin-based glass transfer dyeing ingredients dry mixing ring. C is better to move as '(10) Confucianism is better. · In order to achieve the plasticization of the sentence, the required compression ratio becomes larger. In addition, the Shigong A J screen is shallow and screw-shaped, and it is necessary to improve the productivity and carry out high cycle formation. It is necessary to make the groove of the metering section deeper and the tonnage ratio becomes smaller. In the case of the intermediate cycle forming, the screw length and the screw straightness of the hook are compared; ^n/rnMi^ is always Q. . ^ ^a/D) Become bigger. For the uniform plasticization and promotion of the picture, the money of the end of the H (four) is better, and the range of L is better. 3 Here, the “recurring ratio” refers to the ratio of the volume of the supply unit for one cycle to the volume of the period. The screw length refers to the tip from the hopper to the screw tip. [Ejection. Pressure keeping and cooling step] The injection step is to transfer the molten resin from the tube to the mold. The injection speed and the injection pressure are preferably according to the molding material used.

2254-10M8-PF 24 200932476 The injection speed is emitted. The pressure holding step is a step of continuously applying pressure to the molten resin in the cavity through the gate portion of the mold from the side of the tube of the injection molding apparatus after the molten molding material is ejected. As the volume of the resin in the cooling cavity shrinks, the molten resin can be replenished in the cavity by holding pressure. Therefore, excessive volume shrinkage in the cavity can be suppressed. Furthermore, a certain quality can be maintained by sealing the gate for a time longer than the sealing time. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, which should not be construed as limited. [Material] A cyclic olefin resin (Resin A) which is dry-mixed with a high-concentration dyeing ingredient: manufactured by Topas Advanced Polymers GmbH, trade name "TOPAS5013", and a number average molecular weight of 40,000 Å glass transition temperature of 14 Å. . . Cyclic olefin resin (B1) containing dyeing ingredients in the south concentration:

Manufactured by Advanced Polymers GmbH, the trade name "TOPAS5〇1〇", the number average molecular weight is 30,000, and the glass transition temperature is no. Low molecular weight cyclic olefin resin (B2): manufactured by T〇pas Advanced Polymers GmbH, trade name [T0PAS TM], number average molecular weight 4400, glass transition temperature 67 °C. [Method for Measuring Molecular Weight] The number average molecular weight of the above-mentioned molding material was measured under the following conditions. (Measurement conditions) 2254-10158-PF 25 200932476 Apparatus: Shodex SYSTEM-21CRI) Solvent: Toluene (Nacalai HPLC grade)

Column: Polymer Laboratories, MTXED-C (1) Flow rate: 0. 8ml / min Temperature: 40 ° C Sample concentration: 0.2w / v % (pre-measured with 薄膜.2#m membrane filter) Injection amount: 10 0 # 1 Standard sample: PS of molecular weights 1〇9〇〇〇〇, 706000, 427000, 190000, 96400, 37900, 18100, 1 0200, 5970, 2630, 1 050, 500 (0. lw/ v% concentration of polystyrene) Analysis: Evaluation of the molecular weight of the converted PS. The number of times of repeated measurement: 2 times <Preparation of high-concentration dyeing ingredients> The cyclic olefin resin (A4B1) and low molecular weight in the formulation shown in Table 2 The mixture of the cyclic dilute-based resin (B2) was put into the extruder (TEX30C manufactured by Sakamoto Steel Co., Ltd.) 'At the tube temperature 19 〇 ° C, the amount of extrusion l 〇 kg / hr' screw rotation number 15 rpm , a length of 2 5jnm, a width of 2. 5mm 'thickness of 2. 5mm of the example 1b and the high concentration dyeing ingredients of the comparative examples 1, 2. Although the high-concentration dyeing ingredients can be extruded in the first embodiment, the rubber strips are easily broken, and half of them become long rubber particles, and it cannot be said that the extrusion is good. <Preparation of injection-molded article> Resin colloidal particles of the cyclic olefin-based resin (A), resin granules of high-concentration dyeing ingredients of the examples or the comparative examples in the formulations shown in Tables 1 and 2 (Comparative Example).

2254-10158-PF 26 200932476 3In the case of the sorrow of the smoky squirrel (A), it is produced as a resin shoulder sister 4λ, and the original injection molding machine (SE75D produced by Sumitomo Heavy Industries, Ltd.) Molded product. Forming conditions, using 7-angle flat plate (film wrap) as the mold, tube temperature 270 °C 'mold temperature lire' shot out of 15Ws, 30 megax3 〇S, cooling 4Gs' metering 5 捍, screw rotation The number is _ turn per minute, the background dust is 15 MPa, and the VP switching position is brewing. c ^ The molded article is 70mm in length, 70mm in width and 2mm in thickness. [Evaluation 1] ❹ 计量 The measurement time at the time of molding of the injection molded articles of the above Examples and Comparative Examples was measured. The number of times is 30 times. Calculate the average of the measurement time (individual, and the longest measurement time and the shortest measurement time. The results are shown in Table 1 ° [Evaluation 2] The injection molded article ig of the example and the comparative example is placed in the magnetic field. The stirrer is stirred at 500 rpm for 2 small &quot; station ★ from the book to spray the molded product to dissolve. Then 'visually evaluate the amount of insoluble matter in the solution. The situation of evaluating the insoluble matter is 5', the case of insoluble matter is 4, not small The dimorphism is 3' insoluble matter, and the evaluation result of A 2 乂 It is shown in the table ^ is the case of not more than the number of things is the same. [Evaluation 3] In addition to changing the injection speed to 4〇mm/s In the same manner as in the comparative example, the injection molded article was obtained by the example of the above-mentioned "paying main" injection. The evaluation was carried out by visual inspection. The helmet was sprayed with a helmet, and the shape of the mask was small. The case of the mark eve is X. The evaluation results are shown in the table b.

2254-10158-PF 27 200932476 [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Composition of high-concentration dyeing ingredients Resin A ( 5013) 25 75 50 Resin B1 (5010) 50 60 70 60 50 90 25 Resin B2 (TM) 50 40 30 40 50 10 75 75 25 50 Tg (°C) 78 85 92 85 78 103 71 78 118 99 Composition Resin A 100 100 100 100 100 100 100 100 100 100 High Concentration Dyeing Ingredients 10 10 10 10 80 10 10 10 10 10 Evaluation Example Gel Rate 4 4 4 4 4.5 3.5 4.5 4.5 3.5 4.5 Spray Marking 〇〇〇〇 ◎ 〇 ◎ ◎ 〇 ◎ Measurement time (AVG) 29.0 12.1 10.1 12.6 33.2 9,3 42.4 41.9 10,2 28.5 Measurement time (R) 23.3 3.6 1.9 2.3 26.2 1.2 25.7 28.6 1.5 22.5 *High concentration dyeing of Example 4 Slip agent

[Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Composition of high-concentration dyeing ingredients Resin A (5013) Resin B1 (5010) 100 Resin B2 (TM) 100 TgCC) 67 110 Composition of molded article Resin A 100 100 100 High Concentration dyeing ingredients 5 5 0 Evaluation example Gel rate 5 1 1 Spray mark ◎ XX Metering time (AVG) &gt; 60 8.8 8.6 Metering time (R) - 0.9 1.9 The metering time of Comparative Example 1 averaged over 60 seconds, the longest The difference between the measurement time and the shortest measurement time cannot be measured. In contrast, Examples 1 to 10 of 28

2254-10158-PF 200932476 The measurement time is all within 60 seconds, and the difference between the longest measurement time and the shortest measurement time is only 28.6 seconds even if it is the longest. Therefore, by using a low-molecular-weight cyclic olefin-based resin and a cyclic olefin resin in a high-concentration dyeing, the productivity of the injection-molded article is improved. In particular, in Examples 2 to 4, 6, and 9, the average measurement time is very short, and since the difference between the longest measurement time and the shortest measurement time is also very short, the productivity can be improved and the injection molding can be obtained. The quality stability of the product.

In Comparative Examples 2 and 3 in which the low molecular weight cyclic olefin-based resin was not used at all, the spray marks and insolubles (gels) of many (10) to # often were used. In contrast to the fact that the 'm~1() spray mark is small', there is almost no confirmation that the material (coag/r) is obtained by using a high-concentration dyeing ingredient containing a low molecular weight cyclic olefin resin. The appearance characteristics of the molded article are lowered. [Simple diagram description] None [Main component symbol description] None

2254-10158-PF 29

Claims (1)

200932476 X. Patent application scope: 1. A method for producing an injection molded article, which uses a cyclic olefin tree stalk and a low molecular weight ring having a number average molecular weight of 1 () or less: fat, which will contain the above ring The high-concentration dyeing ingredients of the olefin-based resin and the low-molecular-weight cyclic hydrocarbon-based resin and the step of dry-closing the above-mentioned cyclic thin-smoke-type resin are injection-molded. The method for producing an injection-molded article according to claim 1, wherein the high-concentration dyeing ingredient is a content of the cyclic thin-smoke resin of 20% by mass to 95% by mass; the above-mentioned low molecular weight The high-concentration dyeing ingredient having a content of the ring-shaped flue-cured resin of 5% by mass to 8% by mass, and the step of drying and mixing is the mass portion of the above-mentioned cyclic olefin-based resin ι〇〇, from 5 parts by mass to 1〇 The high-concentration dyeing ingredients of the 〇 mass section are mixed. A high-concentration dyeing ingredient for use in a method for producing an injection-molded article according to the above aspect of the invention, wherein the content of the cyclic olefin-based resin is from 20% by mass to 95% by mass; The content of the olefin-based resin is 5% by mass to 3% by mass. 4. The high-concentration dyeing composition according to claim 3, wherein the content of the low molecular weight cyclic olefin resin is from 1% by mass to 7% by mass. 5_ A high-concentration dyeing ingredient as described in claim 3, wherein the glass transition temperature is 100 ° C or less. 2254-10158-PF 30 200932476 VII. Designated representative map: (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: No 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: 2254-10158-PF