WO2001072870A1 - Molded norbornene resin and process for producing the same - Google Patents

Abstract

A colorless norbornene resin molding capable of being brightly colored in any desired tone; and a process for producing the norbornene resin molding. The colorless norbornene resin molding is obtained by polymerizing a norbornene monomer containing a polymeric modifier by bulk polymerization in the presence of a ruthenium complex catalyst. Compared to norbornene resin moldings obtained by conventionally known processes, this norbornene resin molding has markedly improved material properties due to the addition of the polymeric modifier. Since the molding is colorless, it is extremely useful in the field of optical materials, etc. Colored moldings obtained therefrom have the effect of having a bright color tone and an excellent appearance.

Description

 Description Norporene resin molded article and method of manufacturing the same Technical field

 The present invention relates to a norpolene-based resin molded article and a method for producing the same, and more particularly, to a norpolene-based resin molded article obtained by subjecting a norbornene-based monomer to bulk polymerization in the presence of a ruthenium complex catalyst and a method for producing the same. Background technology

 It has been known that elastomers, soft resins and hard resins at room temperature can be obtained by ring-opening polymerization polymerization of norbornene monomers. Used in the manufacture of goods.

 It is also known that various additives and auxiliaries are added to a reaction solution containing a monomer when a norbornene-based monomer is subjected to ring-opening polymerization polymerization in a bulk to produce a molded article. For example, Japanese Patent Application Laid-Open No. 58-12913 discloses that one reactant stream containing a metathesis catalyst system catalyst and the other reactant stream containing a metathesis catalyst system activator. In a method for producing a thermosetting polymer, a reaction mixture is prepared by combining reactant streams, and the reaction mixture is injected into a mold for polymerization, an elastomer is added to at least one of the reactant streams. Is described.

 The catalyst system disclosed in this publication consists of a tungsten-containing compound (catalyst) and an alkylaluminum halide (activator). The disclosed monomer is dicyclopentene, and the reactant stream containing them is Two purposes for adding the elastomer are indicated. One is to adjust the viscosity of the reaction mixture from about 300 to about 1000 cP with an elastomer. Another object is to increase the impact strength of the polymer by a factor of 5 to 10 by adding from about 5 to about 10% by weight of an elastomer, based on the weight of the polymer.

In addition, JP-A-2-28214, JP-A-2-214746, JP-A-5-112633, etc. disclose a colorant (pigment, dye) in the reaction solution. How to add and color Has been proposed. The purpose of adding the colorant is to bulk polymerize norpolene-based monomers in the presence of a catalyst system composed of a compound catalyst such as molybdenum or tungsten and a co-catalyst such as alkylaluminum halide. The resulting molded article usually has a yellow or brown color tone derived from the catalyst, and is for hiding the ground color and improving the appearance. When design is particularly required, it is common practice to add a white pigment to the reaction solution to produce a molded product, adjust the background color to colorless, and then apply any paint. .

 However, it has been difficult to impart a vivid color tone even if an attempt is made to add a coloring agent to the reaction solution to which the elastomer has been added to cause coloring. In addition, when white pigment is added to the reaction liquid for coating after molding, the pigment is liable to settle, and there is a problem that pipes and nozzles for supplying the reaction liquid are easily clogged.

 By the way, molybdenum-based or tandatin-based catalysts have been used as metathesis polymerization catalysts, but recently ruthenium or osmium has been used as a new catalyst that is not easily affected by deactivated components such as moisture and oxygen. Complex compounds are receiving attention. For example, Japanese Unexamined Patent Application Publication No. Hei 9-151 828, Japanese Unexamined Patent Application Publication No. Hei 10-509881, Japanese Unexamined Patent Publication No. Hei 10-80933, Japanese Unexamined Patent Publication No. Hei 10-338 Nos. 739, WO97 / 14738, WO99Z114454, etc. disclose ruthenium or osmium metal carbene complex compounds having various ligands. Have been reported.

 These documents also disclose that various known auxiliaries may be contained in the reaction solution when the norbornene-based monomer is subjected to methenic polymerization. For example, an elastomer or a thermoplastic resin such as polybutadiene, polyisoprene, polystyrene, or polynorbornene is described as a viscosity modifier.

Further, Japanese Patent Application Laid-Open No. 11-322,953 discloses that at least two liquids, a first liquid containing a norbornene-type cycloolefin and a second liquid containing a metathesis polymerization catalyst, are mixed in a liquid flow. Meanwhile, a method for producing a crosslinked polymer that is introduced into a molding die and cured is proposed. Here, additives such as antioxidants, fillers, modifiers, mold release agents, light stabilizers, and flame retardants are added as optional components to improve the physical properties, appearance, and workability of the polymer. Or, it may be contained in the second liquid, and the third liquid may contain a coloring agent or a reaction modifier. Elast as the modifier Rubber, natural rubber, butadiene rubber, polymethyl methacrylate, polyvinyl acetate, polystyrene and the like. Colorants include inorganic pigments such as titanium dioxide, cobalt blue, cadmium yellow, carbon black, and aniline. Organic pigments such as black, fluorinated cysteine, and quinacdrine are exemplified.

 However, according to the findings of the present inventors, the ruthenium complex catalyst, the reaction regulator and the polymerization (molding) conditions disclosed in the above-mentioned Japanese Patent Application Laid-Open No. H11-322953 are employed to When bulk polymerization of norbornene-based monomers to which various modifiers are added is performed, the rise in temperature (temperature rise rate) due to the heat of polymerization is slow, so that the microphase of the modifier phase and the norbornene-based resin phase in the obtained polymer is obtained. The separation structure became large and the polymer became significantly white, and the effect of improving the physical properties of the resin by adding a modifier was hardly recognized. Also, even if a colorant is added to the reaction liquid or a coating is applied after molding using a reaction liquid to which a white pigment is added, it has been difficult to impart a vivid color tone to the molded product.

 As described above, norbornene-based resin molded products have various quality requirements such as improvement of physical properties, improvement of appearance and design, and addition of transparency such as skeleton specifications. Methods to achieve industrial advantage have not yet been established.

 The present invention has been made in view of such circumstances and problems, and is a colorless norbornene-based resin obtained by subjecting a norbornene-based monomer containing a polymer modifier to bulk polymerization in the presence of a ruthenium complex catalyst. The primary purpose is to provide molded articles. Secondly, the present invention relates to such norbornene-based resin molded articles, which are colorless and extremely excellent in transparency, exhibit a remarkable effect of improving the physical properties by adding a polymer modifier, and obtain titanium white pigment and the like. An object of the present invention is to provide a colorless and pure white molded article even if not used, and a molded article which is vividly colored in an arbitrary color tone without using a titanium white pigment or the like. Furthermore, the third object of the present invention is to provide a method for industrially and advantageously producing the norbornene-based resin molded product of the present invention. Disclosure of the invention

In order to achieve the above object, the present inventors have prepared various types of ruthenium complex catalysts in the presence of a ruthenium complex catalyst. We conducted intensive studies on bulk polymerization of norbornene-based monomers to which the above polymer modifier was added. As a result, by adopting specific polymerization (molding) conditions, it is possible to obtain a colorless norporene-based resin molded article, and by an industrially extremely simple method of appropriately selecting a polymer modifier. The polymer modifier phase has a remarkable effect of improving physical properties by being finely dispersed in the resin phase.Moreover, the ground color is colorless and a vivid color tone can be obtained by painting or adding a colorant without using white pigment. The present inventors have found that a molded article that can be imparted or a colorless and transparent molded article having a skeleton specification capable of imparting an arbitrary color tone can be separately formed, and the present invention has been completed.

 Thus, the present invention firstly provides a colorless norpolenene-based resin molded product obtained by bulk polymerization of a norpollene-based monomer containing a polymer modifier in the presence of a ruthenium complex catalyst.

The molded article of the present invention is characterized in that (a) the polymer modifier is selected from the group A (a polymer having a butadiene monomer unit, a styrene-based resin, a thermoplastic norbornene-based resin, and a thermoplastic saturated norportene-based resin). Or a molded article of two or more kinds and having a total light transmittance (thickness of 4 mm) of 80% or more; (b) the polymer modifier is group B (one unit of ethylene monomer; A polymer having at least one monomer unit selected from a monomer unit, an isobutylene monomer unit and an isoprene monomer unit), and an Izod impact value of at least 30 kgc mZ cm ² , and bending strength 5 kg / mm ² or more in a molded article, or, the Roh Ruborunen monomer containing one or more polymeric modifier and a coloring agent selected from (c) the group B, Ruteni Obtained by bulk polymerization in the presence of no catalyst, preferably a molded article formed by colored with no colorant using white color pigment. Further, the molded article of the present invention is more preferably a molded article obtained by using, as the ruthenium complex catalyst, a catalyst in which at least one heteroatom-containing carbene compound is coordinated with ruthenium. It is more preferable that the molded article is obtained by a catalyst obtained by coordinating an imidazolidin-2-ylidene compound or a 4-imidazoline-12- ^ flidene compound having a substituent at the 1,3-position. Secondly, the present invention provides bulk polymerization of a norporene-based monomer containing a polymer modifier in the presence of a ruthenium complex catalyst at a maximum temperature rise rate of 20 ° CZ seconds or more during polymerization. And a method for producing a colorless norbornene-based resin molded product. The ruthenium complex catalyst to be used is preferably a catalyst in which at least one hetero atom-containing carbene compound is coordinated with ruthenium. A catalyst in which a lysine-1-ylidene compound or a 4-imidazoline-2-ylidene compound is coordinated is more preferable. Thirdly, the present invention provides a method for performing bulk polymerization of a norpoleneene-based monomer containing a polymer modifier in the presence of a ruthenium complex catalyst in which at least one heteroatom-containing carbene compound is coordinated with ruthenium. The present invention provides a method for producing a colorless norportene resin molded article characterized by the following. As the hetero atom-containing carbene compound, an imidazolidin-1-ylidene compound or a 41-imidazoline-2-ylidene compound having a substituent at the 1,3-position is preferable. BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a diagram showing a temperature rise curve during the polymerization reaction of Example 1 and Comparative Example 1. The vertical axis shows the internal temperature (° C) of the polymer, and the horizontal axis shows the reaction time (second). The sharply rising curve in the figure is the measurement result of Example 1, and the gentle curve is the measurement result of Comparative Example 1. BEST MODE FOR CARRYING OUT THE INVENTION

 (Ruthenium complex catalyst)

The catalyst used in the present invention is a ruthenium complex catalyst, preferably a ruthenium complex compound in which at least one heteroatom-containing carbene compound is coordinated with ruthenium. For example, a complex compound represented by the following formula 1 or formula 2 may be mentioned.

Two

(Wherein, RR ² are each independently a hydrogen atom or a (halogen atom, SansoHara child, nitrogen atom, sulfur atom, - which may contain a phosphorus atom or a silicon atom) (: ₂ hydrocarbon groups. X ¹ and X ² each independently represent any anionic ligand; L ¹ represents a hetero atom-containing carbene compound; L ² represents a hetero atom-containing carbene compound or any neutral And 2, 3, 4, 5, or 6 of R ¹ , R ² , X ¹ , X ² , L ¹ and are bonded to each other to form a polydentate ligand. May be formed.)

In the above formulas 1 and 2, RR ² is, for example, a hydrogen atom, C ₂ -C ₂ . An alkenyl group, a C ₂ -C _{2 Q} alkynyl group, a _{(2 ()} alkyl group, an aryl group which may have a substituent, a carbonyl group, and a C ₂ -C ₂ group. Arukeniruokishi group, C ₂ ~C _2. Alkynyloxy group, aryloxy group optionally having substituent (s), C _2- (: _2Q alkoxycarbonyl group, (^ ~ (^. Alkylthio group, arylthio group optionally having substituent (s)) , C, -C _2. alkylsulfonyl group, Ci~C _2. alkyl sulfinyl group and the like.

 Examples of the substituent of the aryl group, aryloxy group and arylthio group include a nitro group; a halogen atom such as fluorine, chlorine and bromine; an alkyl group such as a methyl group and an ethyl group; a methoxy group and an ethoxy group. Alkoxy group; and the like. Further, these groups may have the same or different plural substituents.

L ¹ represents a heteroatom-containing carbene compound, and L ² represents a heteroatom-containing carbene compound or any neutral electron-donating compound.

Here, examples of the hetero atom include an N, 〇, P, S, As, Se atom and the like. Among them, N, 0, P, S atoms and the like are preferable for obtaining a stable carbene compound, and N atoms are particularly preferable. A carbene compound is a general term for a compound having a methylene free group in a molecule.

> C: has an uncharged divalent carbon atom represented by). Generally, carbene exists as an unstable intermediate generated during the reaction, but when it has a hetero atom, it becomes a relatively stable carbene compound.

 Examples of such a heteroatom-containing carbene compound include compounds represented by the following formula 3 or 4.

3 4 above formulas, R ^3, R ⁴ are each independently a hydrogen atom or a (halogen atom, oxygen radicals, nitrogen atom, sulfur atom, phosphorus atom, a silicon atom) may include - (: _2. Represents a hydrocarbon group.

The R ³ and R ⁴ are, for example, Alkyl group, C ₂ ~C _2. Alkenyl group, C ₂ ~C _2. Examples thereof include an alkynyl group, a C ₃ -C ₈ cycloalkyl group which may have a substituent, and an aryl group which may have a substituent.

 Specific examples of the above formula 3 include 1,3-diisopropylimidazolidin-2— ^ 2lidene, 1,3-dicyclohexylimidazolidine-2—ylidene, 1,3-diphenylimidazolidin —2— ^ Periden, 1,3-di (methylphenyl) imidazole, 1,3-di (methylnaphthyl) imidazolidin-2, -ylidene, 1,3-dimesitylimidazolidin_2_ylidene, 1,3-di Adamantyl imidazolidine-2-ylidene; 1,3,4,5-tetramethylimidazolidine-2 ^^ lidene;

Specific examples of the above formula 4 include 1,3-diisopropyl_4_imidazoline-l-2 peridene, 1,3-dicyclohexyl-4- imidazoline-12-ylidene, and 1,3-diphenyl-2-imidazoline. 2 periden, 1,3-di (methylphenyl) — 4-imidazoline— 2 —ylidene, 1,3-di (methylnaphthyl) —4 T / JP01 / 02776

—Imidazoline-1—Ilidene, 1,3-dimesityl—4—Imidazoline-1—2-ylidene, 1,3-Diadamantyl—4-imidazoline—2-Ilidene, 1,3,4,5-tetramethyl-4-imidazoline-1— Ilidene, 1,3,4,5-tetratetraphenyl 41-imidazoline-2-ylidene, and the like.

 Further, in addition to the compounds represented by the formulas 3 and 4, 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazo-1-yl Ridene, 3- (2,6-diisopropylphenyl) -2,3,4,5-tetrahydrothiazole-2-ylidene, 1,3-dicyclohexylhexahydropyrimidine-2-ylidene, N, N, N ', Ν'-tetraisopropylformamidinylidene, 1,3,4-triphenyl-1,4,5-dihydro-1H—1,2,4-triazole_5— ^ periden, 3— (2,6— Hetero atom-containing carbene compounds such as diisopropylphenyl) -2,3 dihydrothiazole-2-ylidene.

 As the hetero atom-containing carbene compound, a cyclic compound in which a hetero atom adjacent to the carbene has a bulky substituent is preferable. Specific examples thereof include 1,3-diisopropylimidazolidine-2_ylidene, 1,3-dicyclohexylimidazolidine-1-pyridene, 1,3-di (methylphenyl) imidazolidine-2-ylidene, 1,3-di (methylnaphthyl) imidazolidine—2-ylidene, 1,3 dimesityl imidazolidine—2-ylidene, 1,3-diadamantyl imidazolidine_2_ylidene, 1,3-diphene 1,3-disubstituted imidazolidinylidene carbene compounds such as diimidazolidin_2-ylidene and 1,3,4,5-tetraphenylimidazolidin-12-ylidene;

1,3-diisopropyl—4-midazoline—2-peridene, 1,3_dicyclohexyl—4-imidazoline—1—2—ylidene, 1,3— (dimethylphenyl) —1,4—imidazoline—2—ylidene, 1, 3-di (methylnaphthyl) -14-imidazoline-1-2-ylidene, 1,3-dimesityl-4 _imidazoline-2 -ylidene, 1,3-diadamantyl-4-imidazoline_2-ylidene, 1,3-diph 1,3-disubstituted imidazolinylidene carbohydrates such as phenyl-4-imidazoline-2 _ylidene, 1,3,4,5-tetraphenyl-2-yl 4-imidazoline-2-ylidene Compound; and the like.

As the anionic (anionic) ligands X ¹ and X ^{2 in the} above formulas 1 and 2, any ligand may be used as long as it has a negative charge when separated from the central metal. Further, XX ² may be combined to form a bidentate or higher anionic ligand. Specific examples of X ¹ and X ² include a halogen atom such as F, Br, C and I, a hydrogen atom, an OH group, a substituted aryl group, an alkenyl group, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group. , Alkoxycarbonyl, carboxyl, alkyl or arylsulfonate, alkylthio, alkenylthio, arylthio, alkylsulfonyl, alkylsulfinyl, acetylacetonato, diketonate, substituted cyclopentenyl, etc. Can be mentioned. Of these, a halogen atom is preferred, and a chlorine atom is more preferred.

The neutral electron donating compound may be any ligand as long as it is a ligand having a neutral charge when separated from the central metal, that is, a Lewis base. Specific examples thereof include oxygen, water, carbonyl, amines, pyridines, ethers, nitrils, esters, phosphines, phosphinites, phosphites, stibines, sulfoxides, thioethers, and amides. , Aromatic compounds, cyclic diolefins, olefins, isocyanides, thiocyanates, etc. Of these, phosphines are preferred, and trialkylphosphines and triarylphosphines are more preferred. Examples of the trialkylphosphine include trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine, triisobutylphosphine, tri (sec-butyl) phosphine, tri (t-butyl) phosphine, tripentylphosphine, and the like. Trihexylphosphine, tricyclopropylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, tri (2-methylcyclohexyl) phosphine, tri (3-methylcyclohexyl) phosphine, tri (3-methylcyclohexyl) phosphine , Tri (2,4-dimethylcyclohexyl) phosphine, tri (2,4,6-trimethylcyclohexyl) phosphine, etc. No.

 The triarylphosphines include triphenylphosphine, tri (2-methylphenyl) phosphine, tri (4-methylphenyl) phosphine, tri (3-methylphenylphosphine), tri (4-methylphenyl) phosphine, tri (2 , 4-Dimethylphenyl) phosphine, tri (2,4,6-trimethylphenyl) phosphine, dimethylphenylphosphine, getylphenylphosphine, diisopropylphenylphosphine, dibutylphenylphosphine, methyldiphenylphosphine And ethyl diphenyl phosphine, propyl diphenyl phosphine, butyl diphenyl phosphine and the like.

 Examples of the complex compound represented by the formula 1 include (1,3-dicyclohexylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dicyclohexyl) 4-Imidazoline-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dicyclohexylimidazolidin-2-ylidene) (triphenylphosphine) benzylidene ruthenium dichloride, (1,3-) Dicyclohexyl-1-4-imidazoline_2-peridene) (triphenylphosphine) benzylidene ruthenium dichloride, (1,3-dimesitylimidazolidine-12-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride Do, (1, 3—dimesityl imida Lysine-1 -ylidene) (triphenylphosphine) benzylidene ruthenium dichloride, (1,3-dimesityl-4 -imidazolysine-2 -ylidene) (tricyclohexylphosphine) benzylidene lutemidine dichloride, (1,3-dimesityl) 4 _ imidazolidine-1-2-ylidene) (triphenylphosphine) benzylidene ruthenium dichloride,

[1,3-di (2-methylphenyl) imidazolidine-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (3-methylphenyl) imidazolidine-1-ylidene] (tricyclohexylphosphine) Benzylidene ruthenium dichloride, [1,3-di (4-methylphenyl) imidazolidin-12-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (2-methylphenyl) Imida 1/02776 Zolidine-1-ylidene] (triphenylphosphine) benzylidene ruthenium dichloride, [1,3-di (3-methylphenyl) imidazolidine_2_ylidene] (triphenylphosphine) benzylidene ruthenium dichloride, [1, 3—di (4-methylphenyl) imidazolidine—2-ylidene] (triphenylphosphine) benzylidene ruthenium dichloride,

 [1,3-Di (2-methylphenyl) —4-imidazoline-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3—di (3-methylphenyl) —4-imidazoline—2— [Ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (4-methylphenyl) -4-1-imidazoline-12-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3 —Di (2-methylphenyl) 1-41-imidazoline-1-2-ylidene] (triphenylphosphine) benzylidene ruthenium dichloride, [1,3-di (3-methylphenyl) —4-imidazoline—2-ylidene ] (Triphenylphosphine) benzylidene ruthenium dichloride, [1,3-di (4-methylphenyl) - 4-imidazolin - 2-I isopropylidene (triphenyl phosphine) benzylidene ruthenium dichloride,

 [1,3-Di (2-methyl-1-naphthyl) imidazolidine-1-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (4-methyl-1-naphthyl) imidazolidine 1 2-Ilidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (8-methyl-1 naphthyl) imidazolidine— 2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (1-methyl-2-naphthyl) imidazolidin-1-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (4-methyl-2-naphthyl) imidazo Lysine-1 2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1 3-di (8-methyl-2-naphthyl) imidazolidine one 2- ylidene] (the tricyclo hexyl phosphine) Benjiri Den dichloride,

[1, 3-di (2-methyl-1 naphthyl) 1-41 imidazoline-1 2-iride T / JP01 / 02776] (Tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (4-methyl-1-naphthyl) —4-imidazoline-1-ylidene] (tricyclohexylphosphine) benzylidene Ruthenium dichloride, [1,3-di (8_methyl_1-naphthyl) —4-imidazoline-1-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (1-methyl) — 2 — naphthyl) 1-41-imidazoline— 1—2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (4-methyl-1-naphthyl) 1-4—imidazoline—2—ylidene ] (Tricyclohexylphosphine) benzylidene ruthenium dichloride, [1,3-di (8-methyl-2-naphthyl) -4-1-imi Dazoline—2-ylidene]

(Silphosphine) benzylidene ruthenium dichloride, (1, 34, 5-tetramethylphenyl 4-imidazoline-2-ylidene)

Benzylidene ruthenium dichloride, (1,3-dicyclohexylhexahydropyrimidine-12-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride and other heteroatom-containing carbene compounds and neutral electrons A ruthenium complex compound coordinated with a donating compound;

Bis (1,3-diisopropylimidazolidin-2—ylidene) benzylidene ruthenium dichloride, bis (1,3—dicyclohexylimidazolidine-1-2-ylidene) benzylidene ruthenium dichloride, bis (1,3-diisopropyl mono) 4 ^^ Γmidazoline-2-ylidene) benzylidene ruthenium dichloride, bis (1,3-dicyclohexyl-4 Γ midazoline 1-2-ylidene) benzylidene ruthenium dichloride, bis (1, 3-dimesitylimidazo) Lysine-2-^ f Ridene) Benzylidene ruthenium dichloride, bis (1,3-dimesityl 4- imidazoline-2-^ periden) Ruthenium complex coordinated with two heteroatom-containing carbene compounds such as benzylidene ruthenium dichloride Compounds; and the like. Examples of the complex compound represented by the above formula 2 include (1,3-dicyclohexylimidazolidin-2-ylidene) (tricyclohexylphosphine) phenylidene ruthenium dichloride, and (1,3-dimesylidene). Tylimidazolidine-2-ylidene) (tricyclohexylphosphine) t-butylvinylidene lutene Mudichloride, 1,3-dicyclohexyl 4-imidazoline-2-ylidene) (tricyclohexylphosphine) phenylvinylidene ruthenium dichloride, (1,3-dimesityl-41-imidazoline-2-ylidene) (tricyclohexyl) Ruphosphine) phenylene bilidene ruthenium dichloride,

 [1,3-di (methylphenyl) imidazolidine-1-ylidene] (tricyclohexylphosphine) t-butylvinylidene ruthenium dichloride, [1,3-di (2-methyl-1-naphthyl) imidazolidine—2 _ [Ilidene] (tricyclohexylphosphine) phenylvinylidene ruthenium dichloride, [1,3-di (4-methylphenyl) -4-4-imidazoline-2-2-ylidene] (tricyclohexylphosphine) t-butylvinylidene Ruthenium dichloride, [1,3-di (4-methyl-1-naphthyl) -1-4-imidazoline-2-ylidene] (trisic hexylphosphine) phenylvinylidene ruthenium dichloride, (1,3 , 4,5-Tetraphenylimidazolidin-2-ylidene) (tricyclohexylphosphine) t-butylvinylidene ruthenium Heteroatom-containing carbene compounds such as dichloride, (1,3-dicyclohexylhexahydropyrimidine-12-ylidene) (tricyclohexylphosphine), phenylvinylidene ruthenium dichloride, and neutral electron-donating compounds A ruthenium complex compound coordinated with

 Bis (1,3-diisopropylimidazolidin-2-ylidene) phenylvinylidene ruthenium dichloride, bis (1,3-dicyclohexylimidamidolidine 1-2_ylidene) t-butylvinylidene ruthenium dichloride, bis ( 1,3-diisopropyl-1-4-imidazoline-2-imidene) t-Butylvinylidene lute dimethyldichloride, bis (1,3-dicyclohexyl-14-imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride And a ruthenium complex compound in which two heteroatom-containing carbene compounds are coordinated. These ruthenium complex compounds can be used alone or in combination of two or more.

 Further, in the present invention, the ruthenium complex compound may be

[(p-cymene) cycloruthenium], di-chlorobis [[(p-cymene) chloroosmium], dichloro (pentamethylcyclopenenyl) rhodium A dinuclear ruthenium-carbene complex compound obtained by reacting with a dinuclear metal complex such as ima can also be used.

 These ruthenium complex compounds are described, for example, in Org. Lett., 1999, Vol. 1, page 953, and Terahedron. Lett., 1999, Vol. 40, page 2247. It can be manufactured according to a given method.

 Further, as the metathesis polymerization catalyst for cyclic olefins, a conventionally known ruthenium complex catalyst can be used. For example, a ruthenium or osmium complex catalyst having various ligands described in W097Z29135, JP-A-9-512828, JP-A-10-5088991, and JP-A-11-322953 is used. Can be.

 The amount of the ruthenium complex compound used, that is, the ratio of the polymerization catalyst to the norbornene-based monomer, is usually 1: 2,000 to: L: as the molar ratio of the metal ruthenium / norbornene-based monomer in the catalyst. 2,000,000, preferably 1: 5,000 to 1,000,000, more preferably 1: 10,000 to 1: 500,000.

 The ruthenium complex catalyst can be used by dissolving it in a small amount of an inert solvent, if necessary. Examples of such a solvent include linear aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; cyclopentane, cyclohexane, methyl cyclohexane, dimethylcyclohexane, trimethylcyclohexane, Alicyclic hydrocarbons such as ethyl cyclohexane, getyl cyclohexane, decahydronaphthylene, bicycloheptane, tricyclodecane, hexahydroindenecyclohexane, and cyclooctane; aromatic hydrocarbons such as benzene, toluene, and xylene Nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, and acetonitrile; and solvents such as ethers such as getyl ether and tetrahydrofuran. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, which are industrially widely used, are preferred.

When additives such as an antioxidant and a plasticizer are in a liquid state, they can be used as a solvent for dissolving the catalyst. Examples of liquid antioxidants include 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-4-methylphenol And 2,6-di-t_butyl-4_nonylphenol. (Norbornene monomer)

 The monomer that undergoes ring-opening polymerization in the presence of the above-mentioned catalyst is a norbornene-based monomer having a norbornene ring structure. Examples of such norbornene-based monomers include substituted and unsubstituted bicyclic or tricyclic or higher polycyclic norbornenes.

 Specific examples thereof include norbornene, norbornane, methyl norbornene, dimethyl norbornene, ethyl norbornene, chlorinated norbornene, ethylidene norbornene, chloromethyl norbornene, trimethylsilyl norbornene, phenyl norbornene, cyano norbornene, disyano norbornene, and methoxy carbonyl. Bicyclic norbornenes such as norbornene, pyridyl norbornene, nadic anhydride, nadimide;

Tricyclic norbornenes such as phenyl, alkylidene, aryl substituted, etc .; Tetracyclic norbornenes such as dimethanohexahydronaphthalene, dimethanohexayl hydronaphthylene and their alkyl, alkenyl, alkylidene, aryl substituted, etc .; Hexacyclic norbornenes such as hexacyclohepdecene; dinorbornene; compounds in which two norbornene rings are bonded by a hydrocarbon chain or an ester group; alkyl- and aryl-substituted products thereof And a compound containing a norbornene ring. Further, a monocyclic cycloolefin such as cyclobutene, cyclopentene, cyclooctene, cyclododecene, or a derivative thereof having a substituent may be copolymerized with the norbornene-based monomer.

 The norbornene-based monomers may be used alone or in combination of two or more, but the use of two or more is preferred. When two or more types are used, a resin having various physical properties can be obtained by appropriately combining a monomer having one double bond to be a thermoplastic resin and a monomer having a plurality of double bonds to be a thermosetting resin. Can be obtained. Also, compared with the case where the monomer is used alone, when two or more kinds are used in combination, there is an advantage that a monomer having a high freezing point temperature can be handled as a liquid due to a freezing point drop.

(Polymer modifier) The polymer modifier used in the present invention is not particularly limited as long as it is soluble in a norpoleneene-based monomer. Examples of such a polymer modifier include natural rubber, butyl rubber, polybutadiene, polyisoprene, polyisobutylene, ethylene-propylene copolymer, ethylene-propylene-diene terpolymer (EPDM), ethylene-vinyl alcohol copolymer ( EVA), styrene-based block copolymer, styrene-butadiene rubber (SBR), norbornene rubber, polystyrene, thermoplastic norbornene-based resin, thermoplastic saturated norbornene-based resin, and the like.

 The styrene-based block copolymer is not particularly limited as long as it is a block copolymer having at least one styrene block. Specific examples thereof include styrene-butadiene block copolymer (SB), styrene-isoprene block copolymer (SI), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer. And styrene-butadiene-isoprene-styrene block copolymer (SBIS).

 Further, a hydride obtained by hydrogenating the styrene-based block copolymer by a known method may be used. Specific examples thereof include hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, and hydrogenated styrene-isoprene-styrene block copolymer. And a hydrogenated styrene-butadiene-isoprene-styrene block copolymer. In the hydride, the phenyl group itself of the polystyrene block is not hydrogenated, and only the polyisoprene block / polybutylene block is hydrogenated.

 As such a styrenic block copolymer, those produced industrially and commercially available may be used. For example, they are sold under the names "Quintac" of ZEON CORPORATION, "TUFPLEN" and "TUFTECH" of Asahi Kasei Corporation, "Clayton" of Shell, "Septon" of Kuraray Co., Ltd. Can be selected and used as appropriate.

In the present invention, depending on the purpose of use of the molded article, the polymer modification shown in the following Group A or Group B A filler is preferably used.

 Polymers having one unit such as polybutadiene, styrene-butadiene rubber, styrene-butadiene-styrene block copolymer, etc .; polymers having one unit; polystyrene, poly (α-methylstyrene), poly Styrene resins such as (（-methylstyrene) and poly (ρ-promostyrene); thermoplastic norbornene resins; thermoplastic saturated norbornene resins.

 Polymers having one unit of ethylene monomer such as ethylene-propylene-diene copolymer, ethylene-propylene copolymer, ethylene-vinyl alcohol copolymer, etc .; Α-olefins such as butene copolymers, propylene-11-hexene copolymers, propylene-11-octene copolymers, poly (1-butene), poly (1-1-hexene) Monoolefin having a double bond) Polymer having monomer units; Polymer having isobutylene monomer units such as polyisobutylene, isobutylene-isoprene copolymer, styrene-isobutylene-styrene copolymer; polyisoprene, styrene-isoprene block copolymer Polymer, styrene-isoprene-styrene And polymers having isoprene monomer units such as block copolymerization.

 The content of the butadiene monomer unit, the ethylene monomer unit, the α-olefin monomer unit, the isobutylene monomer unit, and the isoprene monomer unit in the groups Α and 上 記 is not particularly limited, but is usually 5% by weight or more, preferably. Is at least 10% by weight, more preferably at least 20% by weight. When one unit of these monomers is copolymerized with another comonomer, the form of the copolymerization is not particularly limited. For example, it may be a block copolymer or a random copolymer.

The group II polymer modifier functions as a viscosity modifier for the norbornene-based monomer. Also, by adding them to a norbornene-based monomer and performing bulk polymerization, a norbornene-based resin molded article having excellent colorlessness and transparency can be obtained. The test method for the total light transmittance of the transparent plastic in the visible region is specified in JISK 7361-1. The total light transmittance of the molded article (4 mm in thickness) of the present invention is usually at least 80%, preferably at least 85%. Power The molded product is preferably used as it is, or by coloring it with a coloring agent as described below at the time of molding, as a molded product of a skeleton specification such as an OA equipment housing. The group B polymer modifier functions as a viscosity modifier for the norponene-based monomer. Moreover, by their that you to bulk polymerization by the additional inclusion in the norbornene-based monomer, the Izod impact value of 3 0 KGC in mZ cm ² or more and flexural strength obtain 5 kg ZMM ² or more in a norbornene-based resin molded article Can be. Furthermore, a colorless and pure white norbornene-based resin molded article can be obtained without using a titanium white pigment or the like by incorporating the polymer modifier of Group B into a norbornene-based monomer and performing bulk polymerization. . Furthermore, by using a polymer modifier of Group B and a colorant in combination, it is possible to obtain a vividly colored molded article.

 These polymer modifiers can be used in a wide range from liquids having an average molecular weight of 500 to several thousand to solids of several hundred thousand to several hundred thousand. Further, they may be used alone or in combination of two or more. When two or more members belonging to Group A and Group B are used in combination, it is preferable to select each from the same group.

 The polymer modifier is usually used after previously dissolved in a reaction solution containing a norbornene-based monomer. By dissolving the polymer modifier, if the reaction solution containing the monomer has a low viscosity, the viscosity can be adjusted to an appropriate value. The amount of the polymer modifier used is usually 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 2 to 1 part by weight, based on 100 parts by weight of the obtained norbornene resin. 0 parts by weight. If the amount of the group A is too small, the effect of adjusting the viscosity is reduced, and the reaction liquid is apt to entrap bubbles. If the amount of the group B is too small, the effect of imparting impact resistance is small, and if too large, on the other hand, the viscosity of the reaction solution becomes high and the molding operability becomes poor, and the heat deformation temperature and flexural modulus of the resin become small. Could be.

 (Lump ring-opening polymerization)

The polymerization method for obtaining the norbornene-based resin of the present invention is bulky ring-opening polymerization using a ruthenium complex catalyst. As the ruthenium complex catalyst, a complex obtained by coordinating at least one carbene compound containing ruthenium with ruthenium is preferably used. By using this ruthenium catalyst, a thermosetting resin can be obtained at once from a liquid norbornene-based monomer. This polymerization reaction is rapid Existence of heat generation immediately after the start of polymerization is significantly different from that of a conventionally known production method using a ruthenium complex, that is, a conventional method of performing post-curing using a reaction regulator (delaying agent).

 That is, in the present invention, since the activation energy of the polymerization reaction is 90 kJZmol or more and the temperature dependence of the polymerization reaction rate is large, once the heat generation starts and the temperature rises, the polymerization reaction rate becomes extremely high. As a result, the temperature rise at the time of heat generation (temperature rise curve) becomes steep. The maximum heating rate is usually 20 ° C / sec or more, preferably 30 ° C / sec or more. As described above, since the polymerization reaction proceeds rapidly, the phase separation structure does not become excessively large when the polymer modifier undergoes phase separation in the polymerization process.

 Examples of molding methods that can be used include molding methods such as injection, injection, casting, rotation, centrifugation, extrusion, drawing, injection compression, and hand lay-up. Usually, a mold is used. In particular, a method in which a norbornene-based monomer is polymerized in a bulk in a mold by a resin transfer molding (RTM) method or a reaction injection molding (RIM) method is useful.

 The mold is used to obtain a molded product having a predetermined shape. These methods need only be substantially lumpy and may include a small amount of an inert solvent. In such a method, a molding machine conventionally known as an RTM machine or a RIM machine can be used for mixing a reaction solution or a catalyst solution containing a monomer or a catalyst.

 The RTM machine generally includes a monomer-mixed liquid tank, a catalyst-mixed liquid tank, a metering pump, a mixer, and the like. The metering pump feeds the monomer mixture and the catalyst mixture into the mixer at a volume ratio of 100: 1 to 10: 1, and then pours them into a molding die heated to a predetermined temperature, where they are immediately lumped. A molded article can be obtained by polymerization. As a preferable molding method using an RTM machine, a monomer mixture containing a norbornene-based monomer and a complex catalyst in which at least one carbene compound containing a hetero atom is coordinated with ruthenium are mixed with a small amount of a solvent. A method is provided in which a catalyst-containing solution is prepared by dissolving the components in a solution, and these are mixed and molded.

The RIM machine sends two or more kinds of undiluted reaction solutions to a mixing head, mixes them by means of collision energy, and then injects them into a hot molding die, where they immediately form a massive weight. To obtain a molded article. A preferred molding method using a RIM machine is to divide the norbornene-based monomer into two parts, use a liquid in which a ruthenium complex catalyst is dissolved in a small amount of solvent as the third liquid, and mix these three liquids by collision mixing. There is a method of mixing and molding.

 A particularly preferred molding method of the present invention is to use a mold having a split mold structure, that is, a mold having a core mold and a cavity mold, and injecting the reaction liquid into the voids (cavities) to perform bulk polymerization. is there. The core mold and the cavity mold are formed so as to form voids that match the shape of the target molded product. There is no particular limitation on the shape, material and size of the mold. Since it can be molded at a relatively low temperature and a low pressure using a reaction liquid having a relatively low viscosity, not only a metal mold but also various materials such as various synthetic resins and low melting point alloys can be used.

The temperature of the unreacted solution before it is fed into the cavity is preferably 20 to 80 ° C. The viscosity of the reaction solution can be appropriately adjusted by adjusting the amount of the polymer modifier to be added, but is usually 2 to 1000 cP, preferably 5 to 300 cP at 30. The filling pressure (injection pressure) for filling the reaction stock solution into the cavity is usually 0.1 to 100 kgfZcm ² , preferably 0.2 to 50 kgf / cm ² . If the filling pressure is too low, the transfer surface formed on the inner peripheral surface of the cavity tends to be poorly transferred.If the filling pressure is too high, the rigidity of the mold must be increased, which is economical. Not a target.

The mold temperature is usually room temperature or higher, preferably 40 to 200 ° C, particularly preferably 50 to 30 ° C. The mold clamping pressure is usually in the range of 0.1 to: L 00 kgZcm ² . The polymerization time may be appropriately selected, but is usually 10 seconds to 20 minutes, preferably 5 minutes or less.

When the reaction liquid mixed by the above RTM machine or RIM machine is injected into the cavity of the mold, the bulk polymerization reaction starts immediately and is cured. The polymerization reaction is an exothermic reaction. As the curing time (curing one hour) becomes longer, the temperature of the molded product in the mold gradually decreases, and the molded product obtained by bulk polymerization usually adheres to the core mold. The mold can be opened and the molded body can be released from the mold. The adhesion of the molded product to the core mold controls the molding conditions. It is done by doing. The higher the mold temperature or the longer the cure time, the higher the possibility of sticking to the core mold. If the cure time is short, opening the mold may cause the molded product to adhere to the cavity mold and remain. On the other hand, if the curing time is longer, the molded product will cool and shrink, and will adhere to the core mold. However, even if it adheres to the core mold, if the cure time is too long, shrinkage due to cooling of the molded product will proceed to a considerable extent, so that the air ejector or gold will not be excessively cooled while the molded product is not cooled excessively. It is preferable to remove the mold using a mold removal device provided in the mold.

 (Colorless norpolene resin)

 The norbornene-based resin molded product of the present invention is substantially colorless or colorless and transparent. In general, the colorless or white color of plastics is evaluated by:

The yellowness (YI) is specified in 1:15 of J15. The method of evaluating transparency is as described above.

 When the polynorbornene-based resin of the present invention is obtained using the polymer modifier of Group A, the yellowness (YI) at an optical path length of 4 mm by a transmission method is 10 or less, More preferably, it is 5 or less. The total light transmittance is preferably at least 80%, more preferably at least 85%.

 In the case where the norbornene-based resin of the present invention is obtained using the above-mentioned polymer modifier of Group B, the yellowness measured by a reflection method is 10 or less, more preferably 5 or less.

 In addition to the polymer modifier, the colorant, antioxidant, ultraviolet absorber, filler, flame retardant, cross-linking agent, sliding agent, odorant, etc., in addition to the polymer modifier, are used in the norponene resin of the present invention. By blending various additives such as a filler for reducing weight, a foaming agent, and a whisker for smoothing the surface, the properties of the molded article can be further improved. Usually, these additives are dissolved or dispersed in a norbornene-based monomer in advance in reaction injection molding, mixed with at least one undiluted reaction solution, and then polymerized in a mold.

As the antioxidant, there are various antioxidants for rubbers such as hindered phenol, phosphorus, and amine. These antioxidants can be used alone Good, but it is preferable to use them in combination. The mixing ratio of the antioxidant is usually at least 0.5 part by weight, preferably 1 to 3 parts by weight, per norbornane-based monomer. Further, the antioxidant may be one which can be copolymerized with the monomer, and specific examples thereof include norbornenyl phenols such as 5- (3,5-di-tert-butyl_4-hydroxy) benzyl-2-norbornene. Compounds, etc.

-See 8 3 5 2 2 bulletin).

 Examples of the filler include inorganic fillers such as glass powder, talc, calcium carbonate, mica, and aluminum hydroxide. It is preferable that the filler is surface-treated with a silane coupling agent or the like. The use of iodide or peroxide as a crosslinking agent improves heat resistance.

 (Colored norbornene resin)

 Since the norbornene resin of the present invention is colorless or colorless and transparent, it can be colored to any color by simply adding a coloring agent during bulk polymerization. As a result, a colored norbornene-based resin can be obtained. Colorants that can be used are not particularly limited, but dyes, pigments, and the like are preferably used. Dyes are particularly preferred because they can impart vivid dye colors to norbornene resins. In general, pigments are not dissolved in solvents but are dispersed in fine particles in the base material and have low bonding strength to the base material, whereas dyes are soluble in various solvents and are ionic or hydrogen bonded to the base material. , Van der Waals, covalent bond, etc.

There are various types of dyes, and they may be appropriately selected and used. For example, the Dye Handbook (edited by the Society of Synthetic Organic Chemistry, edited by Showa 49, published by Maruzen Co., Ltd., published on July 20, 1949) shows the structure of nitro dyes, nitroso dyes, and azo dyes. , Ketoimine dye, trifenylmethane dye, xanthene dye, acridine dye, quinoline dye, methine dye, thiazole dye, indamine dye, azine dye, oxazine dye, thiazine dye, sulfide dye, aminoketone dye, anthraquinone dye, indigoid dye, Classified as phthalocyanine dyes. In addition, they are classified into direct dyes, acid dyes, basic dyes, mordant dyes, vat dyes, sulfur dyes, azoitic dyes, reactive dyes, cationic dyes, disperse dyes, oxidative dyes, oil-soluble dyes, etc. . Direct dyes are mostly azo dyes, but phthalocyanine dyes and oxazine dyes Some acid dyes include azo dyes, anthraquinone dyes and triphenylmethane dyes. To classify these various dyes, the Dye Handbook

Dyes are specified by C o l o u r I n d e x number and others.

 Among these, the oil-soluble dye is referred to as Solv ent Dyes, and is preferably used as a colorant for molded articles. It has a wide range of solubility, including those that have high solubility in polar solvents such as alcohol and those that have high solubility in non-polar solvents such as gasoline. Those with a molecular weight are common. Many yellow and red colors have azo dyes, and blue and green have many anthraquinone dyes and phthalocyanine dyes.

 Specific examples of such dyes include oil-soluble dyes, azo solvent yellow 1, 2, anthraquinone solvent blue 11, similar phthalocyanine solvent blue 5, and triarylmethane solvent blue 12. Anthraquinone-based Disperse Blue 3 for disperse dyes, azo-based Disperse Blue 13 for acid dyes, anthraquinone-based Acid Blue 41 for acid dyes, and thiazine-based basic yellow 11 for basic dyes, also basic. BULL 9, Vat Yello IV, a vat dye based on anthraquinone, and BAT BULL 20 as well. Regardless of the type of dye, those that are soluble in norpoleneene-based monomers are preferred. Among them, oil-soluble dyes and disperse dyes, among which oil-soluble dyes that are particularly soluble in hydrocarbon solvents, are particularly preferred because they are easily dissolved in norbornene monomers.

 Examples of the pigment include carbon black, graphite, graphite, iron oxide yellow, titanium dioxide, zinc oxide, trilead tetroxide, lead red, chromium oxide, navy blue, titanium black, and the like.

Such coloring agents such as dyes and pigments may be used alone or in combination of two or more. A variety of colors can be created by using two or more colorants in combination. The coloring agent is added to the reaction solution as it is, or a master batch in which the norbornene monomer is dissolved as high as possible is prepared and added to the reaction solution. Mass-batch-If the batch concentration is 5% or more, preferably 10% or more, it is easy to handle for addition. The amount of the colorant to be added is 0.002 to 3.0 parts, preferably 0.01 to 2.0 parts, per 100 parts of the total amount of the monomers in each reaction solution. Addition amount is necessary Is determined according to the degree of coloring. If the amount is small, the coloring effect is low, and if the amount is too large, it is not economical.

 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to these Examples. In these examples,% and ratio are by weight unless otherwise specified.

 In the following Examples and Comparative Examples, the following abbreviations were used as the polymer modifier and the coloring pigment.

 (Polymer modifier)

 SIS: Styrene-isoprene-styrene rubber (trade name: Quintac 3530 or 3421, manufactured by Nippon Zeon Co., Ltd.)

 EPDM: Ethylene-propylene-gen rubber (trade name: EPT X-301 2P, manufactured by Mitsui Chemicals, Inc.)

 IR: Isoprene rubber (trade name: Nipol I R2200L, manufactured by Nippon Zeon Co., Ltd.)

 SBS: Styrene-butadiene-styrene rubber (trade name: Asaprene, manufactured by Asahi Kasei Corporation)

 BR: Butadiene rubber (trade name: Nipol BR 1220, manufactured by Nippon Zeon Co., Ltd.)

 SBR: Styrene-butadiene rubber (trade name: Nipol NS 320 SB, manufactured by Zeon Honhon)

 PS: Polystyrene (trade name: Suyilon G8259, manufactured by Asahi Kasei Corporation)

 ZNR: Amorphous norporene plastic (trade name: ZNR 1060 R, manufactured by Nippon Zeon Co., Ltd.)

 (Color pigment)

 Blue pigment: (Model number: P—BL—1, manufactured by Dainichi Seika Kogyo Co., Ltd.)

 Yellow pigment: (Model: P-420, manufactured by Dainichi Seika Kogyo Co., Ltd.)

 (Example 1) Flat plate molding and physical property measurement

In a 500 ml eggplant-shaped flask equipped with a magnetic stirrer, 1938, and 316.0 g of dicyclopentene (containing about 10% of cyclopentane trimer) were added. In addition, the mixture was stirred and dissolved at 80 ° C for 2 hours under a nitrogen atmosphere. Thereafter, the pressure was reduced while stirring, and only 0.5 g of a low boiling point component was removed (composition liquid 1).

 Thereafter, the temperature was returned to room temperature, and under a nitrogen atmosphere, benzylidene (1,3-dimesitylilimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride (Org. L et t., 1999, vol. 1, Toluene solution (synthesized based on the description on page 953) in toluene (concentration: 20 mmol, Z liter) was added, stirred, and pumped into a mold.

 Here, the mold is for flat plate molding with dimensions of 4 X 200 X 200 mm, and a U-shaped spacer is sandwiched between a chrome plated iron plate with a heater. The mold temperature was set at 80 ° C on the product side and 60 ° C on the back side. In order to measure the temperature of the resin during the polymerization reaction in the mold, a K-type thermocouple (0.1 mm in diameter, with two wire ends welded to the center of the mold and the center of the thickness) ) Was set.

 After the mixed solution was pumped into the mold, the resin temperature in the mold was measured, the mold was removed 3 minutes after the injection, and the flat plate was removed.

 Thereafter, measurement tests of the glass transition temperature (Tg), flexural strength, flexural modulus, tensile yield strength, Izod impact value, and yellowness (YI) of the flat plate were performed. The glass transition point temperature (Tg) was measured according to JIS K 7121, and the Tig was measured to be Tg. Flexural strength and flexural modulus were measured according to JIS K 7203. The tensile yield strength was measured at a tensile speed of 50 Omm / min using a No. 1 type test piece according to JIS K 7113. The Izod impact value was measured on a No. 2 A test piece according to JIS K 7110. The yellowness was measured by a reflection method.

 (Example 2) Flat plate molding and physical property measurement

 As a catalyst solution, benzylidene (1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride (Terah edr on Lett., 1999, Vol. 40, p. 2247) A plate was obtained in the same manner as in Example 1 except that 1.0 ml of a toluene solution (constituted according to the description) of toluene (concentration 40 mmol Z liter) was used. Physical properties of the obtained plate

(Glass transition temperature (Tg), flexural strength, flexural modulus, tensile yield strength, Izod impact value and yellowness) were measured in the same manner as in Example 1. (Comparative Example 1) Flat plate molding and physical property measurement

 After preparing the composition liquid 1 in the same manner as in Example 1, the temperature was returned to room temperature, and under a nitrogen atmosphere, bis (1,3-dichloro-2-propoxy) aluminum chloride in dicyclopentene solution (0.1 mol Z liter) 2 m 1. Toluene solution of benzylidenebis (tricyclohexylphosphine) ruthenium dichloride (manufactured by Schem Chemical) in toluene (concentration: 0.1 mol Z liter) 1.0 ml was added, stirred and pumped into the mold. .

 Here, the same mold as that of Example 1 was used except that the mold temperature was set at 95 ° C on the product side and 60 ° C on the back side. After the mixed solution was pumped into the mold, a flat plate was obtained in the same manner as in Example 1. The physical properties (glass transition temperature (Tg), flexural strength, flexural modulus, tensile yield strength, Izod impact value and yellowness) of the obtained flat plate were measured in the same manner as in Example 1. In this comparative example, the reason why the mold temperature was higher than in the example and the aluminum compound was added was to increase the reaction rate.

 (Example 3) Flat plate molding and physical property measurement

 A flat plate was obtained in the same manner as in Example 1 except that 6.0 g of EPDM was used. The physical properties (glass transition temperature (Tg), flexural strength, flexural modulus, tensile yield strength, Izod impact value and yellowness) of the obtained flat plate were measured in the same manner as in Example 1.

(Comparative Example 2) Flat plate molding and physical property measurement

 A flat plate was obtained in the same manner as in Comparative Example 1, except that 6.0 g of EPDM was used. The physical properties (glass transition temperature (Tg), flexural strength, flexural modulus, tensile yield strength, Izod impact value and yellowness) of the obtained flat plate were measured in the same manner as in Example 1.

(Example 4) Flat plate molding and physical property measurement

A flat plate was obtained in the same manner as in Example 1 except that 6.0 g of IR was used. The physical properties (glass transition temperature (Tg), flexural strength, flexural modulus, tensile yield strength, Izod impact value, and yellowness) of the obtained flat plate were measured in the same manner as in Example 1. Kinds of the polymer modifier used in Examples 1 to 4 and Comparative Examples 1 and 2, the maximum heating rate during polymerization, and physical properties of the flat plates obtained in Examples 1 to 4 and Comparative Examples 1 and 2 ( Glass transition Table 1 summarizes the measurement results of point temperature (T g), flexural strength, flexural modulus, tensile yield strength, Izod impact value and yellowness. FIG. 1 shows the temperature rise curves during the polymerization reaction of Example 1 and Comparative Example 1. The sharply rising curve in the figure is the measurement result of Example 1, and the gentle curve is the measurement result of Comparative Example 1. First

 As is clear from Table 1 and FIG. 1, in Examples 1 to 4, the maximum heating rate during polymerization was higher than in Comparative Examples 1 and 2, and the physical properties of the obtained resin were further improved. You. Further, the resins (flat plates) of Examples 1 to 4 had extremely low yellowness and were found to be colorless by visual observation. On the other hand, Comparative Examples 1 and 2 had a relatively high yellowness and were yellowish by visual observation.

 (Examples 5 to 9) Flat plate molding

 Composition liquid 1 was prepared in the same manner as in Example 1, and using the same catalyst as in Example 1, as a polymer modifier, SBS in Example 5, BR in Example 6, BR in Example 7, SBR in Example 7, In Example 8, a monomer solution containing PS in 5% by weight was prepared, and in Example 9, ZNR was prepared in the same manner as in Example 1, and a flat plate was formed.

Each of the flat plates obtained in Examples 5 to 9 was colorless and transparent, and no void was observed on the surface of the molded product. The glass transition temperatures (T g) of the flat plates obtained in Examples 5 to 9 were measured in the same manner as in Example 1. Further, the total light transmittance was measured in accordance with JISK 73611, and the yellowness was measured by a transmission method. 776

(Comparative Examples 3 to 7) Flat plate molding

 Similar to the preparation method of composition liquid 1 of Example 1, as a polymer modifier, SBS in Comparative Example 3, BR in Comparative Example 4, SBR in Comparative Example 5, PS in Comparative Example 6, PS in Comparative Example 7 A monomer composition containing 5% by weight of each ZNR was prepared, and flat plate molding was performed in the same manner as in Comparative Example 1.

 The flat plates obtained in Comparative Examples 3 to 7 were all translucent yellow. In addition, the physical properties (glass transition temperature (Tg), total light transmittance and yellowness) of the flat plates obtained in Comparative Examples 3 to 7 were measured in the same manner as in Examples 5 to 9.

 (Comparative Example 8) Flat plate molding

 Flat plate molding was performed in the same manner as in Example 1 except that the polymer modifier was not used. The obtained flat plate was colorless and translucent, and voids were observed on the surface of the molded product. In addition, the physical properties (glass transition temperature (Tg), total light transmittance, and yellowness) of the flat plate obtained in Comparative Example 8 were measured in the same manner as in Examples 5 to 9.

 The type of the polymer modifier used in Examples 5 to 9 and Comparative Examples 3 to 8, the maximum heating rate during polymerization, and each physical property of the obtained flat plate (glass transition temperature (Tg), total light transmission) Table 2 summarizes the results of the measurements.

 Table 2

 Example and Comparative Example No.Example 5 Comparative Example 3 Example 6 Comparative Example 4 Example 7 Comparative Example 5 Type of Polymer Modifier SBSSBSBRBRSBRSBR Maximum Heating Rate (° C / sec)〉 50 6.5> 50 5.2> 50 6.2

T g (° C) 153 149 151 152 149 148 Total light transmittance (%) 90 78 91 78 90 78 Void presence None None None None None None Yellowness (transmission method) 1.5 13.2 1.4 13.5 1.5 13.3 Table 2 (continued)

 (Example 10) Molding of colored flat plate

 A flat plate was formed in the same manner as in Example 1 except that 6 g of SBS and 0.15 g of a yellow pigment were used, to obtain a yellow transparent flat plate having no void on the surface.

 (Example 11) Molding of colored plate

 A flat plate was formed in the same manner as in Example 1 except that? 56 and 0.1 g of the blue pigment were used, to obtain a blue transparent plate having no voids on the surface.

 (Example 12) Molding of colored plate

 A flat plate was formed in the same manner as in Example 1 except that 6 g of EPDM and 1.0 g of a blue pigment were used, to obtain a blue opaque flat plate having no voids on the surface. Industrial applicability

 The norbornene-based resin molded product of the present invention exhibits a remarkable effect of improving the physical properties by adding a polymer modifier as compared with those obtained by a conventionally known production method. Since the norbornene-based resin molded product of the present invention is colorless, it is extremely useful in the field of optical materials and the like. Further, according to the present invention, by appropriately selecting the polymer modifier to be added, it is possible to obtain a colorless and highly transparent norpolene-based resin molded article, and a colorless pure white without using a titanium white pigment or the like. The present invention provides a norbornene-based resin molded product. Further, the colored resin of the present invention has a vivid color tone and has an effect of being excellent in design.

Claims

The scope of the claims 1. A colorless norbornene-based resin molded product obtained by bulk polymerization of a norbornene-based monomer containing a polymer modifier in the presence of a ruthenium complex catalyst. 2. The molded article according to claim 1, wherein the polymer modifier is one or more selected from the following group A, and has a total light transmittance (thickness of 4 mm) of 80% or more.  Group A: a polymer having a butadiene monomer unit, a styrene resin, a thermoplastic norbornene resin, and a thermoplastic saturated norbornene resin. 3. The polymer modifier is at least one selected from the following group B, Aizo Tsu preparative impact value 3 0 KGC mZ cm ² or more and flexural claims strength is the 5 kg ZMM ² or more The molded article according to item 1.  Group B: a polymer having at least one monomer unit selected from ethylene monomer units, α-olefin monomer units, isobutylene monomer units, and isoprene monomer units. 4. A white pigment obtained by bulk polymerization of a norbornene-based monomer containing one or more polymer modifiers and a colorant selected from the group 前 記 in the presence of a ruthenium complex catalyst. A norbornene-based resin molded product that is colored without using it. 5. The molded article according to any one of claims 1 to 4, wherein the ruthenium complex catalyst is a catalyst in which at least one carbene compound containing a hetero atom is coordinated with ruthenium. 6. The ruthenium complex catalyst is a catalyst in which ruthenium is coordinated with at least one imidazolidin-2-ylidene compound or a 4-imidazoline-2-ylidene compound having a substituent at the 1,3-position. Molded product described in any one of ~ 5 7. A colorless norbornene characterized in that a norpolene-based monomer containing a polymer modifier is subjected to bulk polymerization in the presence of a ruthenium complex catalyst at a maximum temperature rise rate of 20 ° CZ seconds or more during polymerization. Method for manufacturing system-formed products. 8. The method for producing a molded article according to claim 7, wherein the ruthenium complex catalyst is a catalyst in which at least one carbene compound containing a hetero atom is coordinated to ruthenium. 9. The ruthenium complex catalyst is a catalyst in which ruthenium is coordinated with at least one imidazolidin-2-ylidene compound or a 4-imidazoline-2-ylidene compound having a substituent at the 1,3-position. Or the method for producing a molded article according to 8. 10. Colorless characterized by bulk polymerizing norbornene-based monomers containing a polymer modifier in the presence of a ruthenium complex catalyst in which at least one heteroatom-containing carbene compound coordinates to ruthenium Method for manufacturing a norbornene-based resin molded product. 11. The production of a molded article according to claim 10, wherein the heteroatom-containing carbene compound is an imidazolidine-12-ylidene compound or a 41-imidazoline-2-ylidene compound having a substituent at the 1,3-position. Method.