JPH08208949A - Norbornene bulk polymer - Google Patents

Abstract

PURPOSE: To obtain a norbornene bulk polymer which hardly undergoes discoloration and degradation in elongation when it is in use. CONSTITUTION: This polymer is formed by homogeneously dispersing a hindered amine light stabilizer having a mol.wt. of 350-2,000, pref. 500-1,500, still pref. 600-1,000, a phenolic antioxidant, and a hydrocarbon rubber in a base polymer which is formed by polymerizing a metathesis-polymerizable monomer having a norbornene ring in the presence of a metathesis polymn. catalyst. The bulk polymer contains the rubber in an amt. of 1-30wt.%, pref. 2-15wt.%, still pref. 3-12wt.%. of the sum of the base polymer and the rubber, and the amts. of the light stabilizer and the antioxidant contained are 0.1-2.0wt.% and 0.1-4.0wt.%, respectively, based on the sum of the base polymer and the rubber.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a reaction injection molding (RI) of a metathesis polymerizable monomer having a norbornene ring structure.
M), which relates to the norbornene bulk polymer. More specifically, it relates to a norbornene bulk polymer obtained by RIM which is improved in terms of weather resistance, heat deterioration resistance and discoloration resistance.

[0002]

2. Description of the Related Art Conventionally, dicyclopentadiene (DC
P), ethylidene norbornene (ENB), tricyclopentadiene, norbornene, vinyl norbornene and other cyclic compounds having a norbornene ring structure undergo ring-opening polymerization with a metathesis polymerization catalyst in the absence of a solvent to form a bulk polymer, It is known that a molded body can be easily obtained by using the block polymer. It is also known that a norbornene bulk polymer having improved impact resistance can be obtained by compounding a rubber with the above cyclic compound (Japanese Patent Laid-Open No. 58-129013).

When the above cyclic compound having a norbornene ring structure is used as a raw material, a large-sized molded product can be easily obtained by using an inexpensive mold, and particularly when DCP is used as a main ingredient as a raw material, it is suitable for a polymer. Due to the combination of rigidity and impact resistance, and because DCP is inexpensive and economically advantageous, casings for construction machines, large covers such as golf carts, septic tanks and water meters. It is preferably used for water equipment such as a cover, and for house members such as bay windows.

[0004]

By the way, since the norbornene bulk polymer produced by the metathesis polymerization has a double bond in the polymer, when it is exposed to light, heat or air for a certain period of time, it is oxidized or remains. The double bond reacts with the catalyst, physical properties such as elongation and impact strength are deteriorated, and the surface of the polymer is discolored. As described above, the norbornene bulk polymer generally has poor weather resistance, heat deterioration resistance and discoloration resistance. Therefore, the molded product of the norbornene bulk polymer is
Surface coating is often applied during use. However, coating has a problem in that it not only complicates the process, but also raises the product price, because it causes an increase in the manufacturing process of the molded product.

In addition, when the coating is applied, there are many cases where a poor adhesion of the coating film occurs, or the coating film is peeled off due to this poor adhesion or physical abrasion. When the coating film is peeled off, the polymer resin layer is exposed, the appearance becomes unsightly due to the color difference between the coating film and the resin layer, and the peeled portion cannot be protected.

Further, a method of using a coloring mother liquor in which a pigment is previously dispersed by a homogenizer as a method of mixing a pigment in a raw material monomer and performing a coloring treatment (spot coating) (JP-A-2-2)
9423), a method of adding titanium black (JP-A-1-230626), a method of adding oxygen-free carbon black (JP-A-1-301747), and ultramarine as an activator of a metathesis catalyst. A method of polymerizing after coexisting (JP-A-2-214764), a method of adding a pigment selected from carbon, titanium oxide, iron oxide, and cobalt oxide (JP-A-2-28214), etc. Is proposed. However, with any of the above methods, there is a problem that it is difficult to put into practical use, except for black, because the color changes greatly during use.

Further, the norbornene bulk polymer molded article is irrespective of whether it is colored or not, and even if the surface is stabilized by coating, the inside gradually deteriorates and the elongation decreases, and There is a problem that the impact strength is reduced in proportion.

In particular, in order to improve the weather resistance and heat deterioration resistance of the norbornene bulk polymer, it is common to add auxiliary agents such as antioxidants and light stabilizers to the raw material monomers. As such an auxiliary agent, 2,6-di-t-butyl-
Paracresol, and N, N'-diphenyl-1,4
Polymers to which hindered phenols such as phenylenediamine or aromatic amine compounds have been added as stabilizers have been proposed (USP 4,507,453).
However, such an amine compound has a problem that it tends to migrate to the surface of the bulk polymer, resulting in poor durability.

As a solution to this problem, a polymer to which an aromatic amine having a norbornene ring has been added has been proposed (JP-A-1-256518). However, such compounds are extremely difficult to obtain and practically difficult to use.

Also disclosed is a polymer in which a hindered phenol compound and an aromatic amine compound are added in a mixing ratio of 0.1 to 10 (USP 4,822,83).
9). However, when the present inventors actually evaluated these compounds by a test, it was found that the improvement of physical properties was insufficient and further improvement was desired.

The present invention has been made in order to solve the above-mentioned problems, and stabilizes the physical properties, that is, delays the decrease of elongation particularly under the use environment, and even if it decreases, the elongation is reduced. The objective is to provide a norbornene bulk polymer in which the discoloration is maintained relatively large and the discoloration is small.

[0012]

A bulk polymer of norbornene according to claim 1 of the present invention is a basic polymer produced by polymerizing a metathesis polymerizable monomer having a norbornene ring structure in the presence of a metathesis polymerization catalyst. Norbornene in which a hindered amine light stabilizer having a molecular weight of 350 to 2000, preferably 500 to 1500, more preferably 600 to 1000, a phenolic antioxidant, and a rubber made of a hydrocarbon are uniformly dispersed. It is a bulk polymer, and the weight ratio of the rubber to the total amount of the base polymer and the rubber is 1 to 30%, preferably 2 to 15%,
It is more preferably 3 to 12%, and the weight ratio of the hindered amine light stabilizer and the phenolic antioxidant to the total amount of the base polymer and the rubber is 0.1 to 2.0 for the hindered amine light stabilizer. %, And the phenol-based antioxidant is 0.1 to 4.0%.

The norbornene bulk polymer according to claim 2 of the present invention is the norbornene bulk polymer according to claim 1 in a weight ratio of 0.005 to 4 with respect to the total amount of the base polymer and the rubber. 0.000%, preferably 0.01-
It is characterized in that it contains 2.00%, more preferably 0.05 to 1.00% of pigment.

The components of the present invention will be described in detail below.

(Metathesis Polymerizable Monomer Having Norbornene Ring Structure) Dicyclopentadiene (DCP), ethylidene norbornene (ENB), tricyclopentadiene, norbornene, vinyl norbornene, etc. It is preferably used as a metathesis-polymerizable monomer having Among them, DCP can be obtained at low cost, and is economically preferable. Any of these may be used as a raw material monomer, or a combination thereof may be used. Especially a small amount of ENB for DCP
A compound containing tricyclopentadiene or tricyclopentadiene is advantageous in terms of physical properties and production cost of the obtained norbornene bulk polymer.

In the present specification, the metathesis polymerization reaction proceeds without adding anything other than the catalyst to the metathesis polymerizable monomer, and the pure norbornene polymer obtained as a result is called a basic polymer. .

(Metathesis Polymerization Catalyst) As a main catalyst (metathesis polymerization catalyst), a tungsten chloride derivative (for example, one described in JP-A-58-129013) or a molybdate amine derivative (for example, JP-A-58-9013) is used. 58-127728) and an alkylaluminum derivative which is a catalyst activator is used as a cocatalyst. Specifically, a solution A in which a cocatalyst is mixed with a metathesis polymerizable monomer and a solution B in which a main catalyst is mixed with a metathesis polymerizable monomer are prepared, and these solution A and solution B are mixed immediately before molding. A norbornene bulk polymerization molding is produced.

Hindered amine light stabilizer (HAL
S), a phenolic antioxidant, a rubber, a pigment, and other additives which are optionally added are added in advance to either one or both of the solution A and the solution B, and the solution A is added immediately before molding. And Solution B are mixed. Do not add the above HALS or the like to the solution A and the solution B, prepare a solution C prepared by adding the above HALS or the like to a separately prepared metathesis polymerizable monomer, and mix the solution A, the solution B and the solution C immediately before molding. You may Examples of the above-mentioned other additives include a fluidization modifier, a thickener, a filler, an antistatic agent, a flame retardant, a polymer denaturant, a sliding agent, a fiber reinforcing agent, and a foaming agent. Yes, these can be used as needed.

(Hindered amine light stabilizer (HAL
S)) Hindered amine compounds are known as having a basic structure in which the 2,2,6,6-position of the piperidinyl group has a functional group substituted with an alkyl group.
As typical compounds, (1) bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate (molecular weight 480): As a product, "TINUVIN 770" manufactured by Ciba-Geigy Japan Ltd.
(“” Is a trade name, the same applies hereinafter), “Mark LA-77” manufactured by Adeka Argus Chemical Co., Ltd., and “Sanol LS-770” manufactured by Sankyo Co., Ltd.

(2) Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (molecular weight 50
8): As a product, "SANOL LS-76" manufactured by Sankyosha Co., Ltd.
There is 5 ".

(3) Succinic acid-bis (2,2,6,6)
-Tetramethyl-4-piperidinyl) ester (molecular weight 397): As a product, "T
INUVIN780 ”is available.

(4) 2- (3,5-di-t-butyl-
4-Hydroxybenzyl) -2n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl) (molecular weight 685): As a product, there is "TINUVIN 144" manufactured by Ciba-Geigy Japan.

(5) Tetrakis (1, 2, 2, 6, 6
-Pentamethyl-4-piperidyl) -1,2,3,4-
Butane tetracarboxylate (molecular weight 847): As a product, "Adeka Stab LA-5" manufactured by Asahi Denka Co., Ltd.
There is 2 ”.

(6) Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate (molecular weight 791): Asahi Denka Kogyo Co., Ltd. "Adeka Stab LA-57" is available.

(7) 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-
Condensation product of piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol (molecular weight about 2000): As a product, there is "ADEKA STAB LA-63P" manufactured by Asahi Denka Co., Ltd.

(8) 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol, β, β, β ', β'-tetramethyl-
Condensate with 3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol (molecular weight about 1900): As a product, "Adeka Stab LA-68LD" manufactured by Asahi Denka Co., Ltd. There is.

(9) 4-benzoyloxy-2,2
6,6-Tetramethylpiperidine (molecular weight 260): As a product, there is "SANOL LS-774" manufactured by Sankyosha.

(10) (2,2,6,6-tetramethyl-4-piperidinyl) methacrylate (molecular weight 22
4): As a product, "M" made by Adeka Argus Chemical Co., Ltd.
arkLA-87 ”.

Among the HALS as described above, those substituted with a hydrogen group are more effective as a light stabilizer than those substituted with an alkyl group at the 1-position of the pepyridinyl group.

In the present invention, of the above HALS, those having a molecular weight of 350 to 2000, preferably 500 to 1500, and more preferably 600 to 1000 are used. The reason for this is that if the molecular weight is less than 350, HALS easily migrates to the surface of the molded product formed of the bulk polymer, resulting in poor durability of the molded product. Also,
When the molecular weight is more than 2000, the solubility in the raw material monomer is poor, the molding operation becomes difficult, and the metathesis polymerization reaction is hindered.

Further, in the present invention, HALS is added to the mixture of the above-mentioned monomer and rubber so as to be 0.1 to 2.0% by weight of the total weight of the metathesis-polymerizable monomer and the rubber consisting of hydrocarbon. To be done. Such a range is set because the effect as a light stabilizer cannot be reliably obtained when the amount of HALS added is less than 0.1% by weight, and 2.0% by weight is set. This is because if it exceeds the range, the metathesis polymerization reaction is inhibited and it becomes difficult to obtain a polymer. Even if a polymer is obtained, the unreacted monomer is contained in the polymer, and as a result, the polymer exhibits a soft state, which is not practical. Further, HALS is generally expensive, and it is not economical to use it in a large amount.

HAL for metathesis polymerizable monomers
The method of adding S is not particularly limited, but from the viewpoint of ensuring the stability of the catalyst, HALS is dissolved in the liquid main catalyst (metathesis polymerization catalyst), and this solution is used as the monomer, rubber and phenol. It may be added to the mixture of the system antioxidant.

(Phenolic Antioxidant) In the present invention, a hindered phenolic antioxidant is used as the antioxidant. Specifically, (1) 2,6-di-t-butyl-4-methylphenol (BHT) (2) 2,6-di-t-butyl-4-n-butylphenol (3) Triethylene glycol- Bis [3- (3-t-
Butyl-5-methyl-4-hydroxyphenyl) propionate]: As a product, there is “IRGANOX245” manufactured by Ciba-Geigy Japan.

(4) 2,4-bis-(-n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine: As a commercial product,
There is "IRGANOX565" made by Ciba-Geigy Japan.

(5) Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate: As a product, there is "IRGANOX1010" manufactured by Ciba-Geigy Japan.

(6) 1,3,5-trimethyl-2,4
6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene: As a commercial product, there is "Ethyl 330" manufactured by Ethyl Corporation.

(7) 4,4'-methylene-bis (2,6
-Di-t-butyl-4-phenol): As a product,
"Ethyl 702" manufactured by Ethyl Corporation
There is.

The amount of such a phenolic antioxidant added is 0.1 to 4.0% by weight based on the total amount of the metathesis-polymerizable monomer and the rubber. If the amount is less than 0.1% by weight, the effect as an antioxidant cannot be obtained.
This is because the antioxidant effect is not improved even if the amount is larger than the above range, which is economically disadvantageous, and the heat resistance of the norbornene polymer is lowered.

The method of adding the antioxidant to the solutions A and B and the order of addition are not particularly limited, but the antioxidant may be added to either or both of the solutions A and B. Good.

The mixing ratio of HALS and the phenolic antioxidant is preferably set within the range of 4/1 to 0.5 / 10, and more preferably 1/0, for the purpose of exerting a synergistic effect. It is particularly preferable to set it within the range of 1 to 2/10.

(Rubber Composed of Hydrocarbon) In the present invention, rubber composed of hydrocarbon is used. Such a rubber is substantially composed of carbon and hydrogen, but may contain a small amount of another element within a range that does not inhibit the metathesis polymerization reaction. The molecular weight is not particularly limited as long as it exhibits usual properties as a rubber. Rubber is generally a polymer having a molecular weight of 4,000 or more. As such rubber, styrene / butadiene / styrene block rubber (SBS), styrene / isoprene / styrene block rubber (SIS),
Styrene / butadiene block rubber (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene / propylene rubber (EPD)
M, EPT, EPR) and the like. Such a rubber has good solubility in a norbornene-based metathesis-polymerizable monomer, and is present in a state of being uniformly dispersed in the norbornene bulk polymer after polymerization.

The amount of such a rubber added to the polymerizable monomer is 1 to 30% by weight, preferably 2 to 15% by weight, more preferably 3 to 3% by weight based on the total amount of the monomer and the rubber.
It is 12% by weight. If the amount of rubber added is less than 1% by weight, the elongation of the polymer will be small and the impact strength will be weak. Further, the effect of adding the HALS and the antioxidant is reduced. Conversely, if the amount of rubber added is more than 30% by weight,
The viscosity of the solution A or solution B containing rubber becomes high,
The molding process becomes difficult, and the effect of adding a large amount is not recognized.

Therefore, the presence of a proper amount of rubber within the above range makes the dispersion state in the polymerizable monomers such as HALS and the above antioxidant and in the rubber appropriate, and a good bulk polymer can be obtained.

(Coloring Material) When it is necessary to color the norbornene bulk polymer, a coloring material such as a pigment or dye is used. In the present invention, a pigment that does not inhibit the metathesis polymerization reaction is preferably used. Specifically, titanium white, carbon black, zinc white, rouge, chromium oxide, white alumina, yellow iron oxide, calcium carbonate,
Examples thereof include inorganic pigments such as talc, molybdenum red, navy blue, aluminum hydroxide, and graphite, and organic pigments such as anthraquinone-based, quinacdrine-based, polyazo-based, and phthalocyanine-based pigments.

The amount of the colorant added is 0.005 to 4.000% by weight, preferably 0.01 to 2.00% by weight, and more preferably 0.05, based on the total amount of the polymerizable monomer and the rubber. Is set to ˜1.00% by weight. Addition amount is 0.
If it is less than 005% by weight, the desired coloring cannot be obtained, and if it exceeds 4.000% by weight, it is economically disadvantageous. Especially for carbon black, the weather resistance is remarkably improved by adding about 1% by weight.

The method of adding the coloring material, the order of addition, etc. are not particularly limited, but they may be added to the above solution B in advance or to the above solution C, and the solution A and the solution B may be added immediately before the reaction. Alternatively, it is preferable to mix the solution A, the solution B, and the solution C.

(Polymerization / Molding / Mold) When the above solution A, solution B, and solution C were prepared, they were also added and mixed immediately before molding, and the resulting mixture was placed in a predetermined mold. Then, the polymerization reaction and the molding are performed simultaneously. The injection operation is so-called resin injection method, in which the mixture is filled in a mold while mixing with a static mixer, or so-called RIM method, in which each liquid is mixed while being collided and immediately filled in the mold (collision mixing). Etc. are applicable. Generally, the RIM method is preferred.

According to such a method, the molding process can be carried out at a low pressure, and a die having a relatively low strength can be used. Usually, an inexpensive and simple mold such as an electroforming mold, a resin mold, and a thermal spray mold is used, but as a cheaper mold, a sand mold, a cement mold, a paper mold, or the like can be used.

The molding temperature in the RIM method is room temperature to
Temperature range of 100 ℃, molding pressure vacuum ~ 100M
Pa. The wall thickness of the molded product is 2 mm or more, preferably 3 mm or more, and more preferably 5 mm or more.

[0050]

According to the norbornene bulk polymer according to claim 1, the hindered amine light stabilizer mixed in the metathesis polymerizable monomer having a norbornene ring structure is
Molecular weight 350-2000, preferably 500-150
0, and more preferably 600 to 1000 is used, so that the above-mentioned light stabilizer having such a molecular weight is very familiar to the norbornene bulk polymer, and can be reliably and uniformly dispersed in the polymer. It is dispersed, and deterioration of the polymer due to light reception is suppressed.

That is, the light stabilizer has a molecular weight of 35.
If it is less than 0, the disadvantage that the durability of the molded article becomes poor due to the migration of the stabilizer to the surface of the bulk polymer occurs, but such an inconvenience does not occur because the molecular weight is 350 or more. Also, when the molecular weight exceeds 2000, there is a disadvantage that the molding operation becomes difficult due to poor solubility in the metathesis polymerizable monomer, but since the molecular weight is 2000 or less, No inconvenience will occur.

Further, the rubber which is an elastic material in the norbornene block polymer is the weight ratio of the base polymer and the rubber,
99-70: 1-30, preferably 98-85: 2-1
5, more preferably 97 to 88: 3 to 12 are mixed in such a proportion that it is mixed, so that the elastic force of this rubber makes the norbornene bulk polymer very tough.

When the amount of rubber added is less than 1% by weight, the elongation of the polymer is reduced and the impact strength is not weakened. On the contrary, the amount of rubber added is more than 30% by weight. As a result, the viscosity of the rubber-containing monomer increases, and the molding process becomes difficult.

Further, since the above-mentioned bulk polymer contains a proper amount of the phenolic antioxidant, the deterioration of the polymer due to the oxidation can be surely prevented.

According to the norbornene bulk polymer according to the above-mentioned claim 2, the weight ratio is 0.005 to 4.000%, preferably 0.01 to the total amount of the base polymer and the rubber.
Since the pigment is contained in an amount of .about.2.00%, more preferably 0.05 to 1.00%, the above polymer is colored by this pigment. Then, the disadvantage that the desired coloring cannot be obtained due to the addition amount being less than 0.005% by weight is avoided, and the uneconomical situation due to exceeding 4.000% by weight is avoided.

[0056]

EXAMPLES The present invention will now be described in more detail by way of examples. In Example 1 below, preparation of a metathesis-polymerizable monomer liquid and a polymerization catalyst, and a test for examining the combined use effect of the above-mentioned monomer, HALS, a phenol-based oxidant, and rubber, in Example 2, HALS Regarding the test concerning the effect of the molecular weight, Example 3 describes the test concerning the effect of the colorant.

Example 1 First, a liquid of a metathesis-polymerizable monomer was prepared. As the same monomer, commercially available DC
P and ENB are mixed at a ratio of 95% by weight: 5% by weight,
Add molecular sieves 13X to this mixture for half a day.
Water and other impurities were adsorbed and removed, and the supernatant was collected as a monomer mixture for testing.

Next, a main catalyst (metathesis polymerization catalyst) solution was prepared. In this example, high-purity tungsten hexachloride was used as the main catalyst. 198 g (0.5 mol) of this tungsten hexachloride was mixed with 90% of toluene which had been dried in advance.
To 0 ml under nitrogen atmosphere, 9.25 g of t-butanol dissolved in 50 ml of toluene was added and stirred for 1 hour, then 110.5 g (0.5 mol) of nonylphenol and toluene. 50 ml of
Was added to the above stirrer and a nitrogen purge was performed with stirring for 1 hour.

Thereafter, at room temperature of 25 to 30 ° C., 100 g of acetylacetone was added to the mixture subjected to the above-mentioned nitrogen purge, and as a result, hydrogen chloride gas produced as a by-product was expelled, and the mixture was purged with nitrogen gas until hydrogen chloride gas was no longer detected. Purged. Then, the toluene that had flown out partly was replenished to obtain a 0.5 mol / liter stock solution of a tungsten main catalyst.

Next, a predetermined additive (HALS and rubber) is added to and dissolved in the above-mentioned monomer mixture solution, and then the above-mentioned tungsten main catalyst stock solution is fractionated so that the concentration of tungsten becomes 8 mmol / liter. Solution B was added and mixed as described above to obtain a solution B.

On the other hand, a cocatalyst stock solution was prepared in parallel with the preparation of the main catalyst. In this example, di-n was used as the cocatalyst.
-Octyl aluminum chloride, tri-n-octyl aluminum, and diglyme were used. These were weighed 43 g, 312 g and 134 g, respectively, and mixed with the above-mentioned monomer mixed solution and diluted to 1000 ml to prepare a 1.0 mol / liter cocatalyst stock solution.

Next, a predetermined additive (hindered phenolic antioxidant and rubber) is added to the above monomer mixture.
Was dissolved, and then the above cocatalyst stock solution was separated and mixed so that the concentration of the aluminum compound was 24 mmol / liter to obtain a solution A.

In the preparation of Solution A and Solution B as described above, the above-mentioned "ADEKA STAB LA-57" was used as the HALS added to Solution B, and the above-mentioned hindered phenol antioxidant added to Solution A was used. "Ethy
1 702 ”was used. As the rubber to be added to the solutions A and B, the above SBS (trade name "Clayton" manufactured by Shell Japan Co., Ltd.) was used.

Then, as an example, the mixing ratio of the rubber and the total amount of the solution A and the solution B (solutions A and B) was 5% by weight: 95% by weight, and the HALS "(solution A, B) + rubber" was used. No. 1-1, which was set to 1.0% by weight, and the addition ratio of the antioxidant to “(solution A, B) + rubber” was 1.0% by weight. The mixing ratio is the same as above, and the addition ratio of HALS to “(solution A, B) + rubber” is 0.5% by weight and the addition ratio of antioxidant to “(solution A, B) + rubber”. Is the same as the above Test No. 1-2, the mixing ratio of the rubber and the solutions A and B is the same as above, and the addition ratio of the HALS to the “(solution A, B) + rubber” is 1.0% by weight,
Test numbers 1-3 in which the addition ratio of the antioxidant to “(solution A, B) + rubber” was set to 2.0% by weight, and
The mixing ratio of the rubber and the solutions A and B was 10% by weight: 90% by weight, the addition ratio of HALS to the “(solution A, B) + rubber” was 1.0% by weight, and the addition of the antioxidant “(solution A ，
B) + rubber ", and the above-mentioned four types of mixtures of test numbers 1-4 in which the addition ratio to 10.0 wt% was set,
A molding process was performed by a predetermined polymerization reaction.

As a comparative example, the mixing ratio of the rubber and the solutions A and B was 5% by weight: 95% by weight, "(solutions A and B)".
+ Addition of HALS to rubber "was 2.0% by weight and no antioxidant was added. Test number 1-
5. The mixing ratio of the rubber and the solutions A and B is 5% by weight: 95% by weight, the addition ratio of the antioxidant to “(solution A, B) + rubber” is 2.0% by weight, and HALS is Test No. 1-6 with no addition, Test No. 1 with addition ratio of HALS to solutions A and B without rubber and 1.0% by weight, and addition ratio of antioxidant to 1.0% by weight
7. Test No. 1-8 in which the mixing ratio of the rubber and the solutions A and B was 5% by weight: 95% by weight, and HALS and the antioxidant were not added, and the rubbers in the solutions A and B,
The above-mentioned 5 kinds of mixtures of Test No. 1-9 to which neither HALS nor antioxidant was added were prepared, and these were also subjected to molding treatment by a predetermined polymerization reaction in the same manner as above.

The molding process accompanied by the polymerization reaction was carried out as follows. First, the solution A and the solution B are transferred to separate tanks, and predetermined amounts of the solutions A and B are sent to a static mixer (mixing device) through a gear pump, whereby the solution A and the solution B are mixed with each other in a predetermined mold. Injected. Then, a polymerization reaction accompanied by heat generation was started at the same time as the injection, and a molded product was obtained after about 5 minutes. The mold used in this test is a rectangular parallelepiped having a cavity size of 300 mm in length × 300 mm in width × 5 mm in thickness.
It is heated to 0 ° C. When there was no sudden heat generation in the mold, the mold was opened after 1 hour and the contents were taken out and used as a molded article to be evaluated.

Tensile strength (Mpa), elongation (%) and impact strength (kJ / m ² ) were adopted as the evaluation items of the molded product obtained as described above. The tensile strength and elongation were tested based on JISK-7113, and the impact strength (notched Izod impact strength) was JISK-69.
Measured at 23 ° C. according to 11. The color was visually observed.

In order to investigate changes in physical properties over time, the results of the measurement conducted 2 to 30 days after the molded product was obtained are used as the initial physical properties, and after the initial measurement, 100
After being exposed to a temperature environment of ° C for 400 hours, the measurement results at room temperature were taken as the physical properties after aging, and it was confirmed how the physical properties change after long-term use.

Table 1 shows the test conditions and test results.

[0070]

[Table 1]

As shown in Table 1, in the examples of the present invention (Test Nos. 1-1 to 1-4) in which HALS, phenolic antioxidant and rubber were added to the polymerizable monomer, The physical properties are in a good state in which tensile strength, elongation and impact strength are properly balanced, and the physical properties after aging hardly change from the initial physical properties, and the present invention is very stable in physical properties. It turns out to be excellent.

On the other hand, in the comparative example, HALS was added to the mixture of the polymerizable monomer and the rubber at 2.
When 0% by weight is added (Test No. 1-5), the obtained molded article is very soft, the metathesis polymerization reaction is inhibited, and it is understood that the molded article is not practical.
Further, when the antioxidant and the rubber are added but the HALS is not added (Test No. 1-6), the initial physical properties are comparable to those of the examples, but in the physical properties after aging, particularly the impact strength is greatly reduced, The problem is that it deteriorates quickly. When HALS and an antioxidant were added but rubber was not added (Test No. 1-7), only the tensile strength was abnormally large, but the elongation and impact strength were extremely weak, and the physical properties were well balanced. Molded product cannot be obtained. Further, when only the rubber is added and the HALS and the antioxidant are not added (Test No. 1-8), the initial physical properties are comparable to those of the examples, but the physical properties after aging with respect to elongation and impact strength are remarkably deteriorated. ing. In addition, when neither HALS, antioxidant nor rubber is added to the polymerizable monomer (Test No. 1-9), only the tensile strength is abnormally increased, but other physical properties are remarkably inferior. .

(Example 2) In Example 2, HAL
In order to investigate the influence of the molecular weight of S, H of test number 1-1
The type of ALS was variously changed depending on the molecular weight, and the other conditions were the same as those in Test No. 1-1, and the molding treatment was performed. Examples are Test No. 2-1 to Test No. 2
-6, and the comparative examples are Test No. 2-7 to Test No. 2-9.
Is. Table 2 shows the test conditions and the test results.

[0074]

[Table 2]

As shown in Table 2, HALS has a molecular weight of 3
In the case of 50 or less (test numbers 2-7 and 2-9),
The color changes significantly after aging, and the elongation also decreases significantly. The test number 2-9 is USP 4,822.
839 is an additional test result. In addition, the molecular weight of HALS is 2
If it exceeds 000 (Test No. 2-8), the polymerization reaction is inhibited and a molded product cannot be obtained.

On the other hand, in the case of the embodiment, HALS
All have a molecular weight in the range of 350 to 2000, and it can be seen that the physical properties after aging are superior to those of the comparative examples.

Example 3 In Test No. 1-1 above, phthalocyanine blue (manufactured by Dainippon Seika Chemicals Co., Ltd.) was used as a colorant at a ratio of 0.1% by weight with respect to the rubber and the solutions A and B. Molding treatment was performed under the same conditions as Test No. 1-1 except that the solution B was added.

The color of the obtained molded product was light blue, the tensile strength was 45 MPa, the elongation was 50%, and the impact strength was 4.
It was 7 kJ / m ² .

This molded product was subjected to 40 ° C. in a temperature environment of 100 ° C.
Tensile strength, elongation, and impact strength after standing for 0 hour are 47 MPa, 11%, and 42 kJ /, respectively.
It was m ² , and showed very stable physical properties. Also, 40
The color tone after a lapse of 0 hours was light blue which was slightly brownish, the degree of discoloration was small, and the color was stable.

Further, in order to evaluate the weather resistance, the molded product was subjected to weathering for 250 hours by sunshine carbon according to JISA-1415, and then the physical properties were measured. Tensile strength was 45 MPa and elongation was 30%.
The impact strength was 44 kJ / m ² , which was comparable to the initial physical properties, and almost no color change was observed.

On the other hand, for comparison, in Test Nos. 1-6, the above phthalocyanine blue (manufactured by Dainippon Seika Chemicals Co., Ltd.) was used as a colorant in an amount of 0.1% by weight based on the rubber and the solutions A and B. Molding treatment was performed under the same conditions as Test Nos. 1 to 6 except that it was added to Solution B in proportion. The color of the obtained molded product was light blue as described above, and the tensile strength, elongation, and impact strength were 45 MP, respectively.
a, 40%, and 45 kJ / m ² .

This molded product was tested in a temperature environment of 100.degree.
Tensile strength, elongation, and impact strength after 00 hours are
It was 49 MPa, 4%, and 32 kJ / m ² , respectively, and the physical properties after aging were remarkably deteriorated. Also,
The color changed to light blue with a strong brown color added, giving the impression of deterioration.

A weather resistance evaluation test similar to the above was carried out. As a result, the tensile strength was 46 MPa, the elongation was 10%, the impact strength was 35 kJ / m ² , and the color tone was an aged color with a strong brown color added. Became. From this, by adding the pigment in a predetermined mixing ratio in a state where the mixing ratio of the HALS, the antioxidant and the rubber according to the present invention is applied, a good color tone in which an aged color is hard to appear is obtained. I understand that it will be.

[0084]

As described in detail above, the norbornene bulk polymer according to claim 1 of the present invention is a basic polymer formed by polymerizing a metathesis polymerizable monomer having a norbornene ring structure in the presence of a metathesis polymerization catalyst. In the coalescence, the molecular weight is 350 to 2000, preferably 500 to 1500,
More preferably, it is a norbornene bulk polymer in which a hindered amine light stabilizer of 600 to 1000, a phenolic antioxidant, and a rubber composed of a hydrocarbon are uniformly dispersed, and the basic polymer and the rubber are combined. The weight ratio of rubber to the total amount is 1 to 30%, preferably 2 to 15
%, More preferably 3 to 12%, and the weight ratio of the hindered amine light stabilizer and the phenolic antioxidant to the total amount of the base polymer and the rubber is 0.1 to 2 for the hindered amine light stabilizer. 0.0% and 0.1-4.0% of phenolic antioxidants.

Therefore, the hindered amine light stabilizer mixed in the metathesis-polymerizable monomer having a norbornene ring structure has a molecular weight of 350 to 2000, preferably 5
Since those having a molecular weight of from 0 to 1500, more preferably from 600 to 1000 are used, the above-mentioned light stabilizer having such a molecular weight is very familiar to the bulk polymer of norbornene, and surely and uniformly. It is dispersed in the polymer, and deterioration of the polymer due to light reception is suppressed.

That is, the light stabilizer has a molecular weight of 35.
If it is less than 0, the disadvantage that the durability of the molded article becomes poor due to the migration of the stabilizer to the surface of the bulk polymer occurs, but such an inconvenience does not occur because the molecular weight is 350 or more. Also, when the molecular weight exceeds 2000, there is a disadvantage that the molding operation becomes difficult due to poor solubility in the metathesis polymerizable monomer, but since the molecular weight is 2000 or less, No inconvenience will occur.

Further, the rubber which is an elastic material in the norbornene bulk polymer has a weight ratio of the basic polymer and the rubber of
99-70: 1-30, preferably 98-85: 2-1
5, more preferably 97 to 88: 3 to 12 are mixed in such a proportion that it is mixed, so that the elastic force of this rubber makes the norbornene bulk polymer very tough.

When the amount of rubber added is less than 1% by weight, the elongation of the polymer becomes small and the impact strength is not weakened. On the contrary, the amount of rubber added is more than 30% by weight. In this case, the viscosity of the rubber-containing monomer becomes high, and the molding process becomes difficult.

Furthermore, since the appropriate amount of the phenolic antioxidant is contained in the above-mentioned bulk polymer, deterioration of the polymer due to oxidation can be reliably prevented.

According to the norbornene bulk polymer according to claim 2 of the present invention, the weight ratio to the total amount of the base polymer and the rubber is 0.005 to 4.000%, preferably 0.01 to 4. 2.00%, more preferably 0.05 to 1.0
Because of the 0% pigment content, the pigment colors the polymer. Then, the disadvantage that the desired coloring cannot be obtained due to the addition amount being less than 0.005% by weight is avoided, and the uneconomical situation due to exceeding 4.000% by weight is avoided.

Front Page Continuation (72) Inventor Barry Woodfine London London Double Sea 1 Buoy 7 AA High Holborn 174/177 Alton House Koube Steel Europe Limited

Claims (2)

[Claims] 1. A basic polymer produced by polymerizing a metathesis-polymerizable monomer having a norbornene ring structure in the presence of a metathesis polymerization catalyst has a molecular weight of 350 to 20.
00, preferably 500-1500, more preferably 600-1000, a norbornene bulk polymer in which a hindered amine light stabilizer, a phenolic antioxidant, and a rubber composed of a hydrocarbon are uniformly dispersed, The weight ratio of the rubber to the total amount of the base polymer and rubber is 1 to 30%, preferably 2 to 15%, more preferably 3 to 12%, and the weight ratio to the total amount of the base polymer and rubber is. The weight ratio of the hindered amine light stabilizer and the phenolic antioxidant is 0.1 to 2.0% for the hindered amine light stabilizer and 0.1 for the phenolic antioxidant.
Norbornene bulk polymer, characterized in that it is 1-4.0%. 2. A weight ratio of 0.005 to 4.000%, preferably 0.01 to 2.00%, and more preferably 0.05 to 1 based on the total amount of the base polymer and rubber. .0
The norbornene bulk polymer according to claim 1, characterized in that it contains 0% of pigment.