JP2022000499A - Unsaturated bond-containing cycloolefin copolymer and resin modifier containing it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cycloolefin polymer having excellent compatibility with a resin and a resin modifier using the cycloolefin polymer.
An unsaturated bond-containing cycloolefin copolymer having a number average molecular weight of 800 to 50,000 and having a carbon-carbon double bond, wherein the number of carbon-carbon double bonds is unsaturated. An unsaturated bond-containing cycloolefin copolymer having 0.1 to 20 atoms per 1000 carbons constituting the contained cycloolefin copolymer.
[Selection diagram] None

Description

The present invention relates to an unsaturated bond-containing cycloolefin copolymer and a resin modifier containing the same.

Known raw materials for modified polyolefins into which specific functional groups such as carboxyl groups have been introduced, and resin modifiers using low molecular weight polyolefins obtained by thermally decomposing polyolefins (patented patents). Document 1 etc.).

However, the low molecular weight polyolefin described in Patent Document 1 and the like is not sufficiently compatible with a copolymer of cycloolefin and ethylene (called a cycloolefin copolymer), and it is difficult to use it as a resin modifier for a cycloolefin copolymer. There was a problem that there was.

Japanese Unexamined Patent Publication No. 2019-94481

An object of the present invention is to provide a cycloolefin copolymer having excellent compatibility with a cycloolefin copolymer and a resin modifier using the same.

The present inventors have arrived at the present invention as a result of studies for achieving the above object.
That is, the present invention is an unsaturated bond-containing cycloolefin copolymer having a number average molecular weight of 800 to 50,000 and having a carbon-carbon double bond, and the number of carbon-carbon double bonds is unsaturated. It is an unsaturated bond-containing cycloolefin copolymer having 0.1 to 20 bonds per 1000 carbons constituting the bond-containing cycloolefin copolymer.

The unsaturated bond-containing cycloolefin polymer of the present invention has excellent compatibility with cycloolefin copolymers.

The unsaturated group-containing cycloolefin copolymer in the present invention is preferably a polymer composed of a cycloalkene having a norbornene skeleton and an acyclic monoolefin as a constituent monomer.

Examples of the cycloalkene having a norbornene skeleton include monocycloalkenes having a norbornene skeleton and having 7 to 25 carbon atoms {norbornene (bicyclo [2.2.1] -2-heptene), tricyclo [4.3.0. 1 ^2,5 ] -3-decene, tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] -3-dodecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] -4-pentadecene, pentacyclo [7.4.0.1 ^{2,5. 19 and 12} . 0 ^8,13] -3-pentadecene, pentacyclo [8.4.0.1 ^{2,5. 19 and 12} . 0 ^8,13] -3-hexadecene, pentacyclo [6.6.1.1 ^3,6. 0 ^2,7 . 0 ^9,14] -4-hexadecene, hexacyclo [6.6.1.1 ^3,6. 1 ^{10, 13} . 0 ^2,7 . 0 ^9,14] -4-heptadecene, heptacyclo [8.7.0.1 ^2,9. 1 ^{4, 7 4} . 1 ^{11, 17} ． 0 ^3,8 . 0 ^12,16 ] -5-eikosen, heptacyclo [8.7.0.1 ^3,6 . 1 ^10,17 . 1 ^{12, 15} ． 0 ^2,7 . 0 ^{11, 16]} -4-eicosene, heptacyclo [8.8.0.1 ^2,9. 1 ^{4, 7 4} . 1 ^{11, 18} . 0 ^3,8 . 0 ^12,17 ] -5-Heneikosen, Octacyclo [8.8.0.1 ^2,9 . 1 ^{4, 7 4} . 1 ^{11, 18} . 1 ^{13, 16} . 0 ^3,8 . 0 ^12,17 ] -5-docosen, and nonacyclo [10.9.1.1 ^4,7 . 1 ^{13, 20} . 1 ^{15, 18} . 0 ^2,10 . 0 ^3,8 . 0 ^{12, 21} . 0 ^14,19] -5-pentacosene and the like.

Among the cycloalkenes having a norbornene skeleton, tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] -3-dodecene, norbornene (bicyclo [2.2.1] -2-heptene).

Preferred acyclic monoolefins include acyclic monoolefins having 2 to 10 carbon atoms.
Of the acyclic monoolefins having 2 to 10 carbon atoms, the acyclic monoolefin having 4 or more carbon atoms is an acyclic monoolefin having a double bond at the end. Examples of these acyclic monoolefins include ethylene, propylene, α-olefins having 4 to 8 carbon atoms (1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and the like).
Of these, ethylene and propylene are preferable.

The molar ratio [cycloalkene / olefin] of the cycloalkene having a norbornene skeleton constituting the unsaturated bond-containing cycloolefin copolymer and the acyclic monoolefin varies depending on the target resin, but is preferably 2/98 to 50. / 50, more preferably 5/95 to 40/60, and particularly preferably 10/90 to 30/70.

The unsaturated bond-containing cycloolefin copolymer of the present invention has a number average molecular weight of 800 to 50,000, preferably 1,000 to 18,000. When the number average molecular weight is in this range, the compatibility with the reforming resin becomes good without floating on the surface of the reforming resin when used as a resin modifier.
As a method for adjusting the unsaturated bond-containing cycloolefin copolymer to the above-mentioned number average molecular weight, a cycloolefin copolymer (a cycloolefin copolymer having no carbon-carbon double bond; A method of thermally reducing (described as a cycloolefin copolymer) by the method described below is preferable.

The number average molecular weight of the unsaturated bond-containing cycloolefin polymer is obtained by gel permeation chromatography (GPC) under the following conditions.
Equipment: "HLC-8120" [manufactured by Tosoh Corporation]
Column: "TSKgelGMHXL" [manufactured by Tosoh Corporation] (2 bottles) and "TSKgel Multipore HXL-M" [manufactured by Tosoh Co., Ltd.] (1 bottle) are linked. Sample solution: 0.3 wt% orthodichlorobenzene solution Injection volume: 100 μL
Flow rate: 1 mL / min Measurement temperature: 135 ° C
Detection device: Refractive index detector Reference material: Standard polystyrene (TSKstandardPOLYSTYRENE)
12 points (molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2 , 890,000) [manufactured by Tosoh Corporation]

The unsaturated bond-containing cycloolefin copolymer of the present invention is an unsaturated bond-containing cycloolefin copolymer having a carbon-carbon double bond, and is a carbon-carbon double bond component (hereinafter referred to as a double bond). The number (which may be described) is 0.1 to 20 (preferably 1 to 10, more preferably 2 to 9) per 1000 carbons constituting the unsaturated bond-containing cycloolefin copolymer. If the double bond is less than 0.1, the affinity of other resins with functional groups and the like is insufficient, and the function as a resin modifier is insufficient. On the other hand, if it exceeds 20, the heat resistance of the unsaturated bond-containing cycloolefin copolymer is lowered, which causes coloring and the like, making it difficult to use as a resin modifier.

The number of double bonds can be measured by nuclear magnetic resonance spectroscopy (NMR method).
In the present invention, the carbon-carbon double bond means a carbon-carbon double bond contained in a structure derived from a constituent monomer of a cycloolefin copolymer.

As a method for obtaining an unsaturated bond-containing cycloolefin copolymer having the above-mentioned number of double bonds, a known method for cycloolefin copolymer (for example, Japanese Patent Publication No. 43-9368, Japanese Patent Publication No. 44-29742). And the method of heat-reducing according to the manufacturing method described in Japanese Patent Publication No. 6-70094), and among them, the method of heat-reducing by the method described later is preferably mentioned.

The unsaturated bond-containing cycloolefin copolymer of the present invention is preferably a heat-reduced product of the cycloolefin copolymer, and is obtained by heat-decomposing the cycloolefin copolymer under the following conditions. It is more preferable that it is a thing. The thermal reduction means an operation of cutting a part of the main chain by a thermal decomposition reaction of the polymer to reduce the molecular weight.

As the cycloolefin copolymer to be thermally reduced, the number average molecular weight obtained by addition-copolymerizing the cycloalkene having a norbornene skeleton with the acyclic monoolefin exceeds 800 to 50,000. Any cycloolefin copolymer can be used without limitation, and commercially available products (for example, Apel series manufactured by Mitsui Chemicals Co., Ltd., TOPAS series manufactured by Polyplastics Co., Ltd., etc.) may be used.

The heat reduction is carried out by using the cycloolefin copolymer at 300 to 450 ° C. for 0.5 to 10 hours under the atmosphere of a gas having no reactivity with the cycloolefin copolymer (hereinafter referred to as an inert gas). It is preferable to heat it.

Examples of the inert gas used in the heat reduction include argon, nitrogen, carbon dioxide gas, steam and the like, and nitrogen is preferable. The inert gas is preferably aerated in the reaction vessel at a flow rate of 0.1 to 100 L / min during heating.
The heating temperature is preferably 300 to 450 ° C, more preferably 320 to 430 ° C. When the reaction temperature is in this range, the coloration of the unsaturated bond-containing cycloolefin copolymer is reduced, and the generation of odor can be suppressed, which is preferable. Hereinafter, the fact that the coloring is reduced and the generation of odor can be suppressed is described as having a good color tone and odor.
The reaction time is preferably 0.5 to 10 hours, more preferably 1 to 7 hours. When the reaction time is in this range, the color tone and odor of the unsaturated bond-containing cycloolefin copolymer are good, and the heat is uniformly reduced, which is preferable.

The pressure at the time of heat reduction is preferably normal pressure (atmospheric pressure) to 200 kg / cm ^{2, and} more preferably normal pressure to 150 kg / cm ² . Within this range, the color tone and odor of the unsaturated bond-containing cycloolefin copolymer will be good.

As the method of heat reduction, either a batch method or a continuous method may be used.
When the batch method is used, the inert gas is aerated in a reaction vessel made of stainless steel or the like equipped with a stirrer, the cycloolefin copolymer as a raw material is put in, and the mixture is heated at a predetermined temperature for a predetermined time under stirring. The heat reduction can be carried out at.
When the continuous method is used, the inert gas is aerated in a continuous reaction vessel such as a tubular reactor and an extruder, the cycloolefin copolymer as a raw material is put in, and the mixture stays in the reaction vessel at a predetermined temperature for a predetermined time. The heat reduction can be carried out by heating and melting while adjusting the input amount of the raw material.
Among them, the continuous method is preferable, and the tubular reactor used in the continuous method is preferably a reaction vessel in which two or more tubes having different inner diameters are connected in series and a static mixer as a part of the tubular reactor. And the like using.

When heating for heat reduction, a phenol-based antioxidant may be added, and as the phenol-based antioxidant, 2,6-di-tert-butyl-4-methylphenol, 2 Hindered phenols such as -tert-butyl-4-methylphenol, 6-tert-butyl-2,4-methylphenol, 2,6-di-tert-butylphenol, and 2-tert-butyl-4-ethylphenol. Examples include compounds.

In thermal reduction, a catalyst can also be used for the purpose of promoting the decomposition reaction. The catalyst to be added includes radical generation catalysts [peroxides such as benzoyl peroxide, di-tert-butyl peroxide, and dicumyl peroxide; 2,2'-azobis (isobutyronitrile), 2,2'. -Azobisos (2,4-dimethylvaleronitrile) and azonitriles such as 4,4'-azobis (4-cyanovalerian acid)] and cracking catalysts (silica-alumina, silica-magnesia, activated clay, etc.) and the like. ..

By thermally reducing the cycloolefin copolymer, a carbon-carbon double bond is generated, and an unsaturated bond-containing cycloolefin copolymer can be produced.
In that case, the molar ratio [dichloroalkene / olefin] of the cycloalkene having a norbornene skeleton constituting the unsaturated bond-containing cycloolefin copolymer to the acyclic monoolefin constitutes the cycloolefin copolymer before thermal reduction. The molar ratio of cycloalkene to acyclic monoolefin tends to be maintained as it is.

The resin modifier of the present invention contains the unsaturated bond-containing cycloolefin copolymer described above.
The weight ratio of the unsaturated bond-containing cycloolefin copolymer contained in the resin modifier is preferably 90% by weight or more based on the total weight of the resin modifier.
The resin modifier may contain known stabilizers, antioxidants, ultraviolet absorbers and the like, in addition to the unsaturated bond-containing cycloolefin copolymer.

The resin modifier of the present invention can be used as a resin modifier for the purpose of improving the molding processability of various thermoplastic resins, improving the dispersibility of pigments and fillers, and improving the coatability and adhesiveness, and in particular. It can be suitably used as a resin modifier used in a cycloolefin copolymer. The amount of the resin modifier added is preferably 0.05 to 50 parts by weight, more preferably 0.1 to 30 parts by weight, based on the weight (100 parts by weight) of the thermoplastic resin to be added.
Further, the resin modifier can be used together with other known resin modifiers (stabilizers, antioxidants, ultraviolet absorbers, etc.).
Further, the resin modifier of the present invention may be added after being dispersed in a thermoplastic resin to be added at a high concentration in advance as a masterbatch.
Further, the resin modifier of the present invention may be further reacted with another compound and used as an acid-modified cycloolefin copolymer, and further, a polyamide resin, a polyester resin, a polyimide resin and a polyamide having it as an essential constituent component may be used. It may be used as an imide resin and then used for modifying a thermoplastic resin.

The resin composition of the present invention is a resin composition containing the above-mentioned resin modifier, and is used for molded parts for electric / electronic devices, packaging materials, transport materials, living materials, building materials, etc. Can be done. In addition to the above resin modifiers, the resin composition is a known thermoplastic resin [acrylic (co) polymer resin, vinyl chloride-vinyl acetate copolymer resin, polyester resin, polyurethane resin, polyolefin resin, ethylene-vinyl acetate. Copolymer resin, urea resin, epoxy resin, polyamide resin, cellulose resin, polyolefin resin, etc.], and if necessary, known resin modifiers (colorants, ultraviolet absorbers, mold release agents, antioxidants, etc.) , Flame retardant, antibacterial agent, compatibilizer, filler, ester exchange reaction inhibitor, etc.) may be contained.
The resin modifier contained in the resin composition is preferably 1 to 50% by weight based on the total weight of the thermoplastic resin and the resin modifier. The resin composition of the present invention can be prepared by a known method using the thermoplastic resin and the resin modifier in a reaction vessel, a tubular reactor, an extruder or the like to which a heating device and a stirring device are attached. Examples of the shape of the resin composition include powder and pellets, but the shape is not limited to these shapes.

The molded product of the present invention is a molded product made of the above-mentioned resin composition, and can be used for parts of electric / electronic devices, packaging materials, transport materials, living materials, building materials and the like. The molding of the resin composition can be performed by using a known molding apparatus (injection molding machine or the like) for the resin composition.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto.

<Example 1: Thermal reduction of cycloolefin copolymer>
Nitrogen inlet, thermometer, 4-necked flask cycloolefin copolymer [manufactured by Mitsui Chemicals, Inc. of 3L equipped with exhaust gas distillation tube and a stirring bar "APL6011T (tetracyclo ^[4.4.0.1 2, 5 .1 ^7,10 ] -3-dodecene-ethylene copolymer, ethylene content 89 mol%) ”, number average molecular weight: 105,000] 1500 g was charged under a nitrogen atmosphere. After that, nitrogen continued to be aerated in Kolben until the end of heat reduction. Next, the temperature was raised by heating with a mantle heater, and the heat was reduced for 2 hours at a temperature of 360 ° C. while stirring. Then, the heat-reduced product was cooled to 200 ° C. and then taken out from the corben to obtain an unsaturated bond-containing cycloolefin copolymer (a2-1) of the present invention. The copolymer (a2-1) had a number average molecular weight of 3,000 and had 8.3 double bonds per 1000 carbons.

<Example 2>
The copolymer (a2-1) obtained in Example 1 was used as it was as a resin modifier, and mixed with a cycloolefin copolymer under the following conditions.
First, 90 parts of the cycloolefin copolymer (“APL6011T” manufactured by Mitsui Chemicals Co., Ltd., number average molecular weight: 105,000) used in Example 1 and the unsaturated bond-containing cycloolefin copolymer (a2) obtained in Example 1 -1) Ten parts were kneaded by a twin-screw extruder under the conditions of 280 ° C. and a residence time of 30 seconds to pelletize.
Next, the pellet was set under the conditions of a cylinder temperature of 280 ° C., an injection pressure of 800 kg / cm ² , an injection speed of 200 mm / s, and a mold temperature of 80 ° C., and a spiral flow test metal having a flow path with a width of 10 mm and a thickness of 1 mm. A molded piece was produced by injection molding using an injection molding machine (trade name "PS40E5ASE", Nissei Jushi Kogyo Co., Ltd.) to which a mold was attached.
The obtained molded pieces were evaluated as a test piece for appearance evaluation and a test piece for evaluation of injection molding processability (fluidity).
The appearance of the obtained test piece was colorless and transparent, and the distance flowing through the flow path of the spiral flow test mold was 1200 mm.
When only the cycloolefin copolymer (“APL6011T”, number average molecular weight: 105,000) used in Example 1 was injection-molded under the same conditions, the distance flowing through the flow path of the spiral flow test mold was 850 mm. Met.

<Example 3>
The pellets obtained in Example 2 were set under the conditions of a cylinder temperature of 280 ° C, an injection pressure of 800 kg / cm ² , an injection speed of 200 mm / s, and a mold temperature of 80 ° C. A molded piece of 100 × 100 × 2 mm was produced using Kogyo Co., Ltd., and the smoothness of the surface of the molded piece was evaluated. The smoothness was evaluated by measuring the surface roughness with a "digital microscope VHX-600" manufactured by KEYENCE.
The surface roughness of the obtained test piece was measured and found to be 0.70 μm.
The surface roughness when only the cycloolefin copolymer (“APL6011T” manufactured by Mitsui Chemicals, Inc., number average molecular weight: 105,000) used in Example 1 was injection-molded under the same conditions was 1.2 μm. ..

<Example 4: Thermal reduction of cycloolefin copolymer>
Nitrogen inlet, thermometer, cycloolefin copolymer four-necked flask 3L equipped with exhaust gas distillation tube and a stirrer bar [APL6015T (tetracyclo ^[4.4.0.1 2,5 ^.1 7,10] -3 -Dodecene-ethylene copolymer, number average molecular weight: 120,000, ethylene content 73 mol%)] 1500 g was charged under a nitrogen atmosphere. After that, heat reduction was performed by the same method as in Example 1. Then, the heat-reduced product was cooled to 200 ° C. and then taken out from the corben to obtain an unsaturated bond-containing cycloolefin copolymer (a2-2) of the present invention. The copolymer (a2-2) had a number average molecular weight of 5,000 and had 7.8 double bonds per 1000 carbons.

<Example 5: Thermal reduction of cycloolefin copolymer>
Cycloolefin copolymer [TOPAS8007F-04 (norbornene (bicyclo [2.2.1] -2-heptene) and ethylene) in a 3L 4-necked flask equipped with a nitrogen introduction pipe, a thermometer, an exhaust gas distilling pipe and a stirring rod. Polymer, number average molecular weight: 110,000, ethylene content 67 mol%)] 1500 g was charged under a nitrogen atmosphere.
After that, heat reduction was performed by the same method as in Example 1. Then, the heat-reduced product was cooled to 200 ° C. and then taken out from the corben to obtain an unsaturated bond-containing cycloolefin copolymer (a2-3) of the present invention. The copolymer (a2-3) had a number average molecular weight of 4,000 and had 8.0 double bonds per 1000 carbons.

<Comparative Example 1>
Instead of unsaturated bond-containing cycloolefin copolymer (a2-1), pyrolyzable low molecular weight polyolefin (trade name "Sunwax LEL250", number average molecular weight: 3,000, manufactured by Sanyo Kasei Kogyo Co., Ltd.) 10 parts A test piece was prepared and evaluated in the same manner as in Example 2 except that the above was used. The appearance of the obtained test piece was cloudy, and the distance flowing through the flow path of the spiral flow test mold was 900 mm.

Since the molded product of the resin composition in Example 2 using the unsaturated bond-containing cycloolefin copolymer of the present invention obtained in Example 1 as a resin modifier is colorless and transparent, the unsaturated bond of the present invention is unsaturated. It can be seen that the bond-containing cycloolefin copolymer has excellent compatibility with the cycloolefin copolymer. Since the resin composition using the unsaturated bond-containing cycloolefin copolymer of the present invention has a long flow distance through the flow path of the spiral flow test mold, the unsaturated bond-containing cycloolefin copolymer of the present invention is co-weighted. It can be seen that the resin modifier using the coalescence functions as an excellent modifier for improving fluidity with respect to the cycloolefin copolymer.
Further, in the resin composition using the unsaturated bond-containing cycloolefin copolymer of the present invention in Example 3, the unsaturated bond-containing cycloolefin copolymer of the present invention is used because the surface roughness of the molded piece is small. It can be seen that the resin modifier used is functioning as an excellent surface smoothness imparting agent for the cycloolefin copolymer.

The unsaturated bond-containing cycloolefin copolymer of the present invention can be used as a resin modifier such as a fluidity improving modifier suitable for cycloolefin copolymers.

Claims (5)

An unsaturated bond-containing cycloolefin copolymer having a number average molecular weight of 800 to 50,000 and having a carbon-carbon double bond, and an unsaturated bond-containing cycloolefin having a number of carbon-carbon double bonds. An unsaturated bond-containing cycloolefin copolymer having 0.1 to 20 atoms per 1000 carbons constituting the polymer. The unsaturated bond-containing cycloolefin copolymer according to claim 1, which is a heat-reduced product of a copolymer of cycloolefin and ethylene. A resin modifier containing the unsaturated bond-containing cycloolefin copolymer according to claim 1 or 2. A resin composition containing the resin modifier according to claim 3. A molded product made of the resin composition according to claim 4.