Acid-modified cycloolefin polymer, resin modifier containing same, and method for producing acid-modified cycloolefin polymer

Abstract

To provide an acid-modified cycloolefin polymer having excellent compatibility with a cycloolefin polymer and a cycloolefin copolymer, a resin modifier including the same, and a method for producing an acid-modified cycloolefin polymer.SOLUTION: An acid-modified cycloolefin polymer is a cycloolefin polymer (A) having an unsaturated carboxylic acid (B) and / or an acid anhydride thereof (B') added thereto, and satisfies all of the following (1)-(2): (1) the acid-modified cycloolefin polymer having a number average molecular weight of 800-50,000 and (2) the acid-modified cycloolefin polymer having an acid value of 0.1-60.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an acid-modified cycloolefin polymer, a resin modifier containing the same, and a method for producing the acid-modified cycloolefin polymer. [Background technology]

[0002] Resin modifiers containing acid-modified polyolefins obtained by adding unsaturated carboxylic acids to low-molecular-weight polyethylene, low-molecular-weight polypropylene, or the like are known as resin modifiers used as surface modifiers and electrical property imparting agents for polyolefin resins, as well as dispersants and compatibilizers used when mixing polyolefin resins with other materials (Patent Document 1, etc.).

[0003] However, the resin modifier described in Patent Document 1 and the like has a problem in that it is not sufficiently compatible with cycloolefin polymers and cycloolefin copolymers, which are cyclic olefin resins among polyolefin resins. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-117888 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide an acid-modified cycloolefin polymer having excellent compatibility with cycloolefin polymers and cycloolefin copolymers, a resin modifier using the same, and a method for producing the acid-modified cycloolefin polymer. [Means for solving the problem]

[0006] The present inventors have conducted extensive research to achieve the above object and have arrived at the present invention. Specifically, the present invention relates to an acid-modified cycloolefin polymer which is an adduct of a cycloolefin polymer (A) with an unsaturated carboxylic acid (B) and / or its acid anhydride (B'), and which satisfies all of the following (1) and (2): (1) The acid-modified cycloolefin polymer has a number average molecular weight of 800 to 50,000. (2) The acid-modified cycloolefin polymer has an acid value of 0.1 to 60. [Effects of the Invention]

[0007] The acid-modified cycloolefin polymer of the present invention has excellent compatibility with cycloolefin polymers and cycloolefin copolymers. DETAILED DESCRIPTION OF THE INVENTION

[0008] The acid-modified cycloolefin polymer of the present invention is an adduct of an unsaturated carboxylic acid (B) and / or its acid anhydride (B') to a cycloolefin polymer (A), and is an acid-modified cycloolefin polymer that satisfies all of the following (1) and (2): (1) The acid-modified cycloolefin polymer has a number average molecular weight of 800 to 50,000. (2) The acid-modified cycloolefin polymer has an acid value of 0.1 to 60.

[0009] The acid-modified cycloolefin polymer of the present invention is an adduct of an unsaturated carboxylic acid (B) and / or its acid anhydride (B') to a cycloolefin polymer (A), and is a polymer that has been modified by adding an unsaturated carboxylic acid (B) and / or its acid anhydride (B') to the cycloolefin polymer (A) to introduce a carboxyl group.

[0010] <Cycloolefin polymer (A)> Examples of the cycloolefin polymer (A) in the present invention include a cycloalkene polymer (PA1) having a cycloalkene having a norbornene skeleton as a constituent monomer, and a cycloalkene polymer (PA2) having a cycloalkene having a norbornene skeleton and an acyclic monoolefin as constituent monomers.

[0011] The polymer (PA1) is preferably a saturated polymer obtained by ring-opening metathesis polymerization of a cycloalkene having a norbornene skeleton by a known method, and then completely hydrogenating the double bonds in the polymer (hereinafter referred to as hydrogenation).

[0012] The cycloalkenes having a norbornene skeleton constituting the polymer (PA1) 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 .1 9,12 .0 8,13 ]-3-pentadecene, pentacyclo[8.4.0.1 2,5 .1 9,12 .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 .1 11,17 .0 3,8 .0 12,16 ]-5-eicosene, heptacyclo[8.7.0.1 3,6 .1 10,17 .1 12,15 .02,7 .0 11,16 ]-4-eicosene, heptacyclo[8.8.0.1 2,9 .1 4,7 .1 11,18 .0 3,8 .0 12,17 ]-5-heneicosene, octacyclo[8.8.0.1 2,9 .1 4,7 .1 11,18 .1 13,16 .0 3,8 .0 12,17 ]-5-docosene, 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, etc. The cycloalkene having a norbornene skeleton may be one type or two or more types.

[0013] Among the above cycloalkenes having a norbornene skeleton, preferred are 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.

[0014] The polymer (PA2) is preferably a copolymer obtained by addition copolymerizing a cycloalkene having a norbornene skeleton and an acyclic monoolefin by a known method.

[0015] Preferred cycloalkenes constituting the polymer (PA2) include the same cycloalkenes as those exemplified as the cycloalkenes constituting the polymer (PA1), and preferred cycloalkenes are also the same.

[0016] Preferred examples of the acyclic monoolefin constituting the polymer (PA2) include acyclic monoolefins having 2 to 10 carbon atoms. Among the acyclic monoolefins having 2 to 10 carbon atoms, acyclic monoolefins having 4 or more carbon atoms are acyclic monoolefins having a double bond at the terminal. Examples of these acyclic monoolefins include ethylene, propylene, and α-olefins having 4 to 8 carbon atoms (1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, etc.). Of these, ethylene and propylene are preferred.

[0017] The number-average molecular weight of the acid-modified cycloolefin polymer of the present invention is 800 to 50,000, preferably 1,000 to 18,000. If the number-average molecular weight is less than 800, when the acid-modified cycloolefin polymer is used as a resin modifier, the resin modifier will come off the surface of the resin to be modified, impairing the surface properties. If the number-average molecular weight exceeds 50,000, the reactivity with unsaturated carboxylic acids and their anhydrides will be insufficient, resulting in insufficient compatibilizing ability with cycloolefin polymers and cycloolefin copolymers.

[0018] By using a polymer (PA1) or a polymer (PA2) having a number average molecular weight of 800 to 50,000 (preferably 1,000 to 18,000) as the cycloolefin polymer (A) to which the unsaturated carboxylic acid (B) and / or its acid anhydride (B') is added, the number average molecular weight of the acid-modified cycloolefin polymer can be within this range.

[0019] The number average molecular weight of the acid-modified cycloolefin polymer and the cycloolefin polymer (A) can be determined by gel permeation chromatography (GPC) under the following conditions. Device: "HLC-8120" [manufactured by Tosoh Corporation] Column: "TSKgelGMHXL" [manufactured by Tosoh Corporation] (2 columns) and "TSKgelMultiporeHXL-M" [manufactured by Tosoh Corporation] (1 column) connected together Sample solution: 0.3% by weight orthodichlorobenzene solution Solution injection volume: 100μL Flow rate: 1mL / min Measurement temperature: 135℃ Detector: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 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) [Tosoh Corporation]

[0020] The polymer (PA1) may be a polymer obtained by ring-opening metathesis polymerization of the cycloalkene having a norbornene skeleton under polymerization conditions that result in a predetermined number-average molecular weight, followed by hydrogenation, or may be a polymer obtained by thermally degrading a cycloolefin polymer (PA01) having a number-average molecular weight of more than 800 to 50,000, obtained by ring-opening metathesis polymerization and hydrogenation of the cycloalkene, to a predetermined number-average molecular weight. As the cycloolefin polymer (PA01) having a molecular weight of 800 to more than 50,000 used for thermal degradation, commercially available products (for example, Zeonex series and Zeonor series manufactured by Zeon Corporation) may be used. The thermal degradation refers to a procedure in which a part of the main chain is cut off by a thermal decomposition reaction of the polymer to reduce the molecular weight.

[0021] The polymer (PA2) may be a polymer obtained by addition copolymerizing the cycloalkene having a norbornene skeleton and the acyclic monoolefin under polymerization conditions that result in a predetermined number average molecular weight, or may be a polymer obtained by thermally degrading a cycloolefin polymer (PA02) having a number average molecular weight of more than 800 to 50,000, which is obtained by addition copolymerizing the cycloalkene and the acyclic monoolefin, to a predetermined number average molecular weight. As the polymer (PA02) having a molecular weight of 800 to more than 50,000, commercially available products (for example, the APEL series manufactured by Mitsui Chemicals, Inc. and the TOPAS series manufactured by Polyplastics Co., Ltd.) may be used.

[0022] As the polymer (A), a polymer obtained by thermal degradation of the above-mentioned cycloolefin polymer (PA01) and the above-mentioned cycloolefin polymer (PA02) is preferred, and a polymer obtained by thermal degradation under the conditions described below is more preferred.

[0023] The cycloolefin polymer (A) to which the unsaturated carboxylic acid (B) and / or its acid anhydride (B') is added preferably has a number average molecular weight of 800 to 50,000 and is a polymer having 0.1 to 20 terminal double bonds per 1000 carbon atoms constituting the cycloolefin polymer (a) (hereinafter referred to as per 1000 carbon atoms).

[0024] The cycloolefin polymer (A) preferably has a melt index (MI) of 0.5 to 250, more preferably 1 to 200. The melt index can be measured in accordance with JIS K6758 (temperature 230°C, load 2.16 kgf).

[0025] The cycloolefin polymer (A) preferably has a softening point of 70 to 200°C, more preferably 90 to 180°C.

[0026] The cycloolefin polymer (A) preferably has a melt viscosity at 160°C of 10 to 30,000 mPa·s, more preferably 30 to 20,000 mPa·s.

[0027] The unsaturated carboxylic acid (B) and its acid anhydride (B') added to the cycloolefin polymer (A) include unsaturated carboxylic acids and their acid anhydrides having 3 to 9 carbon atoms, such as (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, allylsuccinic anhydride, and nadic anhydride. Of these, maleic acid and maleic anhydride are preferred.

[0028] The total weight proportion of structural units derived from the unsaturated carboxylic acid (B) and its acid anhydride (B') contained in the acid-modified cycloolefin polymer is preferably 0.1 to 10% by weight, more preferably 1 to 8% by weight, based on the total weight of the acid-modified cycloolefin polymer. This range is preferable because the acid-modified cycloolefin polymer has good compatibility with cycloolefin polymers and cycloolefin copolymers, and the acid-modified cycloolefin polymer is less likely to be discolored, making it suitable for use as a resin modifier.

[0029] The weight proportion of structural units derived from the unsaturated carboxylic acid (B) and its acid anhydride (B') contained in the acid-modified cycloolefin polymer can be quantified by measuring the nuclear magnetic resonance spectrum (NMR) of the acid-modified cycloolefin polymer.

[0030] The acid-modified cycloolefin polymer has an acid value (unit: mgKOH / g) of 0.1 to 60, preferably 1 to 50 from the viewpoint of the modifying properties as a resin modifier and the mechanical strength of the molded product. The acid value of the acid-modified cycloolefin polymer is measured by titration using a KOH / methanol solution containing phenolphthalein as an indicator in accordance with the acid value measurement method by neutralization titration described in JIS K 0070-1992. When the acid-modified cycloolefin polymer has an anhydride group, the acid value of the acid anhydride group in the neutralization titration method is measured as the half-esterified acid value after half-esterification with methanol. The acid value of the acid-modified cycloolefin polymer can be adjusted by adjusting the weight ratio of the unsaturated carboxylic acid and its acid anhydride used in the production method of the acid-modified cycloolefin polymer described below to a predetermined weight ratio.

[0031] The acid-modified cycloolefin polymer of the present invention is preferably an acid-modified cycloolefin polymer obtained by the method for producing an acid-modified cycloolefin polymer described below.

[0032] The resin modifier of the present invention essentially contains the above-mentioned acid-modified cycloolefin polymer {an adduct of an unsaturated carboxylic acid (B) and / or its acid anhydride (B') to a cycloolefin polymer (A)}, but may also contain a cycloolefin polymer (A) to which neither the unsaturated carboxylic acid (B) nor the acid anhydride (B') has been added. The weight proportion of the cycloolefin polymer (A) to which neither the unsaturated carboxylic acid (B) nor its acid anhydride (B') is added, contained in the resin modifier, is preferably less than 50% by weight based on the total weight of the resin modifier. The resin modifier may contain known resin additives (stabilizers, antioxidants, ultraviolet absorbers, etc.) in addition to the acid-modified cycloolefin polymer. The weight of the resin additive contained in the resin modifier is preferably less than 10% by weight based on the total weight of the resin modifier.

[0033] The resin modifier of the present invention can be mixed with a thermoplastic resin and used as a molding processability improver for various thermoplastic resins, a dispersant for pigments and fillers, an improver for paintability and adhesion, etc. The weight of the resin modifier added to the thermoplastic resin is preferably 0.05 to 50 parts by weight, more preferably 0.1 to 30 parts by weight, per 100 parts by weight of the thermoplastic resin. The resin modifier may also be used together with other known resin additives (stabilizers, antioxidants, ultraviolet absorbers, etc.). The resin modifier of the present invention may be added as a masterbatch in which it is dispersed at a high concentration in the thermoplastic resin to which it is to be added. Furthermore, the resin modifier of the present invention may be further reacted with other compounds to form polyamide resins, polyester resins, polyimide resins, and polyamideimide resins containing the acid-modified cycloolefin polymer as an essential component, and then used to modify thermoplastic resins.

[0034] The resin modifier of the present invention can be preferably used as an additive for resin compositions containing cycloolefin polymers and cycloolefin copolymers. By adding and mixing the resin modifier with cycloolefin polymers and cycloolefin copolymers, it is possible to modify the dispersibility, coatability, adhesiveness, etc. of pigments and fillers, and by adding and mixing the resin modifier with other thermoplastic resins, it is possible to impart excellent compatibility of the cycloolefin polymers and cycloolefin copolymers to the other thermoplastic resins.

[0035] In addition, the resin modifier of the present invention can be preferably used as a compatibilizer (also referred to as a polymer alloy compatibilizer) used in the production of a polymer alloy obtained by mixing a plurality of polymers. Polymer alloys in which the resin modifier of the present invention can be preferably used include polymer alloys of cycloolefin polymers or cycloolefin copolymers (hereinafter also referred to as cycloolefin (co)polymers) and polyamide resins (such as nylon 6, 6,6, nylon 11 and nylon 12), polymer alloys of cycloolefin (co)polymers and polyester resins (such as polyethylene terephthalate, polybutylene terephthalate and polycarbonate), polymer alloys of cycloolefin (co)polymers and polyimide resins, and polymer alloys of cycloolefin (co)polymers and polyamide-imide resins.

[0036] When used as a compatibilizer for polymer alloys, the content of the resin modifier of the present invention contained in the polymer alloy is preferably 0.1 to 30% by weight, more preferably 1 to 15% by weight, based on the total weight of the resin and resin modifier constituting the polymer alloy. When used as a compatibilizer for polymer alloys, it is also preferable to react the resin modifier of the present invention with other compounds to form a polyamide resin, polyester resin, polyimide resin, or polyamideimide resin containing an acid-modified cycloolefin polymer as an essential constituent component, and then use the resulting resin modifier.

[0037] When the resin modifier of the present invention is mixed with a thermoplastic resin for use, the resin modifier and the thermoplastic resin can be mixed by melt-kneading them using a known kneading machine (extruder, Brabender, kneader, or Banbury mixer).

[0038] The method for producing an acid-modified cycloolefin polymer of the present invention comprises a step of mixing and heating a cycloolefin polymer (a) and an unsaturated carboxylic acid (b) and / or an anhydride thereof (b') in the absence of a radical polymerization initiator, and satisfies all of the following (1) to (3): (1) The cycloolefin polymer (a) has a number average molecular weight of 800 to 50,000. (2) The cycloolefin polymer (a) has carbon-carbon double bonds, and the number of carbon-carbon double bonds is 0.1 to 20 per 1000 carbon atoms constituting the cycloolefin polymer (a). (3) The total weight proportion of the unsaturated carboxylic acid (b) and its acid anhydride (b') is 0.1 to 14% by weight based on the total weight of the cycloolefin polymer (a), the unsaturated carboxylic acid (b) and its acid anhydride (b').

[0039] The cycloolefin polymer (a) used in the method for producing an acid-modified cycloolefin polymer of the present invention is the cycloolefin polymer (A) exemplified in the above-mentioned acid-modified cycloolefin polymer, and is a cycloolefin polymer having carbon-carbon double bonds, in which the number of carbon-carbon double bonds (hereinafter referred to as double bonds) is 0.1 to 20 (preferably 1 to 10, more preferably 2 to 7) per 1000 carbons constituting the molecular chain. If the number of double bonds in the cycloolefin polymer (a) is less than 0.1 per 1000 carbon atoms, the acid modification by the unsaturated carboxylic acid or its anhydride does not proceed well, and the function as a resin modifier becomes insufficient, whereas if it exceeds 20, the obtained heat resistance decreases. The number of double bonds can be measured by nuclear magnetic resonance spectroscopy (NMR).

[0040] Of the cycloolefin polymers (a), the polymer (a1) can be obtained by thermally degrading the above polymer (PA01) under the following conditions. Among the cycloolefin polymers (a), the polymer (a2) can be obtained by thermally degrading the polymer (PA02) under the following conditions. The polymer (a1) is a cycloalkene polymer having a cycloalkene having a norbornene skeleton as a constituent monomer, and the polymer (a2) is a cycloalkene polymer having a cycloalkene having a norbornene skeleton and an acyclic monoolefin as constituent monomers.

[0041] The thermal degradation of the polymer (PA01) and the polymer (PA02) can be carried out by heating the polymer (PA01) and the polymer (PA02) in an atmosphere of a gas that is not reactive with the polymer (PA01) and the polymer (PA02) (hereinafter referred to as an inert gas), preferably at 300 to 450°C, more preferably for 0.5 to 10 hours.

[0042] Examples of inert gases used in the thermal degradation include argon, nitrogen, carbon dioxide, and water vapor, with nitrogen being preferred. The inert gas is preferably passed through 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 within this range, the color tone and odor of the cycloolefin polymer (a1) and the cycloolefin polymer (a2) become good. Here, good color tone and odor means little coloring and no unpleasant odor. The reaction time is preferably 0.5 to 10 hours, more preferably 1 to 7 hours. When the reaction time is within this range, the color and odor of the polymer (a1) and the polymer (a2) become good, and homogeneous thermal degradation can be achieved, which is preferable.

[0043] The pressure during thermal degradation is normal pressure (atmospheric pressure) to 200 kg / cm 2 is preferable, and more preferably normal pressure to 150 kg / cm 2Within this range, the color tone and odor of the polymer (a1) and the polymer (a2) will be good.

[0044] The thermal degradation may be carried out by either a batch method or a continuous method. (1) When using the batch method, thermal degradation can be carried out by passing an inert gas through a stainless steel or other reaction vessel equipped with a stirrer, adding the raw material polymer (PA01) or polymer (PA02), and heating it at a predetermined temperature for a predetermined time while stirring. (2) When a continuous method is used, thermal degradation can be carried out by passing an inert gas through a continuous reaction vessel such as a tubular reactor or an extruder, placing the raw material polymer (PA01) or polymer (PA02) in it, and heating and melting the raw material while adjusting the amount of raw material input so that the raw material remains in the reaction vessel at a predetermined temperature for a predetermined time. Among these, a continuous method is preferred, and preferred tubular reactors for use in a continuous method include a reaction vessel in which two or more tubes having different inner diameters are connected in series, and a tubular reactor in which a static mixer is used as part of the tubular reactor.

[0045] When heating for thermal degradation, a phenolic antioxidant may be added. Examples of the phenolic antioxidant include hindered phenolic compounds such as 2,6-di-tert-butyl-4-methylphenol (BHT), 2-tert-butyl-4-methylphenol (BHA), 6-tert-butyl-2,4-methylphenol (24M6B), 2,6-di-tert-butylphenol (26B), and 2-tert-butyl-4-ethylphenol (24M6B).

[0046] In thermal degradation, a catalyst can be used to promote the decomposition reaction. Examples of catalysts that can be added include radical-generating catalysts (peroxides such as benzoyl peroxide, di-tert-butyl peroxide, and dicumyl peroxide; azonitriles such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 4,4'-azobis(4-cyanovaleric acid)) and cracking catalysts (silica-alumina, silica-magnesia, activated clay, etc.).

[0047] By the thermal degradation, the bonds within the molecules of the polymer (PA01) and the polymer (PA02) are broken, and double bonds are generated. By mixing and heating the cycloolefin polymer (a) and the unsaturated carboxylic acid (b) and / or its anhydride (b'), the unsaturated carboxylic acid and its acid anhydride described below are added to the double bond, thereby obtaining an acid-modified cycloolefin polymer.

[0048] The unsaturated carboxylic acid (b) and its acid anhydride (b') used in the production method of the present invention include the same acids as the unsaturated carboxylic acids and their acid anhydrides exemplified as the unsaturated carboxylic acid (B) and its acid anhydride (B') constituting the acid-modified cycloolefin polymer, and the preferred acids are also the same.

[0049] The method for producing an acid-modified cycloolefin polymer of the present invention comprises a step of mixing and heating the cycloolefin polymer (a) and the unsaturated carboxylic acid (b) and / or its anhydride (b') in the absence of a radical polymerization initiator.

[0050] In the production method of the present invention, the step of mixing and heating the cycloolefin polymer (a) and the unsaturated carboxylic acid (b) and / or its anhydride (b') can be carried out by heating the cycloolefin polymer (a) and the unsaturated carboxylic acid (b) and / or its anhydride (b') in a reaction vessel while mixing them in the absence of a radical polymerization initiator.

[0051] In the step of mixing and heating the cycloolefin polymer (a) and the unsaturated carboxylic acid (b) and / or its anhydride (b'), the total weight proportion of the unsaturated carboxylic acid (b) and its anhydride (b') is 0.1 to 10% by weight, and preferably 1 to 15% by weight, based on the total weight of the cycloolefin polymer (a), the unsaturated carboxylic acid (b) and its anhydride (b'). If it is less than 0.1% by weight, the function as a resin modifier becomes insufficient, and if it exceeds 10% by weight, the color tone deteriorates.

[0052] The heating temperature in the step of mixing and heating the cycloolefin polymer (a) and the unsaturated carboxylic acid (b) and / or its anhydride (b') is preferably 100 to 270°C (more preferably 130 to 240°C), and the heating time is preferably 0.5 to 30 hours (more preferably 1 to 20 hours). The mixing and heating of the cycloolefin polymer (a) and the unsaturated carboxylic acid (b) and / or its anhydride (b') can be carried out using a known reactor equipped with a known mixing device and heating device, and can be carried out using the same continuous reaction vessels as those exemplified for the thermal degradation, such as stainless steel reaction vessels, tubular reactors, and extruders.

[0053] In the step of mixing and heating the cycloolefin polymer (a) and the unsaturated carboxylic acid (b) and / or anhydride thereof (b'), there is no limitation on the order in which the cycloolefin polymer (a) and the unsaturated carboxylic acid (b) and / or anhydride thereof (b') are charged into a reaction vessel, and they may be mixed in advance in a known mixer before being charged into the reaction vessel.

[0054] In the production method of the present invention, a cycloolefin polymer (a) and an unsaturated carboxylic acid (b) and / or an anhydride thereof (b') are mixed and heated in the absence of a radical polymerization initiator. The unsaturated carboxylic acid and its anhydride bond to the double bond of the cycloolefin polymer (a), thereby producing an acid-modified cycloolefin polymer. By carrying out the reaction in the absence of a radical polymerization initiator, the addition of the unsaturated carboxylic acid (b) and / or its anhydride (b') to the double bond of the cycloolefin polymer (a) proceeds preferentially, and the acid-modified cycloolefin polymer is effectively used as a resin modifier. When the reaction is carried out in the presence of a radical polymerization initiator, a hydrogen abstraction reaction by radical species generated by the radical polymerization initiator causes unsaturated carboxylic acid (b) and its anhydride (b') to be randomly added to sites other than the double bonds of the cycloolefin polymer (a), and the proportion of unsaturated carboxylic acid (b) and its anhydride (b') added to the terminal of the cycloolefin polymer (a) decreases, which presumably reduces the effect as a resin modifier and worsens the effect as a resin modifier (such as compatibility with cycloolefin polymers and cycloolefin copolymers).

[0055] The reaction rate of the addition reaction of the unsaturated carboxylic acid (b) and its anhydride (b') to the double bond of the cycloolefin polymer (a) can be calculated by nuclear magnetic resonance spectroscopy (NMR method).

[0056] The acid-modified cycloolefin polymer obtained by the production method of the present invention is preferably an acid-modified cycloolefin polymer having an unsaturated carboxylic acid or an acid anhydride thereof structure in the carbon-carbon double bond.

[0057] The production method of the present invention may further include a degassing step in which unreacted volatile matter and the like are degassed under reduced pressure. The degree of reduced pressure in the degassing step is preferably 0.07 to 2.7 kPa, more preferably 1 to 10 mmHg. The treatment time under reduced pressure is preferably 0.1 to 5 hours, more preferably 0.5 to 3 hours. [Example]

[0058] The present invention will be further explained below with reference to examples, but the present invention is not limited thereto.

[0059] <Production Example 1: Production of Cycloolefin Polymer by Thermal Degradation 1> A 3 L four-neck flask equipped with a nitrogen inlet tube, a thermometer, an exhaust gas distillation tube, and a stirrer was charged with cycloolefin polymer [ZEONOR1020R manufactured by Zeon Corporation, Tricyclo[4.3.0.1 2,5 1500 g of hydrogenated 2-3-decene polymer (number average molecular weight: 33,000) was charged under a nitrogen atmosphere. Nitrogen was continuously circulated through the flask until the end of the thermal degradation. The flask was then heated with a mantle heater, and the mixture was stirred at 370°C for 8 hours for thermal degradation. The product was then cooled to 200°C and removed from the flask. The resulting polymer (a1-1) had a number average molecular weight of 4,500 and 5.4 double bonds per 1,000 carbon atoms.

[0060] <Example 1: Production of Acid-Modified Cycloolefin Polymer 1> 400 g of the polymer (a1-1) obtained in Production Example 1 (hereinafter referred to as low-molecular-weight cycloolefin polymer (a1-1)) and 34.0 g of maleic anhydride [7.8 wt % based on the total weight of the low-molecular-weight cycloolefin polymer (a1-1) and maleic anhydride] were charged into a 1 L four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser, and a stirring rod, and while passing nitrogen through the flask, the flask was heated with a mantle heater, the temperature was increased, and the mixture was reacted at 195°C for 10 hours with stirring. After the reaction, the pressure inside the system was reduced while the temperature was maintained at 195°C, and then a degassing step was carried out for 1 hour under a pressure of 0.7 kPa to remove volatile components. After cooling to 160°C, the reaction product containing the acid-modified cycloolefin polymer 1 was taken out. The acid value of the acid-modified cycloolefin polymer 1 (hereinafter abbreviated as MP-1) was measured to be 19.9, and the number average molecular weight was 4,700. It was confirmed by NMR that polymer (a1-1) had reacted with maleic anhydride to produce an acid-modified cycloolefin polymer, and the weight ratio of the unsaturated carboxylic acid and its acid anhydride constituting the acid-modified cycloolefin polymer was 3.5 wt % based on the weight of MP-1.

[0061] <Production Example 2: Production of Cycloolefin Polymer by Thermal Degradation 2> Cycloolefin copolymer ["APL6015T", manufactured by Mitsui Chemicals, Inc., tetracyclo[4.4.0.1 2,5 .1 7,10 The same procedure as in Production Example 1 was carried out, except that the copolymer was ethylene-3-dodecene copolymer, ethylene content 73 mol %, number average molecular weight: 120,000, and thermal degradation was carried out at 360°C for 2 hours. The resulting polymer (a2-1) had a number average molecular weight of 3,000 and 8.3 double bonds per 1,000 carbon atoms.

[0062] <Example 2: Preparation of Acid-Modified Cycloolefin Polymer 2> The same procedure as in Example 1 was carried out except that 400 g of polymer (a2-1) obtained in Production Example 2 and 49.0 g of maleic anhydride [10.9 wt % based on the total weight of polymer (a2-1) and maleic anhydride] were used, to obtain acid-modified cycloolefin polymer 2. The acid value measured for acid-modified cycloolefin polymer 2 (hereinafter abbreviated as MP-2) was 30.1, and the number average molecular weight was 3,200. It was confirmed by NMR that the polymer (a2-1) had reacted with maleic anhydride to produce an acid-modified cycloolefin polymer, and the weight ratio of the unsaturated carboxylic acid and its acid anhydride constituting the acid-modified cycloolefin polymer was 5.3 wt% based on the weight of MP-2.

[0063] <Comparative Example 1> 400 g of polymer (a1-1) obtained in Production Example 1, 70.6 g of maleic anhydride [15.0 wt % based on the total weight of polymer (a1-1) and maleic anhydride], and 600 g of xylene were charged into a 2 L four-neck flask equipped with a nitrogen inlet tube, dropping funnel, thermometer, condenser, and stirrer. While passing nitrogen through the flask, the contents were heated with a mantle heater until the temperature rose to 195°C and the mixture was dissolved. Next, 1.5 g of di-tert-butyl peroxide was added via the dropping funnel, and the mixture was allowed to react for 4 hours. After the reaction, the mixture was dexylene-free under reduced pressure, and finally degassed at 195°C and under a reduced pressure of 5 mmHg for 1 hour to obtain a comparative acid-modified cycloolefin polymer (hereinafter abbreviated as MP-3). The acid value measured for MP-3 was 85.8, and the number average molecular weight was 5200. The reaction between polymer (a1-1) and maleic anhydride was confirmed by NMR, and the weight ratio of the unsaturated carboxylic acid and its acid anhydride constituting the acid-modified cycloolefin polymer was 15.0 wt% based on the weight of MP-3.

[0064] <Comparative Example 2> 400 g of polymer (a2-1) obtained in Production Example 2, 70.6 g of maleic anhydride [15.0 wt% based on the weight of polymer (a2-1)], and 600 g of xylene were charged into a 2 L four-neck flask equipped with a nitrogen inlet tube, dropping funnel, thermometer, condenser, and stirrer. While passing nitrogen through the flask, the contents were heated with a mantle heater until the temperature rose to 195°C and the contents were dissolved. Next, 1.5 g of di-tert-butyl peroxide was added via the dropping funnel, and the mixture was allowed to react for 4 hours. After the reaction, the mixture was dexylene-free under reduced pressure, and finally degassed for 1 hour at 195°C under a reduced pressure of 5 mmHg to obtain a comparative acid-modified cycloolefin polymer (hereinafter abbreviated as MP-4). The acid value measured for MP-4 was 85.8, and the number average molecular weight was 3500. The reaction between polymer (a2-1) and maleic anhydride was confirmed by NMR, and the weight ratio of the unsaturated carboxylic acid and its acid anhydride constituting the acid-modified cycloolefin polymer was 15.0 wt% based on the weight of MP-4.

[0065] Example 3 Using MP-1 obtained in Example 1 itself as a resin modifier for improving the compatibility of the polymer alloy, nylon 6 and a cycloolefin polymer were mixed under the following conditions. First, 70 parts of nylon 6 [trade name: UBE Nylon 6 1013B (manufactured by Ube Industries, Ltd.)], 30 parts of a cycloolefin polymer [trade name: ZEONOR1020R (manufactured by Zeon Corporation)], and 5 parts of the MP-1 obtained in Example 1 were melt-mixed in a twin-screw extruder (cylinder temperature: 280°C), and then further extruded at a cylinder temperature of 280°C and an injection pressure of 800 kg / cm. 2 Test specimens were prepared by injection molding at a mold temperature of 80°C. The prepared test specimen was fractured in liquid nitrogen, and the fracture surface was observed under an electron microscope. The observed image was analyzed to measure the number-average particle diameter of the cycloolefin polymer dispersed in nylon 6. The number-average particle diameter of the dispersed particles was 1 μm.

[0066] Example 4 The same procedures as in Example 3 were carried out except that MP-2 obtained in Example 2 was used instead of MP-1, and a cycloolefin copolymer [trade name: APL6015T, manufactured by Mitsui Chemicals, Inc.] was used instead of the cycloolefin polymer [trade name: ZEONOR1020R, manufactured by Zeon Corporation]. The number average particle size of the cycloolefin copolymer particles dispersed in nylon 6 was 2 μm.

[0067] <Comparative Example 3> The same procedure as in Example 3 was carried out except that MP-3 obtained in Comparative Example 1 was used instead of MP-1. The number average particle size of the cycloolefin polymer particles dispersed in nylon 6 was 25 μm.

[0068] <Comparative Example 4> The same procedure as in Comparative Example 3 was carried out, except that MP-4 obtained in Comparative Example 2 was used instead of MP-1. The number average particle size of the cycloolefin copolymer particles dispersed in nylon 6 was 30 μm.

[0069] <Comparative Example 5> Except for not using the acid-modified cycloolefin polymer, nylon 6 and cycloolefin polymer were melt-mixed in the same manner as in Comparative Example 3. The number average particle size of the cycloolefin copolymer particles dispersed in nylon 6 was 35 μm.

[0070] <Example 5> The MP-1 obtained in Example 1 was used as a resin modifier for improving the compatibility of the polymer alloy, and polyester and cycloolefin polymer were mixed under the following conditions. First, 70 parts of polyester [trade name: NES-2040 (manufactured by Unitika Ltd.)], 30 parts of cycloolefin polymer [trade name: ZEONOR1020R (manufactured by Zeon Corporation)], and 5 parts of MP-1 obtained in Example 1 were melt-mixed in a twin-screw extruder (cylinder temperature: 280°C), and then further extruded at a cylinder temperature of 280°C and an injection pressure of 800 kg / cm. 2 Test specimens were prepared by injection molding at a mold temperature of 80°C. The prepared test piece was fractured in liquid nitrogen, and the fracture surface was observed under an electron microscope. The observed image was analyzed to measure the number-average particle diameter of the cycloolefin polymer dispersed in the polyester. The number-average particle diameter of the dispersed particles was 2 μm.

[0071] <Comparative Example 6> Except for not using the acid-modified cycloolefin polymer, the polyester and the cycloolefin polymer were melt-mixed in the same manner as in Example 5. The number average particle size of the dispersed particles of the cycloolefin copolymer dispersed in the polyester was 25 μm.

[0072] Example 6 The MP-1 obtained in Example 1 was used as a resin modifier to improve the dispersibility of the filler, and the filler and cycloolefin polymer were mixed under the following conditions. First, 30 parts of glass fiber [trade name "FT157C", manufactured by Asahi Fiberglass Co., Ltd., fineness 2,200 tex, fiber diameter 16 μm], 70 parts of cycloolefin polymer [trade name: ZEONOR1020R (manufactured by Zeon Corporation)], and 5 parts of MP-1 obtained in Example 1 were melt-kneaded in a twin-screw extruder (cylinder temperature 300°C), and then further extruded at a cylinder temperature of 300°C and an injection pressure of 800 kg / cm. 2 A test piece was prepared by injection molding at a mold temperature of 80°C, and the bending strength (in accordance with ASTM D790) was measured. The bending strength of the test piece was 140 MPa.

[0073] <Comparative Example 7> Except for not using the acid-modified cycloolefin polymer, a test piece was prepared by melt-kneading glass fiber and cycloolefin polymer and injection molding in the same manner as in Example 6. The bending strength of the test piece was 80 MPa.

[0074] In Examples 3 and 4, in which nylon 6 and a cycloolefin polymer were mixed using the acid-modified cycloolefin polymer composition of the present invention as a resin modifier, the dispersed particle size of the cycloolefin polymer was smaller than in the comparative examples, demonstrating that the acid-modified cycloolefin polymer composition of the present invention has an excellent effect as a compatibilizer for polymer alloys. Furthermore, from Example 6 and Comparative Example 6, it can be seen that the acid-modified cycloolefin polymer composition of the present invention imparts excellent adhesion between the cycloolefin polymer and glass fiber, and that molded articles obtained by molding a resin composition comprising a cycloolefin polymer, glass fiber, and the acid-modified cycloolefin polymer composition have excellent mechanical properties. Examples 1, 3, 5 and 6 are reference examples. [Industrial Applicability]

[0075] The acid-modified cycloolefin polymer of the present invention can be used as a resin modifier, particularly for polymers containing cycloolefin as a constituent monomer.

Claims

1. The polymer is an adduct of a cycloolefin polymer (A) with an unsaturated carboxylic acid (B) and / or its acid anhydride (B'), and satisfies all of the following (1) to (3): A resin modifier comprising an acid-modified cycloolefin polymer, wherein the total weight ratio of structural units derived from an unsaturated carboxylic acid (B) and an acid anhydride (B') thereof contained in the acid-modified cycloolefin polymer is 5.3 to 10% by weight based on the total weight of the acid-modified cycloolefin polymer. (1) The acid-modified cycloolefin polymer has a number average molecular weight of 800 to 50,000. (2) The acid-modified cycloolefin polymer has an acid value of 0.1 to 60. (3) The resin modifier is used in a resin composition containing a cycloolefin polymer and a cycloolefin copolymer.

2. A method for producing an acid-modified cycloolefin polymer, comprising a step of mixing and heating a cycloolefin polymer (a) and an unsaturated carboxylic acid (b) and / or an anhydride thereof (b') in the absence of a radical polymerization initiator, wherein the method satisfies all of the following (1) to (4): (1) The number average molecular weight of the cycloolefin polymer (a) is 800 to 50,000. (2) The cycloolefin polymer (a) has carbon-carbon double bonds, and the number of carbon-carbon double bonds is 0.1 to 20 per 1,000 carbon atoms constituting the cycloolefin polymer (a). (3) The total weight ratio of the unsaturated carboxylic acid (b) and its acid anhydride (b') is 10.9 to 14% by weight based on the total weight of the cycloolefin polymer (a), the unsaturated carboxylic acid (b), and its acid anhydride (b'). (4) The acid-modified cycloolefin polymer is used in a resin composition containing a cycloolefin polymer and a cycloolefin copolymer.