JP5584952B2 - Process for producing unsaturated carboxylic acid grafted polyolefin - Google Patents

Description

  The present invention relates to an unsaturated carboxylic acid grafted polyolefin and a process for producing the same.

  Polyolefin is used in a wide range of fields because of its excellent mechanical strength, transparency, moldability, hygiene, etc., but since it is a nonpolar polymer for use as a laminate, various polar substances are used. The material has a problem inherent to low adhesion. In order to improve this problem, various improvements have been attempted so far. However, the adhesiveness is not sufficient, and in order to further improve the adhesiveness, for example, an unsaturated carboxylic acid or a derivative thereof is used. Grafted modified polyolefin resins have been proposed.

  As an example, it is known that an unsaturated carboxylic acid-grafted polyolefin is produced by dissolving a polyolefin in a solvent and grafting an unsaturated carboxylic acid, and examples of the solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, and aliphatic hydrocarbons such as pentane, hexane and heptane (Patent Document 1).

  However, these aromatic hydrocarbons have a relatively high boiling point, the reaction temperature is as high as 160 ° C., and the energy cost is high, and there is a possibility that the cost is high in the recovery process. On the other hand, aliphatic hydrocarbons such as hexane cannot be said to have sufficient solubility of polyolefin, and it is necessary to increase the melting temperature, and the energy cost is still high. Furthermore, the products obtained by these reactions have poor thermal stability, and problems of gel formation are often pointed out. For this reason, the manufacturing method of the unsaturated carboxylic acid graft polyolefin by which generation | occurrence | production of gel was suppressed and the new unsaturated carboxylic acid graft polyolefin which does not use said solvent was desired.

  Moreover, although the acid-modified polyolefin resin composition produced as described above has an effect of improving adhesiveness, improvement in adhesiveness is still required as the demand for adhesive polymers increases.

  On the other hand, as a method for producing an unsaturated carboxylic acid grafted polyolefin without using a solvent, a melting method in which an unsaturated carboxylic acid is grafted in a state where the polyolefin is melted is generally known. A method using an extruder without using a vessel is generally used. For example, a method using a twin-screw extruder having a vent port is mentioned (Patent Document 2).

  However, in the melting method, since the residence time in the extruder is relatively short, the graft reaction time cannot be secured, so it is generally difficult to increase the amount of unsaturated carboxylic acid compared to the graft reaction using a reactor. In addition, since the grafting reaction is localized, the product quality has an inherent disadvantage that it tends to be non-uniform. For this reason, the obtained product contained a gel and had problems to be improved such as generation of fish eyes when processed into a film. In addition, since it is necessary to melt the resin in the reaction, the reaction temperature becomes high, for example, 250 ° C. As a result, the unsaturated carboxylic acid volatilizes and evaporates, so it is not only necessary to charge an excess of unsaturated carboxylic acid. Due to the above-mentioned problem of the reaction time, the unsaturated carboxylic acid grafted polyolefin obtained by this method is not grafted with a sufficient amount of unsaturated carboxylic acid, and has, for example, adhesion to different materials such as metal materials and inorganic substances. Had the problem of being low. From these backgrounds, there has been a demand for a production method for obtaining an unsaturated carboxylic acid grafted polyolefin having improved adhesion, and an unsaturated carboxylic acid grafted polyolefin film that is excellent in adhesiveness with different materials and does not contain a gel. .

Japanese Patent Laid-Open No. 9-3138 JP 2002-187914 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an unsaturated carboxylic acid grafted polyolefin having excellent adhesiveness with not only plastic materials but also different materials and having a wide range of usefulness. .

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention does not include a gel insoluble in xylene heated to 140 ° C., and the graft amount of unsaturated carboxylic acid or a derivative thereof (hereinafter simply referred to as unsaturated carboxylic acid) is 0.1 to 10% by weight. It is an unsaturated carboxylic acid graft polyolefin characterized by these, and its manufacturing method.

  The present invention is described in detail below.

  The unsaturated carboxylic acid grafted polyolefin of the present invention does not contain a gel insoluble in xylene heated to 140 ° C. Including a gel insoluble in xylene heated to 140 ° C. not only greatly deteriorates the appearance of the product when it is formed into a film, but also depending on the amount of the gel, mechanical properties such as adhesive strength and durability are deteriorated and peeled off. Such problems arise.

  Moreover, the unsaturated carboxylic acid grafted polyolefin of the present invention has an unsaturated carboxylic acid graft amount of 0.1 to 10% by weight, preferably 0.5 to 8% by weight. If it is less than 0.1% by weight, the adhesiveness is insufficient and the practicality is lacking. On the other hand, if it exceeds 10% by weight, the melt viscosity of the polymer is high and the moldability is impaired, and the toughness as the adhesive layer is also inferior, so that it is not practical.

  Examples of the unsaturated carboxylic acid in the present invention include unsaturated monocarboxylic acids and derivatives thereof, unsaturated dicarboxylic acids and derivatives thereof, and acid anhydrides of unsaturated dicarboxylic acids and derivatives thereof. Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, and the like. Derivatives of unsaturated monocarboxylic acids include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl ( Examples include meth) acrylate, isopropyl (meth) acrylate, and butyl acrylate. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, and tetrahydrophthalic acid. Desaturated dicarboxylic acids include monomethyl maleate, dimethyl maleate, monoethyl maleate, and maleic acid. Examples include diethyl, monomethyl fumarate, dimethyl fumarate, monoethyl fumarate, and diethyl fumarate. Examples of the acid anhydrides of unsaturated dicarboxylic acid and derivatives thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride and the like. These may be used alone or in combination of two or more. In particular, from the viewpoint of adhesiveness, maleic anhydride alone or a combination of maleic anhydride and (meth) acrylic acid esters is preferable.

  Examples of the polyolefin in the present invention include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (L-LDPE), and very low density polyethylene (V-LDPE). Etc. Examples of linear low density polyethylene (L-LDPE) include ethylene-α-olefin copolymers such as ethylene-1-butene copolymer, ethylene-1-hexene copolymer, and ethylene-1-octene copolymer. Can be mentioned. Other ethylene copolymers such as ethylene-4-methylpentene-1 resin, ethylene-vinyl acetate copolymer (EVA) and saponified products thereof, ethylene-vinyl alcohol resin (EVOH), ethylene-propylene copolymer (EPM), etc. , Polypropylene homopolymer, polypropylene block copolymer, polypropylene random copolymer, and the like, and chlorinated products of these polyolefins can be used in the same manner.

  The polymerization method for synthesizing these polyolefins may be a generally known method, including high-pressure radical polymerization, medium-low pressure polymerization, solution polymerization, slurry polymerization, etc., and the catalyst used is a peroxide catalyst, Ziegler-Natta. Examples of the catalyst include metallocene catalysts, and polyolefins polymerized with these catalysts can be used.

  The melt mass flow rate (MFR), which is a measure of the molecular weight of the polyolefin used as a raw material of the present invention, is not particularly limited, but the solubility in a solvent is good even when heated, and the material strength of the final graft reaction product is increased. In order to maintain, it is preferably 0.01 to 50000 (g / 10 minutes), more preferably 0.01 to 100 (g / 10 minutes).

  Methods for chlorinating polyolefins are known. For example, a method of chlorinating polyolefins by bringing a solution dissolved in a halogen-based solvent such as carbon tetrachloride into contact with a chlorine-containing gas under ultraviolet irradiation (for example, JP 47-8643), a method of chlorinating olefins by blowing chlorine gas into a slurry in which polyolefin powder is suspended in water (for example, Japanese Examined Patent Publication No. 36-4745), a polyolefin without using a solvent. Is heated above its melting point and brought into contact with chlorine gas in a molten state, whereby a polyolefin is chlorinated without using a radical generator, ultraviolet irradiation or the like (for example, JP-A-3-199206) Is disclosed. The chlorinated polyolefin used in the present invention can be produced by any of these methods, and the production method of the chlorinated polyolefin is not limited.

  The method for producing an unsaturated carboxylic acid grafted polyolefin according to the present invention comprises an alcohol compound and / or an epoxy compound contained as an impurity in 1,1,2-trichloroethane as a solvent when an unsaturated carboxylic acid is grafted to a polyolefin in a solvent. 1,1,2-trichloroethane from which is removed is used.

  The grafting reaction of unsaturated carboxylic acid is carried out by using a radical generator as a catalyst and a polyolefin in 1,1,2-trichloroethane from which alcohol compounds and / or epoxy compounds contained as impurities in 1,1,2-trichloroethane are removed. This is done by reacting with an unsaturated carboxylic acid.

  Furthermore, in the method for producing an unsaturated carboxylic acid graft polyolefin of the present invention, the reaction temperature is 40 to 130 ° C. If the reaction temperature is less than 40 ° C., a sufficient amount of unsaturated carboxylic acid is not grafted and the quality is inferior. It is not preferable from both sides. The reaction temperature is preferably 60 to 130 ° C.

  The reaction pressure is 1 MPa or less because a high-pressure reaction requires a special reaction apparatus and the reaction operation is complicated, leading to an increase in production cost. Preferably it is 0 to 0.7 MPa. In this reaction, depending on the reaction temperature and the type of polyolefin to be reacted, the grafting reaction proceeds from a uniform solution state to a suspended state, but the grafting reaction proceeds in the uniform solution state as much as possible. It is preferable to select the temperature appropriately.

  As the radical generator, an azo compound or an organic peroxide is used. Examples of the azo compound include α, α-azobisisobutyronitrile, azobiscyclohexanecarbonitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and the organic peroxide includes Examples include benzoyl peroxide, acetyl peroxide, t-butyl peroxide, and t-butyl perbenzoate.

  The amount of azo compound or organic peroxide added is not particularly limited, but the product maintains the graft amount of unsaturated carboxylic acid and prevents increase in melt viscosity of the resin to prevent deterioration of moldability. In order to maintain the quality, the amount is preferably 0.05 to 5 parts by weight, more preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the polyolefin.

  The unsaturated carboxylic acid and polyolefin used in the production method of the present invention are as described above.

  After completion of the grafting reaction, a stabilizer is added as necessary. It is preferable to use an antioxidant that is added to the stabilizer to eliminate radicals generated during the grafting reaction and stop the grafting reaction, and is usually added to polyolefins. For example, phenolic antioxidants, phosphorous antioxidants. Agents, sulfur-based antioxidants, and composite antioxidants thereof are preferably used.

  As the reaction vessel used for the grafting reaction, a vessel used for a batch-type reaction can be used. Any material can be used as long as it can withstand the above reaction temperature and reaction pressure, and the material is usually made of stainless steel. If necessary, it is possible to use a glass lining and fluorine coating treated on the inner surface.

  In the method of separating the unsaturated carboxylic acid grafted polyolefin produced by the graft reaction from the solvent, both are separated by a commonly used method such as steam distillation or a vented extruder.

  It is important that 1,1,2-trichloroethane used as a reaction solvent in the present invention is reacted by removing an alcohol compound and / or an epoxy compound from 1,1,2-trichloroethane. Commercially available 1,1,2-trichloroethane often contains 0.5 to 2.0% by weight of an alcohol compound and / or an epoxy compound as impurities. The alcohol compound here is a compound having a hydroxyl group, and examples thereof include ethyl alcohol and butyl alcohol. The epoxy compound here is a compound having an epoxy group, and examples thereof include 1,2-epoxypropane and 1,2-epoxybutane.

  Unsaturated carboxylic acid-grafted polyolefin synthesized with 1,1,2-trichloroethane containing an alcohol compound and / or epoxy compound as an impurity is colored pale yellow and has poor thermal stability, resulting in gel formation. The tendency is strong. That is, when it is used for film applications, it has a problem that it is difficult to be colored because it is inferior in color tone and transparency. Product value is lost. Even when it is used as a raw material for an adhesive, the gel component is not dissolved in a solvent, so that it cannot be practically used as an adhesive raw material.

  Unsaturated carboxylic acid grafted polyolefin synthesized using 1,1,2-trichloroethane from which alcohol compound and / or epoxy compound has been removed as a solvent is colorless and transparent, has good thermal stability, no gel generation, and only plastic material In other words, it becomes an unsaturated carboxylic acid grafted polyolefin having commercial value and excellent adhesion to different materials.

  The unsaturated carboxylic acid grafted polyolefin according to the present invention is, for example, an unsaturated carboxylic acid grafted polyethylene, an unsaturated carboxylic acid grafted ethylene / propylene copolymer, an unsaturated carboxylic acid grafted ethylene according to the kind of the raw material polyolefin as described above. -Butene copolymer, unsaturated carboxylic acid grafted ethylene / hexene copolymer, unsaturated carboxylic acid grafted ethylene / vinyl acetate copolymer, unsaturated carboxylic acid grafted polypropylene, etc.

  Other resins can be blended in the unsaturated carboxylic acid grafted polyolefin of the present invention. Examples of the other resin include not only the above polyolefin resin not subjected to graft reaction, but also styrene resins such as polystyrene, poly-α-methylstyrene, polystyrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene resin, and the like. Acrylic resins such as acrylic acid and polymethyl methacrylate-polyvinyl chloride resin, polyvinylidene chloride resin, polyamide, polyester, polycarbonate resin, fluorine resin, silicone resin, polyphenylene oxide resin (PPO), polyphenylene sulfide resin (PPS), polyimide, polysulfone, polyethersulfone, polyether-etherketone, polybutylene terephthalate resin (PBT), polyoxymethylene resin (POM), epoxy resin Polyurethanes, urea resins, phenol resins, melamine resins, cellulose, and petroleum resins. If necessary, it is possible to chemically react a reactive functional group or other resin having a terminal group with the unsaturated carboxylic acid group of the present invention, utilizing the physical interaction between these functional groups. Blending is possible. Furthermore, a coupling agent such as a silane coupling agent or a titanium coupling agent can be added as a third component to improve compatibility with other resins, or to improve adhesiveness.

  An elastomer or a rubber component can be blended with the unsaturated carboxylic acid grafted polyolefin of the present invention. Examples of the elastomer or rubber component include natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber, ethylene-propylene rubber, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin rubber, nitrile rubber, and acrylic rubber. , Urethane rubber, silicone rubber, fluorine rubber and the like. Also, as thermoplastic elastomer (TPE), SBS, SIS and other styrene TPE (SBC), polyolefin TPE (TPO), urethane TPE (TPU), polyester elastomer (TPEE), polymeramide elastomer (TPA), Examples include silicone-based TPE and fluorine-based TPE.

  The following various additives can be mix | blended with the unsaturated carboxylic acid graft polyolefin of this invention. Antioxidants include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, composite antioxidants of these, etc. Other stabilizers include organic phosphite stabilizers, thioether stabilizers Agents, hindered amine light stabilizers and the like. Moreover, as a filler, a spherical filler, a plate-like filler, a fibrous filler etc. are mentioned, for example. Furthermore, as a lubricant, higher fatty acid metal salts such as magnesium salts of higher fatty acids such as stearic acid, oleic acid, lauric acid, alkaline earth metal salts such as calcium salts and barium salts, cadmium salts, zinc salts, lead salts, and Examples thereof include alkali metal salts such as sodium salt, potassium salt and lithium salt. Examples of other additives include flame retardants, antistatic agents, colorants, natural oils, synthetic oils, waxes, plasticizers, nucleating agents, heavy metal deactivators, and the like.

  For mixing the unsaturated carboxylic acid grafted polyolefin of the present invention with other resins, elastomers or rubber components, and various additives, a commonly used kneading method can be used. Single screw extruder, twin screw extruder, Brabender internal A mixer, a Banbury mixer, a roll, a kneader, a Henschel mixer, a V blender, a tumbler mixer, etc. are mentioned.

  The unsaturated carboxylic acid grafted polyolefin of the present invention can be formed into a film by a known method, and as a film forming method, a solution casting method can be used in addition to a melt extrusion method. In the case of using the melt molding method, a normal molding method for processing a polyolefin resin can be used, such as inflation film molding, cast molding, extrusion lamination molding, calendar molding, sheet molding, fiber molding, blow molding, injection molding, rotational molding. And coating molding. In various film moldings, coextrusion molding and multilayer lamination molding using the unsaturated carboxylic acid grafted polyolefin of the present invention in at least one layer on one side are possible. On the other hand, cast film formation using a solvent is also possible.

  As a base material for multilayering, not only resin films such as polyamide, polyester, ethylene-vinyl alcohol resin, but also lamination with different materials such as paper, aluminum foil, stainless steel foil, copper foil and other metal foil, glass etc. Is possible.

  When using the solution casting method, for example, a solution prepared by dissolving the unsaturated carboxylic acid grafted polyolefin of the present invention in a solvent such as 1,1,2-trichloroethane, chloroform or methyl ethyl ketone is cast on a polyethylene terephthalate film, and the solvent is volatilized. A film can be formed by removing the film.

  Multilayer film, multi-layer sheet, multi-layer extrusion lamination molded body, multi-layer film in which monolayer film or mono-layer sheet of unsaturated carboxylic acid grafted polyolefin of the present invention is laminated with other resin, or other materials including inorganic and metal materials It is possible to produce blow containers, multilayer two-color molded bodies, multilayer profile extrusion molded bodies, insert injection molded bodies with metal members, and the like. Specifically, food packaging films, food containers, or gasoline tanks with multilayered EVOH films or sheets as barrier layers, multilayer fibers, steel pipe coatings, stainless steel plates, colored steel plates, copper-laminated laminated films, copper wire surface adhesion Coated products in which the surface or inner surface of a metal material typified by an agent, copper wire coating, etc. is coated with the unsaturated carboxylic acid grafted polyolefin of the present invention, or a multilayer in which the inner layer has a resin and their foams and the surface is a metal Intermediate adhesive layer between surface metal layer and inner resin layer in molded body, intermediate film for laminated glass used for bonding inorganic glass, intermediate film used for bonding optical film and glass, various resins and inorganic filler, nano Examples include compatibilizers, paints, and inks that have increased affinity with fillers or pigments.

  Further, the unsaturated carboxylic acid grafted polyolefin of the present invention can be used as a heat-fusible film, and this heat-fusible film is an intermediate adhesive layer of a laminate composed of various thermoplastic resins and metals, or an insulating material. Can be suitably used as an adhesive intermediate adhesive layer. In this application, the resin of the present invention can be formed into a film and used as a heat-fusible film. Adhesive resins include condensation polymers represented by polyesters such as polyimide, polyphenylene sulfide, polycarbonate, polyamide, and polyethylene terephthalate, coordination polymers such as polymers derived from radical polymerization such as EVOH, metallocene catalysts, and Ziegler catalysts. Various polyolefins obtained by the above are exemplified, and can be suitably used as an intermediate adhesive layer of various laminates formed using glass, metal or the like as a base material layer. Furthermore, if necessary, the resin of the present invention is further laminated on a multilayer laminate formed from a metal material or a resin material, or on a multilayer laminate film by a thermal fusion method, so that it can be easily applied to a metal material or various resin materials. It becomes possible to produce a multilayer laminate or a multilayer laminate film that can be assembled.

  Unsaturated carboxylic acid grafted polyolefin obtained by the present invention is free from gel generation, has improved adhesion, and has a property capable of easily and firmly thermally bonding a wide range of materials including metal materials. Therefore, it can be applied to a very wide range of industries. Furthermore, the present invention provides a low-cost method for producing an unsaturated carboxylic acid grafted polyolefin having improved adhesion to different materials without using aromatic hydrocarbons or aliphatic hydrocarbons from the viewpoint of energy cost.

  EXAMPLES Next, the present invention will be described in more detail based on examples, but these are examples for helping understanding of the present invention, and the present invention is not limited by these examples.

  In addition, the value used in these Examples was obtained based on the following measuring methods.

<Raw material>
The following raw materials were used in the examples of the present invention.

(1) EVA
Ethylene / vinyl acetate copolymer: Ultrasen (registered trademark) 751 manufactured by Tosoh Corporation (vinyl acetate content = 28 wt%, MFR = 5.7 g / 10 min, density = 952 kg / m ³ )
(2) L-LDPE
Ethylene / hexene-1 copolymer: Nipolon-Z (registered trademark) ZF230 (MFR = 2.0 g / 10 min, density = 920 kg / m ³ ) manufactured by Tosoh Corporation
(3) PP
Homopolypropylene: Chisso Polypro XF1811 manufactured by Chisso Petrochemical Co., Ltd. (MFR = 2.5 g / 10 min, density = 900 kg / m ³ )
(4) HDPE
High density polyethylene: Nipolon Hard (registered trademark) 4000 manufactured by Tosoh Corporation (MFR = 5.0 g / 10 min, density = 965 kg / m ³ )
(5) Benzoyl peroxide (BPO)
NIPPER B made by NOF Corporation
(6) Di (2-t-butylperoxyisopropyl) benzene (DBPIB)
Perbutyl P manufactured by Nippon Oil & Fat Co., Ltd.
(7) 2,6-di-tert-butyl-p-cresol (BHT)
API Corporation Yoshinox BHT
(8) Maleic anhydride, acrylic acid, butyl acrylate, 1,1,2-trichloroethane, xylene, methanol, dimethylformamide, BHT, 26% sulfuric acid aqueous solution, thymol blue indicator, N / 20 KOH solution is Kanto Chemical Co., Inc. A first grade reagent manufactured by company was used.

<Adhesion test>
The following resins and metals were used for the adhesion test.

(1) Polyimide film UPILEX (registered trademark) 755 manufactured by Ube Industries, Ltd.
(2) Polycarbonate film Panlite (registered trademark) PC-2151 manufactured by Teijin Chemicals Limited
(3) Polyphenylene sulfide (PPS)
Tosoh Co., Ltd. Sustil (registered trademark) GS40
(4) Copper plate Niraco Co., Ltd. CU-113328 0.10m
(5) Aluminum plate manufactured by Toyo Aluminum Co., Ltd. Count: A1N30H-H18 Thickness: 100 μm
<Acid value>
A polymer sample (1 g) is weighed and dissolved in 100 ml of toluene by heating, and then 10 ml of methanol, 10 ml of dimethylformamide and 0.5 ml of water are added. Subsequently, 1 ml of thymol blue indicator was added, titrated with an N / 20 KOH solution (n-propanol / benzene solution), and the point where the blue-violet color persisted for 1 minute or longer was calculated as the end point.

<Melt Mass Flow Rate (MFR)>
Melt mass flow rate (MFR) conforms to JISK6922-1 for polyethylene, JISK6924-1 for ethylene vinyl acetate copolymer, and JISK6921-2 for polypropylene, respectively. The measurement was performed under the conditions of a measurement temperature of 190 ° C. and a load of 2.16 kgf.

<Measurement of gel fraction>
After 50 mg of polymer was added to 50 ml of xylene and dissolved at 140 ° C. for 12 hours, this solution was filtered through a 200 mesh stainless steel mesh (75 μm), and the unmelted portion on the wire mesh was dried at 105 ° C. for 5 hours. Calculated.

<Measurement of Yellow Index (YI)>
In accordance with JIS K7105 (1981 edition), a heating compression temperature of 150 ° C., a pressure of 10 MPa, 10 minutes, a cooling temperature of 30 ° C., a pressure of 10 MPa using a reciprocating compression molding machine WFA-50 manufactured by Shinto Metal Industries, Ltd. YI of a film having a thickness of 100 μm pressed under conditions of 5 minutes was measured using an SM color computer manufactured by Suga Test Instruments Co., Ltd.

<Amount of 1-butanol and 1,2-epoxybutane in 1,1,2-trichloroethane>
A gas chromatograph apparatus (0.5 μl of 1,1,2-trichloroethane was collected by a microsyringe and attached with a GC capillary column DB-1301 (Agilent Technologies, Inc., length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm)) Shimadzu Corporation GC-14A) was measured under the following conditions.

Injection temperature: 40 ° C
Injection temperature holding time: 4 minutes Temperature rising program 1: 5 ° C / minute (40 ° C to 90 ° C)
Temperature rising program 2: 10 ° C./min (90 ° C. to 190 ° C.)
Final temperature: 190 ° C
Final temperature holding time: 20 minutes Carrier gas: Helium <Adhesion test>
By using a reciprocating compression molding machine WFA-50 manufactured by Shindo Metal Industry Co., Ltd. as a press molding machine, under the press conditions of heating temperature 150 ° C., pressure 10 MPa, 10 minutes, cooling temperature 30 ° C., pressure 10 MPa, 5 minutes. A press film having a thickness of 100 μm was obtained. The film formed to a thickness of 100 μm and the adherend were heat bonded using a heat seal tester TP-701 manufactured by Tester Sangyo Co., Ltd. under the conditions of 180 ° C., 60 seconds, and 0.2 MPa. The adhesive strength was evaluated by a T-type peel test using a Tensilon universal tester RTE-1210 (Orientec Co., Ltd.) as a tensile tester under the condition of a tensile speed (peeling speed) of 300 mm / min.

Example 1
5,000 parts by weight of 1,1,2-trichloroethane manufactured by Kanto Chemical Co., Ltd. and 2500 parts by weight of 26% sulfuric acid aqueous solution were placed in a 10-liter flask with a lower mouth and stirred vigorously. After standing, the lower organic layer was extracted. Next, the extracted organic layer and 5000 parts by weight of distilled water were placed in a 10-liter flask with a lower mouth and stirred vigorously, and after standing, the operation of extracting the lower organic layer was repeated three times to remove impurities 1-butanol and 1, 2-Epoxybutane was removed. Further, 150 parts by weight of molecular sieves 4A was added to the extracted organic layer, and dewatered by stirring with a stirrer.

  Into a 2-liter glass reaction vessel, 1250 parts by weight of 1,1,2-trichloroethane from which 1-butanol and 1,2-epoxybutane were removed by the above operation, 100 parts by weight of EVA, and 2 parts by weight of maleic anhydride were charged. . The temperature of the reactor was raised to 80 ° C., and then maintained at 80 ° C. for 3 hours to uniformly dissolve EVA. During this time, nitrogen gas was introduced into the reactor at a flow rate of 5 liters / minute to eliminate air mixed in the reactor. Next, the temperature of the reactor was raised from 80 ° C. to 110 ° C., and 0.8 parts by weight of BPO was removed from 1-butanol and 1,2-epoxybutane as a graft reaction catalyst (radical generator). The grafting reaction was carried out while continuously adding the catalyst solution dissolved in 50 parts by weight of 2-trichloroethane to the reactor over 3 hours. Subsequently, the reaction was continued for 2 hours at the same temperature. The reactor pressure was kept below 1 MPa throughout the reaction. After completion of the reaction, the pressure was returned to normal pressure and the temperature of the reactor was lowered to 70 ° C. Thereafter, 0.03 part by weight of BHT was added as a stabilizer, and this solution was reprecipitated with methanol to separate the unsaturated carboxylic acid graft EVA as a product from the solvent.

  The product was analyzed and found to have 1.8% by weight of unsaturated carboxylic acid. The gel was 0% by weight, YI was 2, and the hue was good. Moreover, the adhesive strength with copper, aluminum, polyimide, polycarbonate, and PPS was 52, 60, 39, 35, and 36 N / 15 mm, respectively, and it adhered firmly to various adherends. Table 1 shows the results of measurement of gel, hue, and adhesive strength.

実施例２
ラジカル発生剤の添加量を０．１６重量部に変えた以外は実施例１と同一の方法で反応を行い、続いて生成物を分離した。

Example 2
The reaction was carried out in the same manner as in Example 1 except that the amount of radical generator added was changed to 0.16 parts by weight, and then the product was separated.

  The product was analyzed and found to have 1.5% by weight unsaturated carboxylic acid. The gel was 0% by weight, YI was 2, and the hue was good. Moreover, the adhesive strength with copper, aluminum, polyimide, polycarbonate, and PPS was 42, 53, 37, 37, and 35 N / 15 mm, respectively, and it adhered firmly to various adherends. Table 1 shows the results of measurement of gel, hue, and adhesive strength.

Example 3
The reaction was carried out in the same manner as in Example 1 except that the amount of maleic anhydride added was changed to 9.7 parts by weight and the amount of BPO added was changed to 3.0 parts by weight. Subsequently, the product was separated.

  The product was analyzed and found to have 2.1% by weight unsaturated carboxylic acid. The gel was 0% by weight, YI was 4, and the hue was good. Moreover, the adhesive strength with copper, aluminum, polyimide, polycarbonate, and PPS was 60, 66, 36, 35, and 40 N / 15 mm, respectively, and it adhered firmly to various adherends. Table 1 shows the results of measurement of gel, hue, and adhesive strength.

Example 4
The same method as in Example 1 except that the amount of maleic anhydride added was changed to 20 parts by weight, the amount of 1,1,2-trichloroethane added to 2000 parts by weight, and the amount of BPO added to 0.16 parts by weight. The reaction was followed by separation of the product.

  The product was analyzed and found to have 3.0% by weight unsaturated carboxylic acid. The gel was 0% by weight, YI was 4, and the hue was good. Moreover, the adhesive strength with copper, aluminum, polyimide, polycarbonate, and PPS was 73, 80, 40, 39, and 40 N / 15 mm, respectively, and it adhered firmly to various adherends. Table 1 shows the results of measurement of gel, hue, and adhesive strength.

Examples 5-7
Example 1 and the base polymer were changed from EVA to L-LDPE, HDPE, PP, and the addition amount of maleic anhydride was changed to 30 parts by weight and the addition amount of 1,1,2-trichloroethane was changed to 2200 parts by weight ( The reaction was carried out in the same manner as in Example 1 except for Example 6), followed by separation of the product. Table 1 shows the results of measurement of gel, hue, and adhesive strength. There was no gel, and both hue and adhesive strength were excellent.

Examples 8-11
The reaction was carried out in the same manner as in Examples 4 to 7 except that the addition amounts of 1,1,2-trichloroethane, unsaturated carboxylic acid and BPO were changed. Table 2 shows the results of separating the products and measuring the gel, hue, and adhesive strength. There was no gel, and both hue and adhesive strength were excellent.

実施例１２〜１５
原料のポリオレフィンとしてＥＶＡ、Ｌ−ＬＤＰＥ、ＰＰ、ＨＤＰＥを用い、無水マレイン酸をアクリル酸へ変え、またＢＰＯの添加量を変えた以外は実施例１と同様の手法により反応を行った。生成物を分離し、ゲル、色相、接着強度を測定した結果を表２に示す。ゲルはなく、色相、接着強度ともに優れていた。

Examples 12-15
The reaction was carried out in the same manner as in Example 1 except that EVA, L-LDPE, PP and HDPE were used as the raw material polyolefin, maleic anhydride was changed to acrylic acid, and the amount of BPO added was changed. Table 2 shows the results of separating the products and measuring the gel, hue, and adhesive strength. There was no gel, and both hue and adhesive strength were excellent.

Examples 16-17
The reaction was carried out in the same manner as in Example 1 except that maleic anhydride was changed to a maleic anhydride / butyl acrylate mixture and the addition amount of BPO was changed. Table 2 shows the results of separating the products and measuring the gel, hue, and adhesive strength. There was no gel, and both hue and adhesive strength were excellent.

Comparative Example 1
In a state where 100 parts by weight of EVA, 4 parts by weight of maleic anhydride and 0.03 part by weight of DBPIB were uniformly mixed in advance using a Henschel mixer, a twin-screw extruder (manufactured by Toyo Seiki, Labo Plast Mill L / D = 25, φ The reaction was conducted at 140 ° C. for the first barrel, 200 ° C. for the second barrel, and 200 ° C. for the third barrel under the conditions of 30 rpm to obtain maleic anhydride-modified EVA.

  As a result of analysis, the product was found to have a gel content of 0.1% by weight, a YI of 15 and a high yellowness. Moreover, the adhesive strength with copper, aluminum, polyimide, polycarbonate, and PPS was clearly inferior to the polymers obtained in the examples. Table 3 shows the results of measurement of gel, hue, and adhesive strength.

比較例２
変性に用いた樹脂をＥＶＡからＬ−ＬＤＰＥに変えた以外は比較例１と同様の手法により無水マレイン酸変性Ｌ−ＬＤＰＥを得た。

Comparative Example 2
Maleic anhydride-modified L-LDPE was obtained in the same manner as in Comparative Example 1 except that the resin used for modification was changed from EVA to L-LDPE.

  As a result of analysis, the product was found to have 0.08% by weight of gel, YI was 13 and high yellowness. Moreover, the adhesive strength with copper, aluminum, polyimide, polycarbonate, and PPS was clearly inferior to the polymers obtained in the examples. Table 3 shows the results of measurement of gel, hue, and adhesive strength.

Comparative Example 3
Maleic anhydride-modified PP was obtained in the same manner as in Comparative Example 1 except that the resin used for modification was changed from EVA to PP.

  As a result of analysis, the product was found to have a gel content of 0.04% by weight, a YI of 11 and a high yellowness. Moreover, the adhesive strength with copper, aluminum, polyimide, polycarbonate, and PPS was clearly inferior to the polymer obtained in the examples. Table 3 shows the results of measurement of gel, hue, and adhesive strength.

Comparative Example 4
Maleic anhydride-modified HDPE was obtained in the same manner as in Comparative Example 1 except that the resin used for modification was changed from EVA to HDPE.

  As a result of analysis, the product was found to have a gel content of 0.06% by weight, a YI of 11 and a high yellowness. Moreover, the adhesive strength with copper, aluminum, polyimide, polycarbonate, and PPS was clearly inferior to the polymers obtained in the examples. Table 3 shows the results of measurement of gel, hue, and adhesive strength.

Comparative Examples 5-8
A polymer obtained by grafting an unsaturated carboxylic acid in the same manner as in Example 1 except that the reaction solvent was changed from 1,1,2-trichloroethane to xylene and the addition amount of maleic anhydride and the addition amount of BPO were changed. Got. Although the amount of unsaturated carboxylic acid introduced into the base polymer was small and the hue was excellent, it was clearly inferior to the polymers obtained in the examples. Table 3 shows the results of measurement of gel, hue, and adhesive strength.

Comparative Examples 9-12
A polymer grafted with acrylic acid was obtained in the same manner as in Comparative Examples 1 to 4 except that maleic anhydride was changed to acrylic acid. The product contained a gel and was clearly inferior in both hue and adhesion to the polymers obtained by the examples. Table 4 shows the results of measurement of gel, hue, and adhesive strength.

比較例１３〜１６
反応溶剤を１，１，２−トリクロロエタンからトルエンに変更し、さらに、無水マレイン酸を無水マレイン酸及びアクリル酸ブチルの混合物に変え、その添加量を変えた以外は実施例１〜４と同様の手法により不飽和カルボン酸をグラフトしたポリマーを得た。ベースポリマーに導入された不飽和カルボン酸量が少なく、実施例で得られたポリマーに対し明らかに接着性に劣っていた。ゲル、色相、接着強度を測定した結果を表４に示す。

Comparative Examples 13-16
The reaction solvent was changed from 1,1,2-trichloroethane to toluene, maleic anhydride was changed to a mixture of maleic anhydride and butyl acrylate, and the addition amount thereof was changed, and the same as in Examples 1 to 4 A polymer grafted with an unsaturated carboxylic acid was obtained by the method. The amount of unsaturated carboxylic acid introduced into the base polymer was small, and the adhesiveness was clearly inferior to the polymers obtained in the examples. Table 4 shows the results of measurement of gel, hue, and adhesive strength.

Comparative Example 17
Anhydrous malein was grafted onto EVA in the same manner as in Example 1 except that the reaction solvent was changed from purified 1,1,2-trichloroethane to unpurified 1,1,2-trichloroethane. Table 4 shows the analysis results and the adhesion test results of the obtained polymer. The product contained a gel, had a high YI value, was colored, and was inferior in product appearance.

Comparative Example 18
Anhydrous maleate was grafted onto EVA in the same manner as in Example 1 except that the reaction temperature was lowered from 110 ° C. to 35 ° C. The reaction temperature was low, EVA was not completely dissolved in the solvent, and the entire reaction solution was in a jelly form, and a uniform reaction could not be performed. Moreover, since the solution after the reaction was jelly and low in fluidity and could not be treated with a drum dryer, it was precipitated in methanol, then linearized with methanol, filtered, and dried under reduced pressure at 40 ° C. overnight for a polymer. Was isolated. Table 4 shows the analysis results and the adhesion test results of the obtained polymer. The adhesive strength was inferior.

Comparative Example 19
Anhydrous maleate was grafted onto EVA in the same manner as in Example 1 except that the reaction temperature was raised from 110 ° C to 135 ° C. Table 4 shows the analysis results and the adhesion test results of the obtained polymer. The product contained a gel, had a high YI value, was colored, and was inferior in product appearance.

Claims (1)

When a graft reaction of an unsaturated carboxylic acid or a derivative thereof (hereinafter simply referred to as an unsaturated carboxylic acid) to a polyolefin in a solvent, an alcohol compound and / or an epoxy compound contained as an impurity in 1,1,2-trichloroethane is used as a solvent. Using the removed 1,1,2-trichloroethane, having a reaction temperature of 40 to 130 ° C. and a reaction pressure of 1 MPa or less, containing no gel insoluble in xylene heated to 140 ° C., and A method for producing an unsaturated carboxylic acid-grafted polyolefin, wherein the unsaturated carboxylic acid graft amount is 0.1 to 10% by weight.