TW200925171A - Unsaturated carboxylic acid-grafted polyolefin and its manufacturing method - Google Patents

Abstract

To provide an unsaturated carboxylic acid-grafted polyolefin that exhibits excellent adhesive properties not only to a plastic material but also to different kinds of materials and is widely useful. The unsaturated carboxylic acid-grafted polyolefin contains no gel insoluble in xylene heated at 140[deg.]C and has a grafted amount of the unsaturated carboxylic acid of 0.1-10 wt.%. The manufacturing method of the grafted-polyolefin is also provided.

Description

200925171 IX. Description of the Invention [Technical Field] The present invention relates to an unsaturated carboxylic acid grafted polyolefin, a process for producing the same, and use thereof. [Prior Art] Polyolefin is used in a wide range of fields because it is excellent in mechanical strength, transparency, formability, hygiene, etc., but it is used as a laminate because 'polyolefin is a non-polar polymer, so there will be A problem inherent in materials with low adhesion of various polar substances. In order to improve this problem, various improvements have been tried so far, but the adhesion is not sufficient, and the adhesion is further improved. For example, a modified polyolefin resin in which an unsaturated carboxylic acid or a derivative thereof is grafted is proposed. For example, it is known that an unsaturated carboxylic acid grafted polyolefin is produced by dissolving a polyolefin in a solvent to graft an unsaturated carboxylic acid, and an aliphatic hydrocarbon or an aromatic hydrocarbon is used as the solvent, and benzene is exemplified. An aromatic hydrocarbon such as toluene or xylene or an aliphatic hydrocarbon such as pentane, hexane or heptane (Patent Document 1). However, since these aromatic hydrocarbons have a relatively high boiling point and a reaction temperature of 160 ° C, there is a problem that not only the heat energy cost is high but also the cost is high in the recovery step, and benzene or the like is used. From the viewpoint of the toxicity of the carcinogenic substance, it is desirable not to use it. On the other hand, the solubility of the aliphatic hydrocarbon such as hexane and the polyolefin is not sufficient. Therefore, it is necessary to increase the dissolution temperature and the heat cost is also high. That is, the unsaturated carboxylic acid is grafted to the polyolefin in solution -5 - 200925171

先前 Prior art manufacturing techniques have necessitated a high-cost process for wasting heat energy in order to remove the solvent. As described above, in the reaction in which an aromatic hydrocarbon is used in a solvent to graft an acid anhydride to a polyolefin, in order to remove the high-boiling aromatic hydrocarbon solvent to be used from the reactor, water and aromatic hydrocarbons are added by using added water. The solvent is azeotropic and the solvent is removed. However, since water is used in this method, the removal requires a large amount of heat energy, and thus it cannot be called an economically excellent process, so this improvement method is sought. Moreover, the process of adding water to the solution of the polymer to remove the organic solvent, because the polymer becomes a block in the end, requires a complicated and costly process to shape the polymer into a shape suitable for forming, that is, The shape of the particles, etc. Further, the product obtained by such a reaction is referred to as having a problem that the thermal stability is poor and the gel is often generated. Therefore, it is desirable to produce a lower cost manufacturing method of the unsaturated carboxylic acid grafted polyolefin which is inhibited without using the above solvent or gel. Further, the acid-modified polyolefin resin composition produced by the above-described method has an effect of improving the adhesion, but it is required to improve the adhesion as the thickness of the adhesive polymer is required. On the other hand, as a method for producing an unsaturated carboxylic acid grafted polyolefin which does not use a solvent, a melting method of grafting an unsaturated carboxylic acid in a state in which a polyolefin is melted is generally known, and the melting method is based on economic reasons. A method of using an extruder without using a reactor is generally used, and a method of using a two-axis extruder having an exhaust port is exemplified (Patent Document 2). However, the melting method is relatively short because of the short residence time in the extruder. It is not possible to confirm the grafting reaction time. Compared with the grafting reaction using the reactor, it is generally not only to increase the reaction amount of the unsaturated carboxylic acid. Difficulties, the grafting reaction is also local, and has the inherent disadvantage of the quality of the product becoming uneven. Therefore, there is a problem that the obtained product contains a gel, and when a film is formed into a film, fish eye or the like is improved. Further, in the reaction, since the resin must be melted, the reaction temperature becomes a high temperature of, for example, 250 ° C, and as a result, volatilization and evaporation of the unsaturated carboxylic acid are caused, not only the excess of the unsaturated and the carboxylic acid must be charged, In terms of reaction time, the unsaturated carboxylic acid grafted polyolefin obtained by this method may have a non-grafted sufficient amount of unsaturated carboxylic acid, for example, low adhesion to a dissimilar material such as a metal material or an inorganic substance. . From the background of the above, it is desirable to produce a method for producing an unsaturated carboxylic acid grafted polyolefin having improved adhesion, and excellent adhesion to a dissimilar material, and no gel or gel content. Saturated carboxylic acid grafted polyolefin. On the other hand, as a coating material suitable for a metal substrate requiring an insulating protective coating, a polyfluorene oxide composition, a polyvinylidene fluoride Q ethylene composition, an epoxy resin composition, etc., which are blended with a lubricant, are known. Thermosetting tree. Fat composition. However, these thermosetting resin compositions generally require a hardening time of several tenths of a unit of the hardening reaction, so that the workability is poor and the polyoxane composition (polyoxyalkylene-based hardened material) is high in cost. Further, although the epoxy resin composition is inexpensive, it has a weak change in the environmental temperature, and the heat is washed and destroyed, and the adhesive is peeled off from the adherend. In addition, when the metal insulator is made of a plastic such as polyimide or the like, it is extremely difficult to satisfy both the insulating property, the bonding strength with the metal, the mechanical strength such as bending and punching, and the thermal shock similar to that of the epoxy resin composition. 200925171 Intense temperature changes can cause problems such as cracking of the underlying layer and damage to the function of electronic parts. Therefore, it is relatively easy to manufacture, and further, a simple method which can be easily automated by means of continuous lamination or the like, and it is not necessary to apply a special treatment to the metal surface at a relatively low temperature and for a short time, and it is easy and strong to heat up. An insulating elastic layer of a metal substrate, that is, an elastic sheet, an elastic film, an elastic tape, or the like. 0 As a cheap material with excellent electrical insulation, polyolefin is suitable. However, in the use of a laminate, since polyolefin is a non-polar polymer, it has low adhesion to various polar substances and is suitable for metals. The adhesion is also extremely low. Therefore, in order to utilize a polyolefin which is inexpensive and excellent in moldability as a thermally conductive insulating material, various reviews for improving the adhesion are performed. One of the methods proposes, for example, a modified polyolefin resin grafted with an unsaturated carboxylic acid or a derivative thereof (Patent Document 1). Q However, the unsaturated carboxylic acid-grafted polyolefin obtained by such a prior art manufacturing process has a problem of low heat stability and gelation. In addition, although the adhesion as a resin for metal insulation is improved, when used as a laminate for two different materials, for example, a laminate of a metal and a plastic, the obtained laminate cannot withstand heat and seek elasticity. An insulating resin that is more abundant and excellent in adhesion. On the other hand, 'forms, sheets, and the like, such as vinyl chloride, styrene resin, and acrylic resin, which reproduce the high-grade feeling and texture of wood, such as the furniture, the interior wall, the interior parts of the automobile, and the decoration of the keyboard instrument. Film -8- 200925171, etc. (for example, Patent Document 3): However, it is impossible to reproduce the high-grade feeling and texture of real wood, so the use of wood itself as a decorative material is expected to be improved, in order to reproduce the texture and weight of wood. The desire to bring the wood directly to the metal is stronger. 〇

However, when the liquid material is subsequently applied to the metal and the metal, the liquid adhesive is uniformly applied over the entire area, and the coating is completed from the application to the subsequent interval, and then the subsequent layer is ensured. Uniformity is very difficult. In addition, because wood and metal have very different polarities, it is not easy to firmly adhere these different materials. Therefore, it is necessary to laminate a wood and a metal by a thin film at a relatively low temperature and for a short period of time without requiring a special surface treatment for metal or wood. On the other hand, the electronic circuit of an electronic device is generally a three-layer flexible copper laminate which is formed of a copper foil/adhesive/polyimine which is followed by a copper foil and a polyimide film. In the flexible copper clad laminate, a thermosetting epoxy resin is used in the case of the copper foil and the polyimide film described above (for example, Patent Document 4). Further, it is also known that a polyethylene-based thermosetting type adhesive is used in which a copper foil-coated polyimide pigment varnish is bonded to a polyimide under heating, and a metal foil/polyimine is used. The layer is flexible with a copper laminate (for example, Patent Document 5). In order to harden the polyimine, these methods are finally heat-treated at a temperature exceeding 300 °C. As described above, the prior art three-layer flexible copper laminate has a work hardness because it requires an epoxy resin for the subsequent use of the epoxy resin in the manufacturing step thereof, and the hardening reaction requires several tenths of hardening time. In addition, although the epoxy resin group -9 - 200925171 is inexpensive, it may not be able to withstand changes in the ambient temperature, because the material is destroyed by heat and the article is peeled off from the adherend. In addition, the two-layer laminate, in this manufacturing step, not only needs to coat the polyimide varnish, but also slowly increases the heat treatment step, and also needs to be treated at a high temperature of 300 ° C at the end, which requires cumbersome and thermal energy. Consumable manufacturing method.

Therefore, a flexible wiring board which is excellent in bending resistance, cold resistance, flexibility, and thermal punchability by being manufactured by a simple and economical method such as continuous lamination is sought. On the other hand, a film antenna is a film-shaped antenna in which an antenna circuit is formed on a plastic film having transparency by printing, vapor deposition, or the like, and is widely used in various portable terminals and automobile windows because of its thin thickness and light weight. Information terminals such as personal computers and window glass for residential use can also be applied to RFID (Radio Frequency Identification) such as IC TAG. However, the prior art film antenna has a single-sided coating adhesive (for example, Patent Document 6) or an adhesive tape (for example, Patent Document 7) because the film antenna itself does not have the Q property. The method of being glued. However, since this method requires a step of applying an adhesive to the film antenna or attaching the adhesive tape, a film antenna which can be more easily adhered to the adherend is sought. On the other hand, the formation of thin films used in semiconductor devices, flat-panel displays, recording media, etc., is now widely used in the industry by sputtering methods used to sputter the film materials (paired target bodies). Plating film -10-

❹ 200925171 In the forming step, although it is necessary to fix it to the vacuum chamber device as a backing plate used as an electrode, it is used in general, and the bonding of the paired target body and the backing plate is mainly made, for example, in Patent Document 8), and in this bonding The full side and back plate that must be connected, but because of this bonding step is a relatively inexpensive and simple joining method. On the other hand, the prior art, formed on a substrate, has been using a method by lithography. This method removes the desired conductor pattern and then removes it by etching, and forms a negative pattern of the anti-deposition plating to form a conductor pattern on the unlaminated copper substrate. Since these methods require complicated steps, a large amount of processing waste liquid generating brush is applied to the manufacture of electronic parts, which is called printable electric power, and is directly printed on the substrate as a method ink or a conductive paste for manufacturing a circuit board or an electronic part. By means of printable electronics, compared with the prior art method, the mask is made unnecessary, the manufacturing steps in the electricity are simplified in a large width, and the waste liquid such as the etching liquid is used. Will not produce, but also have a large effect. For example, gravure printing, offset printing, and inkjet printing have been reviewed by conductive inks, but inkjet printing has become a manufacturing process for saving heat energy because it wastes the necessary amount of ink where necessary, and in addition, screen printing In the middle, it can be printed at high speed, so it can be reached inside, but at this time, and practice. The prior art uses high-priced solder indium (the synthesis of the target body is cumbersome, so the method of seeking a more circuit pattern is known to have a partial removal method on the substrate, which is formed by an electroless circuit pattern, so in recent years, the ink is printed. The technology has been investigated, and the conductive method has been reviewed. The method of making lithography by using a lithography substrate or the like is a printing method based on the reduction of waste, and inks such as brushing and screen printing are not used. Oil, gravure printing to thermal energy reduction. -11 - 200925171 From this background, the printable conductive ink was reviewed, for example, by dispersing silver nanoparticles using a low molecular weight dispersant such as dodecylamine. A technique such as a conductive ink in an organic solvent (for example, Patent Document 9) 〇

However, since the solution is formed of, for example, only an organic solvent, a low molecular weight dispersant, and metal particles, the solution is applied to a substrate, and when the solvent is volatilized, a low molecular weight dispersant and metal particles are present. The adhesion between the formed film and the substrate such as plastic is low. Therefore, when a conductive ink is used, for example, when a circuit is formed on an insulating plastic film, problems such as peeling of the formed circuit occur. In addition, a silver particle dispersion paste containing an acid anhydride such as phthalic anhydride or an alkylamine such as dodecylamine or a thermosetting type phenol resin (for example, Patent Document 10) is disclosed. The hardening of the film formed thereon takes about one hour, and there is a problem that productivity is low. As a method of forming a metal film on a plastic surface for protecting or decorating a plastic surface, a method of plating (for example, Patent Document 11) or a method of vapor deposition of a metal (for example, Patent Document 12) has been disclosed. These methods have been pointed out that there are problems in that the manufacturing steps such as the pretreatment of the resin surface are complicated, and the vapor deposition time is long and the productivity is low. As a method of protecting and adoring such a plastic molded body, a method of vapor-depositing a metal on a plastic molded body is known, but it is not a method which is excellent in both productivity and cost. For the above reasons, it has been sought to form a film -12-200925171 in a state of being firmly adhered to various substrates of plastic, glass, enamel wafer, metal, etc., and a stable film can be formed by heat treatment for a short period of time. Inorganic fine particle dispersion.

[Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. OBJECTS TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide an unsaturated carboxylic acid graft polyolefin which is excellent not only in adhesion to a plastic material and a dissimilar material but also has wide usefulness. [Means for Solving the Problem] The present inventors have achieved the present invention by carefully examining the above-mentioned problems in order to solve the above problems. That is, the present invention relates to a gel which is characterized in that the gel which is insoluble in xylene heated to 140 ° C at -13 to 200925171 is less than 0.02% by weight, and the graft amount of the unsaturated carboxylic acid is 0.1~ 10% by weight of unsaturated carboxylic acid grafted polyolefin, a process for the production thereof, and uses thereof. Specifically, the present invention has the following constitution. (1) An unsaturated carboxylic acid grafted polyolefin characterized in that the content of the gel insoluble in xylene heated to 140 t is less than 0.02% by weight, and the graft amount of the unsaturated carboxylic acid is 0.1~ 10% by weight. (2) The unsaturated carboxylic acid grafted polyolefin according to (1) above, which is in the form of an insoluble gel in xylene heated to 140 °C. (3) A process for producing an unsaturated carboxylic acid grafted polyolefin according to the above (1) or (2), which is characterized in that, when a unsaturated carboxylic acid is graft-reacted to a polyolefin in a solvent, it is removed. 1,1,2-trichloroethane contained in the 1,1,2-trichloroethane and/or the impurity of the epoxy compound as a solvent, and the reaction temperature is 40 to 130 ° C. The pressure is 1 MPa or less 〇Q (4) A method for producing an unsaturated carboxylic acid grafted polyolefin according to the above (1) or (2), which is characterized in that it has a boiling point of 120 ° C or less at normal pressure. In the solvent, the unsaturated carboxylic acid is grafted into the grafting reaction step of the polyolefin; the solvent is removed by supplying the reaction solution after the grafting reaction to a drum dryer; the unsaturated product is isolated from the reaction product. The separation step of the carboxylic acid grafted polyolefin. (5) A heat-fusible film characterized by comprising the unsaturated carboxylic acid grafted polyolefin described in the above (1) or (2). (6) A multilayer laminate consisting of a metal layer and a resin layer to a layer of -14 to 200925171, and an elastic electrically insulating layer, and the metal layer and/or the resin layer and the elastic electrically insulating layer are The multilayer laminate, which is characterized by an elastic electrically insulating layer, is formed from the unsaturated carboxylic acid grafted polyolefin described in the above (1) or (2). (7) The multilayer laminate according to (6) above, wherein the metal layer and/or the resin layer and the elastic electrically insulating layer are bonded by heating and pressure bonding. (8) The multilayer laminate according to the above (6) or (7), wherein the 0 layer is further contained in an amount of 20 to 40 parts by weight based on 1 part by weight of the unsaturated carboxylic acid graft polyolefin. . (9) A flexible wiring film characterized by having a conductive layer formed of a metal on at least one side of a film formed of the unsaturated carboxylic acid grafted polyolefin described in the above (1) or (2) Circuit. (10) A conductive film characterized by comprising the conductive fine particles of the unsaturated carboxylic acid grafted polyolefin described in the above (1) or (2). (11) The conductive film according to the above (1), wherein the conductive fine particles are gold, silver, copper, molybdenum, nickel, carbon, tin, indium, palladium, rhodium, samarium, bismuth, antimony, aluminum. One or more kinds of fine particles selected from iron, indium, magnesium, platinum, rhodium, tin, zinc, cobalt, chromium, titanium, molybdenum, tungsten, and carbon black. (1) The conductive film according to the above (1) or (1), which contains 30 to 99 parts by weight of conductive fine particles with respect to 100 parts by weight of the unsaturated carboxylic acid graft polyolefin. . (13) A sputtering target, characterized in that the pair of target bodies and the back sheet are subjected to the conductive film -15-200925171 described in any one of the above (1 〇) to (1 2). to make. (14) An inorganic fine particle dispersion containing the unsaturated carboxylic acid graft polyolefin, the inorganic fine particles, and a solvent described in the above (1) or (2). (15) The inorganic fine particle dispersion according to the above (14), wherein the inorganic fine particles are gold, silver, copper, palladium, rhodium, samarium, bismuth, antimony, aluminum, iron, indium, magnesium, platinum, rhodium, tin. At least one type of fine particles selected from zinc, cobalt, nickel, chromium, titanium, giant, tungsten, and carbon black. [Effects of the Invention]

The unsaturated carboxylic acid-grafted polyolefin obtained by the present invention has industrial properties as long as the content of the gel is small and the adhesion is improved, and the properties of a wide range of materials including a metal material can be easily and firmly heated. It is applied to a wide range of applications; and, in view of thermal energy cost, a method for producing a low-cost unsaturated carboxylic acid grafted polyolefin which does not use an aromatic hydrocarbon or an aliphatic hydrocarbon and improves adhesion to a dissimilar material; Furthermore, it can be exhibited in a wide range of applications in which all of the properties of the unsaturated carboxylic acid grafted polyolefin of the present invention are utilized. [Best Mode for Carrying Out the Invention] The present invention will be described in detail below. The unsaturated carboxylic acid grafted polyolefin of the present invention has a gel content of less than 〇·〇2% by weight in the xylene heated to 14 (TC), even in xylene heated to 14 ° C. Containing an insoluble gel, when the content is less than 〇.〇2 -16- 200925171% by weight, although it is excellent in adhesion to a dissimilar material, it is heated to i4 〇 °c in order to make the adhesion more excellent. It is preferred that the gel is not contained insoluble, and the content of the gel which is insoluble in xylene heated to 140 ° C is 0.02% by weight or more 'the appearance of the product not only when the film is damaged by a large width but also because of the gel The amount of the unsaturated carboxylic acid-grafted polyolefin of the present invention, the amount of grafting of the unsaturated carboxylic acid is 0.1 to 0.1%, and the mechanical properties such as adhesion strength and durability of the adhesive are lowered. 10% by weight, preferably 0.5 to 8% by weight, and less than 〇·1% by weight, there is no sufficient adhesion and lack of practicality. Further, when it exceeds 1% by weight, the melt viscosity of the polymer is high and is damaged. In addition to formability, the toughness as the adhesive layer is also poor. In the present invention, examples of the unsaturated carboxylic acid include unsaturated monocarboxylic acids and derivatives thereof, unsaturated dicarboxylic acids and derivatives thereof, acid anhydrides of unsaturated dicarboxylic acids, and derivatives thereof. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, and isocrotonic acid; and examples of the unsaturated fluorinated monocarboxylic acid derivative include methyl (meth) acrylate and ethyl (methyl). Acrylate, η-propyl (meth) acrylate, isopropyl (methyl) propylene sulphuric acid vinegar, butyl acrylate, etc. As the unsaturated diterpenic acid, 'maleic acid, Fuma Examples of the unsaturated dicarboxylic acid derivatives include monomethyl maleate, dimethyl maleate, and monoethyl maleate. Diethyl maleate, monomethyl fumarate, dimethyl fumarate, monoethyl fumarate, diethyl fumarate, etc. as anhydrides and derivatives of unsaturated dicarboxylic acids, Examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride. -17-200925171 used singly or two kinds or more Merger with, in particular of the viewpoint of adhesive property, the maleic anhydride alone or maleic anhydride with (meth) acrylates combination.

In the present invention, examples of the polyolefin include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (L-LDPE), and ultra low density poly. Ethylene (V-LDPE) and the like. Examples of the linear low-density polyethylene (L-LDPE) include an ethylene-α-olefin copolymer such as an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-octene copolymer. Other examples include ethylene-4-methylpentene-1 resin, ethylene-vinyl acetate copolymer (EVA) and its alkali compound, ethylene-vinyl alcohol resin (EVOH), ethylene-propylene copolymer (EPM), and the like. A vinyl copolymer, a polypropylene homopolymer, a polypropylene block copolymer, a polypropylene random copolymer, etc., and the chloride of these polyolefins can also be used similarly. The polymerization method for synthesizing such polyolefins may be a generally known Q method, and may also be a high pressure radical polymerization, a medium pressure polymerization, a solution polymerization, a slurry polymerization, etc., and a catalyst may be used as the peroxide system. A catalyst, a sigma-tano-nata catalyst, an aromatic ring-olefin metal derivative catalyst, or the like can be used, and a polyolefin polymerized by such a catalyst can be used. The melt flow rate (MFR) of a simple standard of the molecular weight of the polyolefin which is a raw material of the present invention is not particularly limited, but is excellent even in the case of heating in order to improve the solubility in a solvent, and further, the last connection is maintained. The material strength of the branched reactant is preferably from 0.01 to 50,000 (g/min), more preferably from 0.01 to 100 (g/10 min). "18- 200925171

A method of chlorinating a polyolefin is known, for example, a method of dissolving a solution in a halogen-based solvent such as carbon tetrachloride, and contacting a chlorine-containing gas under ultraviolet irradiation to chlorinate a polyolefin (for example, JP-A-47-8643); a method of chlorinating an olefin by blowing chlorine gas into a slurry in which a powder of a polyolefin is suspended in water (for example, Japanese Patent Publication No. 3-6-47); a method of heating a polyolefin to a temperature above the melting point and contacting it with chlorine gas in a molten state 'chlorinating the polyolefin without using a radical generating agent, ultraviolet irradiation or the like (for example, special opening 3 - 1 9 9 2 06) Bulletin). The chlorinated polyolefin used in the present invention can be produced by any of these methods, and the method for producing the chlorinated polyolefin is not limited. The unsaturated carboxylic acid graft polyolefin of the present invention may, for example, be an unsaturated carboxylic acid grafted polyethylene, an unsaturated carboxylic acid grafted ethylene/propylene copolymer, or an unsaturated carboxylic acid, depending on the kind of the raw material polyolefin. Branch ethylene·butene copolymer, unsaturated carboxylic acid grafted ethylene/hexene copolymer, unsaturated carboxylic acid grafted ethylene/vinyl acetate copolymer, unsaturated carboxylic acid grafted polypropylene, etc. As a method for producing the unsaturated carboxylic acid grafted polyolefin of the present invention, two methods as disclosed below can be listed. The first production method of the unsaturated carboxylic acid grafted polyolefin of the present invention is carried out by grafting an unsaturated carboxylic acid to a polyolefin in a solvent, and removing 1,1,2-trichloroethane as a solvent system. The impurity is contained in the alcohol compound and/or the epoxy compound 1,1,2-trichloroethane. The grafting reaction of an unsaturated carboxylic acid is carried out by using a radical generating agent as a catalyst to remove 1,1,2-trichloroethane as an impurity and an alcohol compound and/or an epoxy compound. , 1,2-trichloroethane, polyolefin and unsaturated-19-

200925171 is carried out by reacting with a carboxylic acid. Further, the unsaturated carboxylic acid grafted polyolefin of the present invention has a reaction temperature of 40 to 130 ° C, a reaction temperature lower than a sufficient amount of the unsaturated carboxylic acid, and the quality is inferior and the temperature exceeds 130 ° C. The reaction temperature is preferably the reaction pressure because the production of the gel is relatively low on both sides, and the reaction temperature is preferably the reaction pressure. Because the high pressure reaction requires special handling, the reaction operation becomes complicated, and the manufacturing cost is below _ IMPa. Preferably, it is preferably 0 to 0.7 MPa. The type of the polyolefin to be reacted and reacted may be grafted in a uniform turbid state. However, the grafting reaction is carried out as much as possible in the state of the polyolefin. Therefore, the type of the polyolefin is preferably as appropriate. As the radical generator, an azo compound or the like is used, and examples of the azo compound include α,α-azozabicyclohexanecarbonitrile and 2,2'-azobis(2,4-dimethyl group). Examples of the pentyl organic peroxide include peracidified benzamidine, peracidified t-butyl, perbenzoic acid t-butyl, etc. The amount of the azo compound or the organic peroxide added is limited, but in order to maintain the unsaturated carboxylic acid The amount of grafting of the acid, the increase in the melt viscosity of the resin to prevent deterioration of formability, is preferably 0.05 to preferably 0.05 to 3 parts by weight based on 100 parts by weight of the polyolefin. Unsaturated carboxylic acid grafted polyolefin The first manufacturing method used in the manufacturing method is 40 °C, the poor connection is not good, the reaction quality is lowered, and the heat is 60 to 130. (: ° The reaction device is soaring, so the reaction temperature solution From the state to the suspension, the solution temperature is selected as the reaction temperature or the organic peroxide bisisobutyronitrile, the acrylonitrile, etc.; as the acetamidine and the peracid, there is no special, and the product is kept _5 parts by weight, and more Unsaturated carboxylic acid-20- 200925171, polyolefin, same as above. After completion, if necessary, a stabilizer is added, and the stabilizer is added to eliminate the radical generated during the grafting reaction and to stop the grafting reaction. It is generally preferred to use an antioxidant added to the polyolefin, such as a phenolic antioxidant. Phosphorus-based antioxidants, sulfur-based antioxidants, and such composite antioxidants are suitable for use.

The reaction vessel used for the grafting reaction can generally be used in a batch (intermittent) reaction, as long as it can withstand the above reaction temperature and reaction pressure. The material is usually made of stainless steel, and the inner surface can be used if necessary. Glass lining, fluorine coated processor. The method of separating the unsaturated carboxylic acid grafted polyolefin formed by the graft reaction from the solvent is carried out by a method generally used for steam distillation, an extruder equipped with a vent, a drum dryer or the like. It is important that the 1,1,2-trichloroethane used as the reaction solvent in the present invention is subjected to an anti-Q reaction after removing the alcohol compound and/or the epoxy compound from 1,1,2-trichloroethane. The 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 an impurity. The term "alcohol compound" herein means a compound having a hydroxyl group. For example, ethyl alcohol or butanol may be mentioned, and the term "epoxy compound" as used herein means a compound having an epoxy group, and examples thereof include 1,2-epoxypropane or 1,2-ring. Oxybutane and the like. The unsaturated carboxylic acid grafted polyolefin synthesized by using 1,1,2-trichloroethane containing an alcohol compound and/or an epoxy compound as a solvent is colored yellowish, and has poor thermal stability and gelation. The tendency is strong, that is, when using -21, 2009,171, for film use, there is a problem that it is difficult to color due to poor color tone and transparency. In addition, the gel significantly damages the film because it causes fish eyes during film formation. As a result of the appearance of the surface, the price of this commodity is lost. When used as a raw material for an adhesive, the gel component is not dissolved in a solvent, and in fact cannot be utilized as an adhesive material. The unsaturated carboxylic acid grafted polyolefin synthesized by using 1,1,2-trichloroethane as a solvent to remove the alcohol compound and/or the epoxy compound is colorless and transparent, and has excellent thermal stability and no gelation. When it occurs, it is an unsaturated carboxylic acid grafted polyolefin which is excellent not only in adhesiveness with a plastic material but also a dissimilar material, and is commercially expensive. The second production method of the unsaturated carboxylic acid grafted polyolefin of the present invention is carried out by the following series of steps, and the respective steps will be described below. (Step 1) a grafting reaction step (step 2) of grafting an unsaturated carboxylic acid to a polyolefin in a halogen-based solvent having a boiling point of 1 or less under normal pressure (step 2) by a reaction after grafting The solution is supplied to a drum 0 dryer to volatilize and remove a halogen-based solvent having a boiling point of 120 ° C or lower at normal pressure, and the separation step of the unsaturated carboxylic acid-grafted polyolefin of the reaction product is obtained by a polymer. Isolation requires a large amount of thermal energy solution method to carry out the graft reaction of the unsaturated carboxylic acid on the polyolefin, but it is found that the use of a low-boiling and non-combustible halogen-based solvent is used to separate the polymerization from the polymer solution by using a drum dryer. The method of the material can be used to isolate the polymer at a low cost and safely and easily. (Step 1) Grafting reaction step -22-200925171 The grafting reaction step of the unsaturated carboxylic acid is carried out by using a radical generating agent as a catalyst. The unsaturated carboxylic acid is reacted with a polyolefin in a halogen-based solvent having a boiling point of 120 ° C or less under normal pressure. The halogen solvent having a boiling point of 120 ° C or less at normal pressure used as a reaction solvent is used. Examples thereof include 1,1-dichloroethane, 1,2-dichloroethane, dichloromethane, chloroform, trichloroethane, 1,1,2-trichloroethane, carbon tetrachloride, and three. Chlorine solvent such as vinyl chloride or perchloroethylene, bromine 0 solvent such as brominated ethane, monofluorobenzene, 1,4-difluorobenzene, perfluoroheptane, perfluorooctane, dichloropentafluoropropane a solvent containing bromine and fluorine, such as a fluorine-based solvent, bromochloromethane or 1,2-dibromo-1,1-difluoroethane, but the boiling point and the solubility of the polyolefin are 1, 1,2-trichloroethane and chloroform are preferably used. When 1,1,2-trichloroethane is used as a solvent, impurities contained in the solvent, that is, alcohol compounds, and/or epoxy compounds are removed. The reaction temperature is not particularly limited, but in order to improve the efficiency of the graft reaction, the coloring and crosslinking of the unsaturated carboxylic acid grafted polyolefin are prevented, and it is preferably 40 to 130 ° C, more preferably It is preferably 60 to 130 ° C, and the reaction pressure is determined depending on the type of the solvent to be used and the reaction temperature, and is not particularly limited, but in order to eliminate the need for a special reaction device, Preferably, it is 0 to 1 MPa, more preferably 0 to 0_7 MPa. In the present reaction, depending on the reaction temperature and the type of polyorganic hydrocarbon to be reacted, a graft reaction may be carried out from a uniform solution state to a suspension state. However, the grafting reaction is carried out in a uniform solution state as much as possible, so that the reaction temperature is preferably selected depending on the type of the polyolefin. As the radical generating agent, an azo compound or an organic acid compound or the like is used as the azo compound. Examples thereof include α,α-azobisisobutylidene, even-23-200925171 nitrogen bicyclohexanecarbonitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and the like. Examples of the acid compound include peracid benzamidine, peracetate acetamidine, peracidified t-butyl group, and perbenzoic acid t-butyl group.

The amount of the azo compound or the organic peroxide to be added is not particularly limited, but in order to maintain the graft amount of the unsaturated carboxylic acid, the product is prevented from being lowered by preventing an increase in the melt viscosity of the resin. The quality is preferably 0.05 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, per 100 parts by weight of the polyolefin. The unsaturated carboxylic acid or polyolefin used in the production method of the unsaturated carboxylic acid grafted polyolefin is the same as described above. After completion of the graft reaction, a stabilizer is added as necessary, and a stabilizer is added to eliminate the radical generated during the graft reaction and to stop the graft reaction. The antioxidant to be added to the polyolefin is usually used. For example, a phenolic antioxidant, a phosphorus antioxidant, a sulfur-based antioxidant, or a composite antioxidant is preferably used. The reaction vessel used for the grafting reaction can generally be used in a batch (intermittent) reaction, as long as it can withstand the above reaction temperature and reaction pressure. The material is usually made of stainless steel, and the inner surface can be used if necessary. Glass lining, fluorine coated processor. (Step 2) Separation step As a method of separating a solvent from a reaction solution of a polyolefin grafted with an unsaturated carboxylic acid obtained by a graft reaction step, using a drum dryer, after the reaction step is finished, the reaction solution is removed from the reaction solution. The reactor was fed to a heated drum-24-200925171 dryer to isolate the product from the polymer solution. By using a drum dryer, there is no need for a complicated step of removing the reaction solvent to the outside of the reactor by heating, and the polymer can be economically separated by a comparatively low temperature, continuous and short time. The temperature of the drum dryer at this time is not particularly limited. However, in order to suppress coloring, thermal deterioration, and crosslinking of the polymer while continuously promoting drying, it is preferably in the range of 120 to 200 ° C, more preferably 150. At ~165 ° C, the polymer was isolated from the drum in the form of a film and isolated.

The time required for removing the solvent from the polymer solution by the drum dryer may be appropriately selected depending on the type of the solvent to be used and the temperature of the drum dryer, but it is usually 10 seconds to 5 minutes. In addition, chloroform, 1,1,2-trichloroethane, or the like, which is a halogen solvent having a boiling point of 120 ° C or less under normal pressure, which is volatilized by a drum dryer, is used in the upper portion of the drum dryer. The recovery line is recycled and can be reused in the reaction. The isolated polymer can be processed into a soft line, a flake, a strand or a sheet as necessary, and the polymer which has been shaped once is supplied to the 1 axis or, if necessary, to the 2 axis extrusion. The machine is extruded after the polymer is melted, cut in a single strand, or cut in water to pelletize. The extrusion temperature at this time is not particularly limited. However, in order to allow the polyolefin to be sufficiently melted and then smoothly extruded, and to suppress decomposition, coloring, and the like of the polyolefin, it is preferably 100 to 300 ° C, more preferably It is 150~2 5 0 °C. By this method, not only a plastic material, but also an unsaturated carboxylic acid graft polyolefin excellent in adhesion to a dissimilar material and excellent in color, can be obtained at low cost, easily, and safely. -25- 200925171 In the unsaturated carboxylic acid graft polyolefin of the present invention, other resins may be blended. As the other resin, for example, not only the above polyolefin resin to which no graft reaction is applied, but also polystyrene, poly-α-methylstyrene, polystyrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene Acrylic resin such as olefin resin, acrylic resin such as polyacrylic acid or polymethacrylic acid-methyl group, polyvinyl chloride resin, polyvinylidene chloride resin, polyamide, polyester, polycarbonate resin, fluorine Resin, polyoxyalkylene resin, polyphenylene ether resin (0 ΡΡΟ), polyphenylene sulfide resin (PPS), polyimine, polyfluorene, polyether oxime, polyetheretherketone, polyterephthalic acid Butylene glycol ester resin (ΡΒΤ), polyoxymethylene resin (ΡΟΜ), epoxy resin, polyurethane, urea resin, phenol resin, melamine resin, cellulose, petroleum resin, and the like. If necessary, the reactive functional group or other resin of the terminal group may be chemically reacted with the unsaturated carboxylic acid group of the present invention, or may be blended by physical interaction between the functional groups. Further, a coupling agent such as a decane coupling agent or a titanium coupling agent may be added as the third component, and Q may improve compatibility with other resins or improve adhesion. In the unsaturated carboxylic acid graft polyolefin of the present invention, an elastomer or a rubber component may be blended, and examples of the elastomer or rubber component include natural rubber, isoprene rubber, butadiene rubber, and styrene-butylene. Diene rubber, butyl rubber, ethylene-propylene rubber, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin rubber, nitrile rubber, acrylic rubber, urethane rubber, poly Alkane rubber, fluororubber, etc. Further, examples of the thermoplastic elastomer (TPE) include styrene-based TPE (SBC) such as SBS and SIS, polyolefin-based TPE (TPO), and urethane formate B-26-200925171 ester system (TPU). Ester-based elastomer (ΤΡΕΕ), polyamine-based elastomer (TPA), polyoxyalkylene-based TPE, and fluorine-based TPE. In the unsaturated carboxylic acid-grafted polyolefin, the following various additives may be blended; examples of the antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant such as a composite antioxidant; Examples of the stabilizer include an organic phosphite stabilizer, a thioether stabilizer, and a hindered amine light stabilizer; and examples of the chelating agent include a spherical ruthenium-filling agent and a plate-like chelating agent. As the adhesive, for example, liquid and solid bisphenol A epoxy resin, epoxy cresol novolac, epoxy phenol novolac, bisphenol A epoxy resin and epoxy cresol novolac Or a mixture with epoxy phenol novolacs bis bisphenol F epoxy resin, aliphatic epoxy resin, etc.; as the epoxy crosslinking agent, a wrong compound of boron trifluoride, dicyandiamide, polyamine Examples, polyamines, etc.; as a flame retardant, for example, bromination of ethylene bistetrabromophthalimide, decabromodiphenyl oxide, SA YTEX 8010, tetradecbromodiphenoxybenzene, etc. Flame retardant, tri-Q cerium oxide, antimony pentoxide, boric acid , a flame retardant such as FIREBRAKE ZB, a chlorinated flame retardant such as DECLORANE PLUS, etc.; as a slip agent, a magnesium salt of a higher fatty acid such as stearic acid, oleic acid or lauric acid of a higher fatty acid metal salt; An alkaline earth metal salt such as a calcium salt or a barium salt, a cadmium salt, a zinc salt or a lead salt, and an alkali metal salt such as a sodium salt, a potassium salt or a lithium salt; and examples of the other additives include an antistatic agent and a colorant. , natural oils, synthetic oils, waxes, plasticizers, nucleating agents, heavy metal inactivating agents, processing aids, waxes, arc inhibitors, alumina, decane-treated talc, mica, feldspar and wollastonite Drop inhibitors and the like. The amount of the additive to be added is not particularly limited to -27 to 200925171, but in order to exhibit the additive effect of the additive and to maintain the adhesion, it is 20 to 40 parts by weight based on 100 parts by weight of the unsaturated carboxylic acid graft polyolefin. Preferably. Further, the unsaturated carboxylic acid graft polyolefin of the present invention may contain conductive fine particles. Examples of the conductive fine particles include gold, silver, copper, molybdenum, nickel, carbon, tin, indium, palladium, ruthenium, osmium, iridium, osmium, aluminum, iron, indium, magnesium, platinum, rhodium, tin, and zinc. Cobalt, chromium, titanium, giant, tungsten, carbon black, and the like, the unsaturated carboxylic acid grafted polyolefin of the present invention is mixed with other resins, elastomers or rubber components, various additives, and conductive fine particles, and may be mixed with a solution or a conventional one. The kneading method used, as a kneading party, can be exemplified by a single-axis extruder, a two-axis extruder, a Brabender-type compacting machine, a Banbury kneading machine, a drum, a kneading machine, a Henry Shirley kneading machine, and a V Blending machine, drum mixing machine, etc. The unsaturated carboxylic acid-grafted polyolefin of the present invention can be formed into a film by a conventional method, and as a film forming method, a solution casting method can be used in addition to the melt extrusion method. When a melt forming method is used, a general processing method of a polyolefin resin can be used, and examples thereof include blown film forming, tape casting, extrusion lamination molding, calender molding, sheet molding, fiber molding, blow molding, and injection molding. , rotational molding, and coating. In various film forming, the co-extrusion or multi-layer synthesis of the unsaturated carboxylic acid grafted polyolefin of the present invention may be used on at least one side layer, and on the other hand, a cast film using a solvent may be used. Forming. The multilayered substrate is not only a resin film made of polyamine, polyester, or ethylene-B-28-200925171 enol resin, but also a metal foil such as paper, aluminum foil, stainless steel case, or copper foil. Lamination of different materials such as glass. When the solution casting method is used, for example, a solution in which the unsaturated carboxylic acid graft polyolefin of the present invention is dissolved in a solvent such as 1,1,2-trichloroethane, chloroform or methyl ethyl ketone may be cast. On the polyethylene terephthalate film, a film is formed by volatilization to remove the solvent. A single layer film 0 of the unsaturated carboxylic acid grafted polyolefin of the present invention, or a multilayer film, a multilayer sheet, a multi-layered film in which a single layer sheet is laminated with other resins or other materials containing inorganic or metallic materials. A press-molded molded body, a multilayer blow molded container, a multilayered 2-color molded body, a multi-layered shaped extruded body, an embedded injection molded body of a metal member, or the like. Specifically, a food packaging film, a food container, or a gasoline tank, a multilayer fiber, a steel pipe coating, a stainless steel plate, a color steel plate, a copper-clad laminate film, or a copper wire surface in which a EVOH film or a sheet of a barrier layer is multilayered may be mentioned. a coated article coated with the unsaturated carboxylic acid-bonded lychee polyolefin of the present invention on the surface or the inner surface of the metal material represented by the coating agent, the copper wire coating, or the like, or the inner layer having a resin and a foam thereof, and the surface is In the multilayer molded body of metal, the intermediate layer of the surface metal layer and the inner resin layer, the intermediate film for laminated glass used for the inorganic glass, the intermediate film for the optical film and the glass, and the various resins and A compatibilizing agent, a paint, an ink, or the like of an affinity of an inorganic filler, a nanofiller, or a pigment. Further, the unsaturated carboxylic acid grafted polyolefin of the present invention can be used as a heat-soluble film which is suitable as an intermediate layer or a layer of a laminate of various thermoplastic resins and metals. Sexuality is then used in the -29-200925171 layer. In this application, the resin of the present invention can be formed into a film shape and used as a heat-fusible film. Examples of the recyclable resin include a condensed polymer represented by a polyester such as polyimide, polyphenylene sulfide, polycarbonate, polyamine or polyethylene terephthalate, and EVOH. A polymer derived by radical polymerization, a polyolefin obtained by coordination polymerization of an aromatic cycloolefin metal derivative catalyst or a Ziegler catalyst, etc., and is suitable as a substrate made of glass or metal. The middle 0 of the various laminates formed by the layers is used in the next layer. Further, if necessary, the resin of the present invention is laminated by a hot-melting method on a multilayer laminate formed of a metal material or a resin material, or a multilayer laminated film, so that it can be easily fabricated into a metal material. , or a multilayer laminate on various resin materials, or a multilayer laminate film. The specific use of the unsaturated carboxylic acid grafted polyolefin of the present invention is explained in detail below. 1) As a first specific use, it is explained that at least one layer of a metal layer and a resin layer is formed of an elastic electrically insulating layer, and the metal layer and/or the Q-lipid layer and the elastic electrically insulating layer are laminated by a subsequent multilayer. The elastic electrically insulating layer is a multilayer laminate formed from the unsaturated carboxylic acid grafted polyolefin of the present invention. It has been found that this can still provide a layer made from the unsaturated carboxylic acid grafted polyolefin of the present invention, that is, heating and metal layer by means of a film, sheet or tape by a short time, under pressure, and at a relatively low temperature. Sturdy and then, with excellent elastic properties, it is possible to manufacture a multilayer laminate composed of at least one layer of a metal layer and a resin layer and an elastic electrically insulating layer, since the multilayer laminate is a metal layer and/or The resin layer is followed by the elastic electrically insulating layer, so that a multilayer -30-200925171 laminate having excellent thermal repellency which is difficult to achieve with a thermosetting resin can be provided. The multilayer laminate of the present invention may be composed of at least one layer of a metal layer and a resin layer and an elastic electrically insulating layer, and the metal layer and/or the resin layer and the elastic electrically insulating layer may be passed through without any The restriction may constitute a multilayer laminate composed of at least one of a metal layer and a resin layer, which is a strong adhesive property of the elastic electrically insulating layer to the metal layer.

The composition of the multilayer laminate of the present invention may, for example, be a laminate of a metal layer/elastic electrically insulating layer, a resin layer/elastic electrically insulating layer, a metal layer/elastic electrically insulating layer/resin layer, a metal layer. /Layer of three layers of elastic electrical insulating layer / metal layer, metal layer / elastic electric insulating layer / metal layer / elastic electric insulating layer, metal layer / elastic electric insulating layer / resin layer / elastic electric insulating layer, resin A laminate of four layers of a layer/elastic electrically insulating layer/metal layer/elastic electrically insulating layer or the like, but such examples do not limit the invention, and may constitute a laminate of more layers. Further, as long as it is heat-receivable, the thickness of each layer is not limited, and the metal layer or the resin layer is not flat, and the unevenness of the circuit formed of the metal material may be similarly applied. Further, the metal layer is not in a state in which the entire surface of the layer is coated with the metal layer, and the layer may be a layer similarly to the layer formed of the resin layer and the metal layer. The term "metal layer" in the multilayer structure of the present invention means a flat planar metal molded body of a foil, a film, a sheet, a plate or the like formed of a metal, and a molded body having such a shape. The generalized name of the three-dimensional shaped body of the three-dimensional shape of the secondary processing, and the two-dimensional or three-dimensional molded body may have a rectangular shape, or may be formed into a complicated planar shape such as an electronic circuit -31 - 200925171, and therefore, When the layer is not planar, it may have a face that holds a specific and non-constant curvature. The metal system may, for example, be steel, copper, aluminum, tin-plated aluminum, silver-plated copper, honed stainless steel, blasted steel, or the like, and a metal coated with a dissimilar metal. The same applies to the resin layer in the multilayer structure of the present invention, and is a flat planar shape of a film, a film, a sheet, or a plate-like material formed of a thermoplastic resin or a thermosetting resin. The molded article is a general term for various molded bodies of a three-dimensional shape obtained by a method used for molding a general resin such as injection molding, extrusion molding, or injection molding, and the shape of these molded bodies is not limited. , including any shape, therefore, the layer may have a face with a specific and non-constant curvature when it is not planar. In addition, examples of the thermoplastic resin include, for example, polyimine, polyamine, polycarbonate, and polyphenylene sulfide, and examples of the thermosetting resin include an epoxy resin, a phenol resin, and a polyoxyalkylene resin. .弹性 The elastic electrically insulating layer of the multilayer laminate of the present invention is a layer which is thermally fused with a metal layer or the like, and is formed of the unsaturated carboxylic acid grafted polyolefin of the present invention. By forming the elastic electrically insulating layer from the unsaturated carboxylic acid grafted polyolefin, it is possible to produce a laminate having excellent insulating properties, thermal repellency, and adhesion strength. The separation of the unsaturated carboxylic acid grafted polyolefin formed in the grafting reaction and the solvent can be carried out by a commonly used method such as a drum dryer, steam distillation, or an extruder equipped with a vent, but using a drum. Dryers are particularly good at economical use. In the reaction step, the unsaturated carboxylic acid grafted polyolefin is separated from the solvent by the method of -32-200925171. When the drum dryer is used, the reaction solution is continuously fed from the reactor to the heated after the end of the reaction step. A drum dryer that separates the product from the polymer solution. The temperature of the drum dryer at this time is preferably in the range of 120 to 20 CTC, more preferably i50 to 165 t in order to suppress the coloring, thermal deterioration, and crosslinking of the polymer while continuously promoting drying. The film shape was separated from the drum and separated. Further, the 1,1,2-trichloroethane which is volatilized by the drum dryer can be recovered by using a recovery line provided on the upper portion of the drum dryer, and used again for the reaction. The time required for removing the solvent from the polymer solution by the drum dryer can be appropriately selected depending on the type of the solvent to be used and the temperature of the drum dryer, but it is usually 10 seconds to 5 minutes. The isolated polymer can be processed into a soft line, a flake, a strand or a sheet as necessary, and the polymer which has been shaped once is supplied to the 1 axis 'or, if necessary, to the 2 axis extrusion The machine is used to melt the polymer and then extrude it, cut it in a single strand, or cut it in water to pelletize it. The extrusion temperature at this time is not particularly limited. However, in order to sufficiently melt the polyolefin to be melted and to suppress decomposition and coloring of the polyolefin, it is preferably 100 to 300 ° C, more preferably It is 150~2 50 °C. The electroelastic insulating layer in the multilayer laminate of the present invention can be obtained by thinning the unsaturated carboxylic acid grafted polyolefin by a general processing method for processing a polyolefin resin, and can be exemplified by blown film forming and cast forming. Lamination molding, calendering, sheet molding, fiber molding, blow molding, injection molding, rotational molding, and coating molding. Further, in the film formation as necessary, the polyolefin of the graft-unsaturated carboxylic acid of the present invention may be used in a co-extrusion or multi-layered form of at least one side layer in the range of -33 to 200925171.

The multilayered substrate is not only a resin film such as polyamide, polyester or ethylene-vinyl alcohol resin, but also a metal foil such as paper, aluminum foil, stainless steel foil or copper foil, aluminum plate, stainless steel plate or copper plate. Lamination of different materials such as glass. Further, if it is necessary to form a layer having a small thickness, a method in which a polyolefin grafted with an unsaturated carboxylic acid is dissolved in an organic solvent, and the solution is cast onto a substrate such as PET to volatilize the solvent and then peeled off, that is, Thin film formation by solvent casting method. Further, the solution in which the above polyolefin is dissolved in an organic solvent is directly applied to the above-mentioned metal foil, metal foil, metal plate, or the like, or various resins, various kinds of glass, paper, or the like, with a constant film thickness. On the layer of the material, the solvent is then volatilized to obtain a metal foil laminate, a metal foil laminate, a metal sheet laminate, and a resin film layer having a two-layer structure imparting adhesion, insulation, and thermal fusion properties. Compound, resin sheet laminate, resin sheet laminate, glass laminate, paper laminate. On the other hand, casting film using a solvent may be formed by using a solution casting method, for example, by dissolving the resin of the present invention in 1,1,2-trichloroethane, chloroform, methylethyl group. A solution of a solvent such as a ketone is cast on a polyethylene terephthalate film, and a solvent is removed by evaporation to form a film. A single layer film of the unsaturated carboxylic acid grafted polyolefin of the present invention, or a multilayer film, a multilayer sheet, a multilayer extrusion layer which laminates a single layer sheet with other resins or other materials containing inorganic or metallic materials A press-formed body, a multilayer blow-molded container, a multilayer two-color molded body, a multi-layer shaped extruded body, an embedded injection molded body of a metal member, or the like. Specifically, a food packaging film, a food container, or a gasoline tank, a multilayer fiber, a steel pipe coating, a stainless steel plate, a color steel plate, a copper-clad laminate film, which is a multilayered EVOH film or sheet, may be cited as -34-200925171. A coated article coated with the unsaturated carboxylic acid grafted polyolefin of the present invention on the surface or inner surface of a metal material represented by a surface line of a copper wire, a copper wire coating, or the like, or an inner layer having a resin and a foam thereof The intermediate layer of the surface metal layer and the inner resin layer in the multilayer molded body of the metal, the interlayer film for the laminated glass used for the inorganic glass, and the intermediate film for the optical film and the glass. A compatibilizing agent, a coating material, an ink, etc., which improve the affinity of various resins with inorganic fillers, nano-fillers or pigments. In the multilayer laminate of the present invention, the elastic electrically insulating layer may be subjected to an insulating coating using an automatic process followed by a metal layer of a film, a sheet or a tape. For example, by subjecting the film to the lamination of the metal layer by a roller, the method of preheating the metal layer near the melting temperature of the elastic film can be followed by, on the other hand, without preheating. The method of heating and pressure-bonding under the metal layer by a layer rolling machine is also possible, as long as it can be heated to a temperature at which the elastic electrical insulating layer exhibits adhesion, and is not limited to any lamination method, when preheating the metal, Hot air blowing or induction heating can be used. In any case, the use of the resin of the present invention as a thermoplastic means that the automation of the manufacture of the laminate is easily achieved. In the multilayer laminate of the present invention, the elastic electrically insulating layer is melted at a temperature of 40 to 25 (TC, when the temperature is lower than 40 ° C, the melting of the elastic electrical insulating layer is insufficient, and the subsequent strength is lowered) At °c, there is a case where coloring is observed due to thermal deterioration of the elastic electric insulating layer, and in addition, there is a case where the strength of the elastic electric insulating layer is deteriorated due to deterioration of the elastic electric insulating layer, preferably 80~. 200 °C.

The pressure used in the melting of the elastic electrically insulating layer in the multilayer laminate of the present invention is not particularly limited as long as the electrically insulating layer is fused, but in order to maintain the adhesion of the interface, and to suppress the elasticity The thickness of the flow-inhibiting layer of the electrically insulating layer is preferably from 0.01 to 20 MPa, more preferably from 0.01 to 5 MPa, and the pressure at the subsequent pressure can be appropriately selected depending on the kind of the adherend. In the present invention, the elastic electrically insulating layer is suitable for forming a resiliently electrically insulating layer which is firmly adhered to the metal layer when a metal layer such as aluminum or silver copper is plated by flashing tin. It is characterized by a temperature at which the epoxy resin is replaced by melting, and the elastic electrically insulating layer is used, which can be lower than the temperature at which the low melting point metal such as tin plating is softened. Further, since the obtained elastic electrically insulating layer has elasticity, it can be adapted to rapid changes in temperature, bending of the substrate, and the like. These characteristics are such that the large width reduces the risk of damage to the metal plating layer, and is excellent in operability compared with the flow layer coating technique. The multilayer laminate of the present invention is a laminate which is excellent in thermal strength and excellent in adhesion by utilizing an elastic electrically insulating layer, unlike the thermosetting resin which has been conventionally used for heat-shrinking. Moreover, the present invention can be used for the short time and continuous by using the unsaturated carboxylic acid grafted polyolefin as the elastic electrically insulating layer by heating and pressing at a low temperature of 40 to 250 ° C. The multilayer laminate is produced to provide a laminate which is widely used in the industry and a method for producing the same. 2) As a second specific use, it is explained that the metal layer and the layer of -36-200925171 and the wood are sequentially formed, and the metal layer and the wood are successively laminated with the multilayer layer, and the subsequent layer is the present invention. A multilayer laminate of an unsaturated carboxylic acid grafted polyolefin. It has been found that this can still provide a film, sheet or tape made of the unsaturated carboxylic acid grafted polyolefin of the present invention, and the metal layer and the wood are firmly adhered by heating in a short time, under pressure, and at a relatively low temperature. A laminate formed of a metal layer/attach layer/wood can be produced.

The multilayer laminate of the present invention is composed of a metal layer, an adhesive layer and a wood in the order of the metal layer and the wood. The metal layer in the multilayer structure of the present invention means a flat planar metal molded body of a foil, a film, a sheet, a plate or the like made of a metal, and a three-dimensional shaped body having a three-dimensional shape. The general term. In the above-mentioned planar metal molded body, the thickness thereof is not particularly limited, and the so-called three-dimensional molded body includes a specific three-dimensional shape obtained by cutting a metal block. In addition, examples of the metal system include steel, copper, aluminum, tin-plated aluminum, silver-plated copper, and stainless steel. The present invention is not limited thereto, and any metal can be used, and the metal coated on the surface is made of a dissimilar metal. The same applies to the same. The term "wood" in the multilayer laminate of the present invention means a sheet obtained by cutting wood into a sheet, a shaped body in which natural wood itself is formed into a specific shape, and solidification of the pulverized wood by a binder. In the case of a sheet, a film, a sheet, a block-shaped material, or the like, these molded bodies can be subjected to secondary processing such as curved surface processing as needed. When the film is in the form of a sheet or a film, for example, a paper or a paper is used by a suitable method. , Cellulose-based polymer, synthetic resin -37- 200925171 It is also possible to use a reinforcing sheet such as a film or a film. Among them, the meaning of wood can be listed as white birch, bamboo, oak, sapling, sand pear, maple, bird eye maple, red sandalwood, ebony, papaya, cherry, big leafhopper, hedgehog, cedar, peach, African purple The altar or the like is not limited thereto, and may be any shape as long as it can be a molded body having the above-described shape, and can be used without any limitation. Ο

The adhesive layer in the multilayer laminate of the present invention is a layer of a metal layer or a layer of wood, which is composed of the unsaturated carboxylic acid grafted polyolefin of the present invention. By forming the subsequent layer from a polyolefin grafted with an unsaturated carboxylic acid, a laminate having excellent insulating properties, thermal repellency, and strength can be produced. Separation of the unsaturated carboxylic acid grafted polyolefin formed by the grafting reaction with a solvent, separation of the unsaturated carboxylic acid grafted polyolefin with a solvent in a reaction step, and further, volatilization by a drum dryer The recovery of 1,2-trichloroethane, the time required to remove the solvent from the polymer solution by a drum dryer, the processing of the isolated polymer, as described above. In the multilayer laminate of the present invention, the unsaturated carboxylic acid grafted polyolefin can be thinned by a general processing method for processing a polyolefin resin, and examples thereof include blown film forming, tape casting, and extrusion lamination. Molding, calendering, sheet forming, fiber forming, blow molding, injection molding, rotational molding, and coating molding. Further, in the film formation as necessary, the polyolefin obtained by grafting the unsaturated carboxylic acid of the present invention may be used in a co-extrusion molding or a multi-layer composite molding of at least one side. In the production of the multilayer laminate of the present invention, the order of laminating the metal layer, the subsequent layer, and the wood constituting the multilayer laminate is not particularly limited, but an unsaturated carboxylic acid grafted polyolefin having an adhesive layer may be mentioned. After the film is laminated to the metal layer by a heat-pressure-38-200925171 adhesive method, the film of the unsaturated carboxylic acid grafted polyolefin of the adhesive layer is heated by a pressure-bonding method. After laminating the inside of the wood, after manufacturing the heat-pressed wood, the method of heating and pressing the hot-pressed wood to the metal layer is in the state of overlapping the metal layer, the subsequent layer, and the wood, while simultaneously Heating and pressure bonding, etc., but from a construction point of view, the metal or wood 0 of the film of the pressure-bonded unsaturated carboxylic acid grafted polyolefin is preheated on one side of the metal layer or wood, and then The metal/polyolefin film laminate is then applied to the wood, or a two-stage lamination process in which the wood/polyolefin film laminate and the metal are subsequently applied. When the metal layer or the wood is in a flat shape such as a sheet, a foil, a film, or the like, the unsaturated carboxylic acid grafted polyolefin film which becomes an adhesive layer is continuously adhered to the metal layer or wood using an automated process, and the heat of the roll shape can be manufactured. A subsequent metal foil, a thermal adhesive metal film, a thermal adhesive wood sheet, or the like. For example, the method of causing the film to follow the lamination of the metal layer by the step of laminating the metal layer may be followed by preheating the metal layer in the vicinity of the melting temperature of the subsequent layer. On the other hand, the method of heating and pressure-bonding by a laminator without preheating the metal layer can also be used as long as it can be heated to a temperature at which the adhesive layer exhibits adhesion, and is not limited to any lamination method. When preheating the metal, hot air blowing or induction heating can be used. In any case, the use of unsaturated carboxylic acid grafted polyolefins for thermoplasticity is readily achieved by automated automation of laminate manufacture. Like the metal layer, even in the case of wood, the wood can be preheated in the subsequent step of grafting the polyolefin film with the unsaturated carboxylic acid, but at this time, the water is volatilized from the wood, and the color is changed by burning - 39-200925171 The problem, so the preheating temperature is only possible for low temperature, 50~150 °C is more suitable for use. In the multilayer laminate of the present invention, the subsequent layer is melted at a temperature of 40 to 250 ° C. When the temperature is lower than 40 ° C, the subsequent layer may be insufficiently melted, and the subsequent strength may be lowered. Further, when the temperature exceeds 25 ° C. There is a case where coloring is observed due to thermal deterioration of the adhesive layer or the like, and there is a case where the strength of the adhesive layer is deteriorated due to deterioration of the adhesive layer, and it is preferably 80 to 200 °C.

In the multilayer laminate of the present invention, the pressure of the subsequent layer is melted, and the pressure used is not particularly limited as long as the subsequent layer is fused, but in order to maintain the adhesion of the interface, and to suppress the adhesion of the layer. The thickness of the flow suppressing layer is preferably reduced from 〜1 to 20 MPa, more preferably from 0.01 to 5 MPa, and the pressure at the time may be appropriately selected depending on the type of the adherend. The multi-layered laminate of the present invention can provide a strong texture of the metal and the wood with a texture, a sense of weight and a high-grade feeling by using a polyolefin grafted with an unsaturated carboxylic acid which can be firmly adhered to metal or wood as an adhesive layer. Multilayer laminate. 3) As a third specific use, a flexible wiring film having a conductive circuit formed of a metal on at least one side of a film formed of the unsaturated carboxylic acid-grafted polyolefin of the present invention will be described. It has been found that this still provides that the electrically insulating film made of the unsaturated carboxylic acid grafted polyolefin of the present invention is firmly adhered to the metal, and the film followed by the metal is used in lithography and etching for the drug display. A flexible wiring film which is excellent in stability, bending resistance, cold resistance, flexibility, and heat resistance. -40-

200925171 The flexible wiring film of the present invention is a conductive circuit formed on at least one side of a film formed of the present grafted polyolefin. In this configuration, a flexible wiring film having a structure in which two layers of a metal path are formed on one surface of a film made of a branched polyolefin, or a film formed of a grafted polyolefin is electrically conductive on both sides. Made of flexible wiring film. The structure having a three-layer structure may be formed in a thin form formed by grafting a polyolefin with an unsaturated carboxylic acid. The metal used for the flexible wiring film of the present invention may, for example, be copper, aluminum, iron, gold or silver, and copper which is economical and excellent in conductivity is preferable. Although the metal and the plate are easily formed by a circuit, the foil is used as appropriate as the product to be used, but a foil of 100 μm or less may be, for example, a rolled copper foil or an electrolytic copper foil, copper Q handleability, copper. In terms of the relationship of the fracture of the foil, it is generally suitable for use in a range of 5 to 50 μm. This eve 1 is more suitable for surface roughness, Rz (10 points average height is better than 5, and 5μηη or less is better. The unsaturated carboxylic acid formed by grafting reaction is separated by separation, in the reaction step The method for grafting a polyolefin with an unsaturated carboxylic acid, and further, recovering from the polymer solution by a drum dryer by a volatile 1,1, and removing the polymer from the polymer solution by a drum dryer, as described above. The conductive electric charge formed by the unsaturated carboxylic acid metal formed by the unsaturated carboxylic acid metal is composed of a three-layered wiring film of an unsaturated carboxylic acid path, and the double-sided circuit is not particularly limited, and the shape can be used. The thickness of the foil may be preferably as the thickness of the copper foil, from 15 to 100 μm, as copper foil, ί) is 7 μm, and the solvent is separated from the solvent by the olefin and the solvent, and the 2-trichloroethane agent is required. The film of the unsaturated carboxylic acid grafted polyolefin can be produced by a molding process of a generally known resin, and examples thereof include blown film forming, tape casting, extrusion lamination forming, calendering, and the like. Sheet forming, blow molding shape. Further, in the film formation as necessary, the polyolefin of the grafted unsaturated carboxylic acid of the present invention may be used in a co-extrusion or multi-layered form of at least one side layer, and further, a cast film using a solvent. Forming is also possible. When the solution casting method is used, for example, a solution in which the unsaturated carboxylic acid graft polyolefin of the present invention is dissolved in a solvent of 1,1,2-trichloroethane, chloroform, methyl ethyl ketone or the like can be cast. On the polyethylene terephthalate film, a solvent is removed by evaporation to form a film. Further, the film of the unsaturated carboxylic acid-grafted polyolefin may be crosslinked by irradiation with heat, ultraviolet rays, electron beams or the like as occasion demands. In the flexible wiring film of the present invention, a film made of an unsaturated carboxylic acid grafted polyolefin and a metal are subsequently formed by forming a conductive circuit by lithography. The film of the Q-unsaturated carboxylic acid-grafted polyolefin and the method of bonding the metal are not particularly limited, and can be carried out by a conventional method such as double-belt pressurization, hot pressurization, extrusion lamination, roll lamination molding, or the like. It can be attached to the metal with a film, sheet or tape using an automated process. For example, by subjecting the film to a subsequent lamination of the metal layer, the method of subsequently preheating the metal layer near the melting temperature of the film of the unsaturated carboxylic acid grafted polyolefin can be carried out. At this time, it is important to heat the metal below the softening temperature. On the other hand, the method of heating and pressing by a laminating machine can also be -42-200925171, as long as the film which can be heated to the unsaturated carboxylic acid grafted polyolefin exhibits an adhesive temperature, and is not limited thereto. Any lamination method, when preheating the metal, may be performed by hot air blowing or induction heating. In any case, the film of the unsaturated carboxylic acid grafted polyolefin can be used for the thermoplasticity, so that the metal laminated film can be more easily manufactured automatically. In the flexible wiring film of the present invention, the film of the unsaturated carboxylic acid grafted polyolefin is melted at a temperature of 40 to 250 ° C, and when it is lower than 40 ° C, the film 0 is insufficiently melted and the strength is lowered. In the case of more than 250 ° C, the coloring may be observed due to thermal deterioration of the film or the like, and the strength may be lowered due to deterioration of the film, and preferably 80 to 20 CTC 0. The pressure of the film of the unsaturated carboxylic acid grafted polyolefin in the flexible wiring film is followed by the pressure of the film of the unsaturated carboxylic acid grafted polyolefin, and is not particularly limited, but in order to maintain the subsequent The adhesion of the interface is suppressed, and since the thickness of the flow suppressing layer of the adhesive layer is low, it is preferably 0.01 to 20 MPa, more preferably 0.01 to 5 MPa, and the pressure at the subsequent pressure may be appropriately selected depending on the type of the adhesive. select. By the method described above, a film of a metal foil and an unsaturated carboxylic acid grafted polyolefin is rolled out from a roll of a metal foil and a film of a film of a non-saturated carboxylic acid grafted polyolefin, and is heated and pressed. At the time of cooling, the metal laminated film can be continuously obtained in a state where the roll is curled, and the obtained film can be cut or punctured as a wiring film according to a predetermined size. Thus, a flexible wiring film can be produced by lithography of the film. For example, when a positive resist of -43 to 200925171 is used, a wiring pattern for forming an etching resist of a metal surface of a portion where the wiring pattern is formed can be cited. A method of removing the etching photoresist by etching the metal of the portion where the wiring is not formed by etching using the etching liquid itself. In addition, when a negative-type photoresist is used, as opposed to the case of using a positive-type photoresist, it is exposed in a shape which is shielded from the wiring pattern to be formed, and the metal of the wiring pattern portion is protected by a photoresist, and an etching solution is used. A method of removing an etched photoresist by etching a metal in a portion where wiring is not formed. When the printing 0 method is used, the photoresist is not coated on the entire surface of the metal laminated film, and for example, a method of directly printing a positive photoresist such as a wiring pattern, and then exposing and removing the photoresist by etching may be mentioned. Wait. The printing method does not waste light resistance, and is more suitable for mass production of a flexible wiring substrate in an economical manner suitable for mass production. As the positive photoresist, a photodegradable photoresist such as diazonaphthoquinone or the like can be used; as the negative photoresist, a photo-sensitized photoresist such as cyclized polyisoprene can be used; The wavelength of the circuit is appropriately selected depending on the line width of the circuit, and examples thereof include a g line, an i line, a KrF stepper, an ArF step boring machine, and the like; in addition, a liquid photoresist or a film-like dry film can be used as the photoresist. Photoresist, electrodeposited photoresist, etc. After the application of the photoresist, pre-baking for removing the solvent may be carried out as necessary, and as the developing method, either immersion development or spray development may be used. The developer to be used is not particularly limited, and a developer which is generally used can be used. For example, a positive-type resist is used as an alkali-soluble acid by decomposing a portion irradiated with light, and the developer is not used as an aqueous solution. As an organic developer, sodium metasilicate, sodium hydroxide, sodium phosphate, etc. may be mentioned. It is an aqueous solution of a main body, an aqueous solution of an organic base which is a quaternary ammonium salt of a non-metal base, an amine, an alcohol-44-200925171 mixture or the like. Further, examples of the developable negative light include basic compounds such as inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, and aqueous ammonia, or ethylamines and amines. Amines such as a primary amine such as a primary amine, a diethylamine or a di-n-propylamine; a tertiary amine such as a triethylamine or a methyldiethylamine; an amine group such as a dimethylamine or a triethanolamine; An aqueous solution of an organic base 0 such as an alcohol, tetramethylammonium hydroxide, ammonium hydroxide or tetrapropylammonium hydroxide. The developing temperature is not particularly limited as long as it is at least the temperature at which the metal film is thermally deformed, and the developing solution can be washed with water without any problem, and the developing solution is sufficiently washed, and the peeling after drying is preferred. Examples of the release agent include ketones such as acetone and methyl ethyl which are generally used, and alcohols such as methanol, ethanol and isopropyl alcohol. Further, it is also possible to remove the solvent and moisture in the photoresist, and to perform baking after the substrate is improved, and the conditions are preferably selected in accordance with the selected photoresist. There is no particular limitation on the uranium engraving used for engraving, and an aqueous solution of ferric chloride or the like is used. As the etching method, the flexible wiring film of the present invention can be used for dry etching, wet etching, or electrolytic etching, and can be used for, for example, an IC TAG magnetic induction circuit, an induction circuit, a planar antenna, or the like. In particular, it can be effectively used for thermally fusing a flexible wiring film to a non-planar-shaped resin member metal member. In this case, the flexibility and resistance of the flexible wiring film can be utilized, sodium, η-propyl secondary ethanol tetra The lamination of classes. The temperature of the light-based ketone can be used to etch, etc., or to add -45-200925171, and when the circuit is formed on one side of the flexible wiring film, for example, it can be used as a portable telephone. Use of film-shaped electronic circuit components inside the information terminal such as a computer. Further, when the circuit is formed on both sides, in the range where the function of the circuit is not hindered, it can be followed by other resin parts such as polycarbonate or polyphenylene sulfide resin parts. According to the present invention, a flexible wiring film can be produced by forming a circuit pattern by lithography with a metal and a film, and a flexible wiring film excellent in bending resistance, cold resistance, softness, and heat resistance can be provided. 4) As a fourth specific use, a film antenna having a conductive circuit formed of a metal on at least one side of a film formed of the unsaturated carboxylic acid grafted polyolefin of the present invention will be described. It has been found that the electrically insulating film which is still formed by the polyolefin of the graft unsaturated carboxylic acid of the present invention is firmly adhered to the metal, and the film with the metal is used for the performance of the agent used in lithography and etching. It provides stability and provides a film antenna with excellent bending resistance, cold resistance, flexibility, and thermal shock resistance. In the film antenna of the present invention, the film of the conductive circuit of the present invention is laminated on the film of the unsaturated carboxylic acid grafted polyolefin of the present invention without using an adhesive or an adhesive used in the prior art. Further, this film antenna has characteristics that it is more easily thermally bonded to various thermoplastic resins, metals, and the like. The film antenna of the present invention is a conductive circuit formed of a metal on at least one side of a film formed of the unsaturated carboxylic acid grafted polyolefin of the present invention. The film obtained by grafting a polyolefin with an unsaturated carboxylic acid can be used as an antenna because it has an electrical insulating property of -46 to 200925171. The configuration of the film antenna of the present invention includes a film antenna having a structure in which two layers of a conductive circuit are formed on one surface of a film formed by grafting a polyolefin with an unsaturated carboxylic acid, and having a graft by an unsaturated carboxylic acid. A thin film antenna having a three-layer structure of a conductive circuit on both sides of a film made of a polyolefin. In the film antenna having a three-layer structure, the circuit formed on both sides of the film made of the unsaturated carboxylic acid grafted polyolefin may be different.

The metal used in the film antenna of the present invention is not particularly limited, and examples thereof include copper, aluminum, iron, gold, silver, etc. In the above, it is preferable to use copper which is economical and excellent in conductivity. The shape of such a metal may be a case and a plate. However, since the circuit is easy to form, it is preferable to use a foil. The thickness can be appropriately selected depending on the product to be used, and it is preferably ΙΟΟμηη or less. Examples of the copper foil include a rolled copper foil and an electrolytic copper foil. The thickness of the copper foil depends on the handling property and the crack of the copper foil. Use a range of 15~ΙΟΟμιη, but especially suitable for 5~50μηι. Further, as the copper box, those having a small surface roughness are preferable, and Rz (ten-point average height) is preferably 7 μm or less, and 5 μm or less is more preferable. Separation of the unsaturated carboxylic acid grafted polyolefin formed by the grafting reaction with a solvent, separation of the unsaturated carboxylic acid grafted polyolefin with a solvent in a reaction step, and further, volatilization by a drum dryer The recovery of 1,2-trichloroethane, the time required to remove the solvent from the polymer solution by a drum dryer, the processing of the isolated polymer, as described above. The film formed by grafting a polyolefin with an unsaturated carboxylic acid can be produced by a molding process of a generally known resin, and examples thereof include blown film forming, -47-200925171 tape casting, extrusion lamination forming, calendering Forming, sheet forming, blow molding. Further, in the film formation, if necessary, the unsaturated carboxylic acid grafted polyolefin may be used in a co-extrusion or a multi-layered form of at least one side, and may be formed by casting a film using a solvent. When the solution casting method is used, for example, a solution in which an unsaturated carboxylic acid grafted polyolefin is dissolved in a solvent such as 1,1,2-trichloroethane, chloroform or methyl ethyl ketone can be cast to polyparaphenylene. On the ethylene glycol diester film, a solvent is removed by evaporation to form a film. Further, the film of the unsaturated carboxylic acid-grafted polyolefin may be crosslinked by irradiation with heat, ultraviolet rays, electron beams or the like as necessary. In the film antenna of the present invention, a film made of an unsaturated carboxylic acid grafted polyolefin and a metal foil are laminated by heat, and then a conductive circuit can be formed by a method such as lithography. The method of bonding a film and a metal formed by grafting a polyolefin with an unsaturated carboxylic acid is not particularly limited, and may be conventionally carried out by double-belt pressurization, hot pressurization, extrusion lamination, roll lamination molding, and the like. The method can be carried out by using an automated process to adhere to the metal foil with a film, sheet or tape. For example, by subjecting the film to the subsequent lamination of the metal foil, the method of subsequently preheating the metal to the vicinity of the melting temperature of the film of the unsaturated carboxylic acid grafted polyolefin may be carried out. Next, at this time, it is important to heat the metal foil at a softening temperature or lower. On the other hand, the method of heating and pressure-bonding by a laminator may be as long as it is heated to a temperature at which the film formed of the unsaturated carboxylic acid-grafted polyolefin exhibits adhesion, and is not limited to Any lamination method, when preheating the metal, may be performed by hot air blowing or induction heating. In any case, -48-200925171 can utilize the film formed of the unsaturated carboxylic acid grafted polyolefin as the thermoplasticity, making the metal laminated film easier to manufacture automatically. Next, when the film formed by grafting the polyolefin with an unsaturated carboxylic acid has a temperature of 40 to 250 ° C, when the temperature is lower than 40 ° C, the film may be insufficiently melted and the bonding strength may be lowered, and further than 250 ° C may be exceeded. In the case of coloring, the film may be colored due to thermal deterioration of the film, and the film may be deteriorated due to deterioration of the film, and is preferably 80 to 20 °C. The pressure to be used in the film formed of the unsaturated carboxylic acid grafted polyolefin is not particularly limited as long as it is fused by the film of the unsaturated carboxylic acid grafted polyolefin, but in order to maintain the subsequent interface The adhesion is suppressed, and the thickness of the flow inhibiting layer of the adhesive layer is preferably reduced from 0.01 to 20 MPa, more preferably from 0. 0 to 5 MPa, and the pressure may be depending on the type of the adhesive. And choose the right one. By the method described above, a film of a metal foil and an unsaturated carboxylic acid grafted polyolefin is rolled out from a roll of a metal foil and a film of a film of a non-saturated carboxylic acid grafted polyolefin, and is heated and pressed. At the time of cooling, the metal laminated film can be continuously obtained in a state where the roll is curled, and the obtained film can be cut or punctured as a wiring film according to a predetermined size. Therefore, the film can be manufactured by lithography, for example, when a positive type photoresist is used, an antenna pattern of an etched photoresist which forms a metal surface of the formed portion of the antenna pattern can be cited, and the etching liquid is used. A method of removing the metal of the portion where the antenna is not formed by etching, and removing the uranium engraved photoresist. In addition, when a negative photoresist is used, it can be enumerated as opposed to when a positive photoresist is used, in the case of -49- 200925171

曝光 Exposure to the shape of the antenna pattern to be formed, the metal of the antenna pattern portion is protected by a photoresist, and the metal of the portion where the antenna is not formed is removed by etching using an etching solution to remove the photoresist. When the printing method is used, the photoresist is not coated on the entire surface of the metal laminated film, and for example, a positive resist is directly printed in the shape of an antenna pattern, and then exposed, and the photoresist is removed by etching. . The printing method does not waste light resistance, and it is more suitable for mass production of film antennas in an economical manner suitable for mass production. As the positive photoresist, a photodegradable photoresist such as diazonaphthoquinone or the like can be used; as the negative photoresist, a photo-sensitized photoresist such as cyclized polyisoprene can be used; The wavelength is appropriately selected depending on the line width of the circuit, and examples thereof include a g line, an i line, a KrF stepper, an ArF stepper, and the like. Further, as the photoresist, a liquid photoresist or a film-like dry film light can be used. Resistance, electrodeposition photoresist, etc. After the application of the photoresist, prebaking for removing the solvent may be carried out as necessary, and as the developing method, either immersion development or spray development may be used. The developer to be used is not particularly limited, and a developer which is generally used can be used. For example, a positive-type resist is an alkali-soluble acid which is decomposed by exposure to light, and an alkali aqueous solution is not used as the developing solution. Examples of the alkaline developing solution include sodium metasilicate, sodium hydroxide, sodium phosphate, and the like. It is an aqueous solution of a main body, an aqueous solution of an organic alkali which is a quaternary ammonium salt of a non-metal base, an amine, an alcohol mixture or the like. Further, examples of the developable negative photoresist include basic compounds such as inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and aqueous ammonia, or ethylamine and η. a second stage of a first-stage amine such as a propylamine, a diethylamine, a di-n-propylamine or the like, and a third stage such as an amine, a triethylamine or a methyldiethylamine. An aqueous solution of an organic base such as an amine group such as an amine, dimethylethanolamine or triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide or tetrapropylammonium hydroxide. The development temperature is not particularly limited as long as it is at most a temperature at which the metal laminated film is thermally deformed, and can be used without any problem. After the development, the water is washed, the developer is sufficiently washed, and the light is removed after drying. Examples of the release agent include ketones such as acetone and methyl ethyl ketone which are generally used, and alcohols such as methanol, ethanol and isopropyl alcohol. Further, after the development, the solvent and moisture in the photoresist are removed, and the adhesion to the substrate can be improved, and then the baking can be performed. The conditions are preferably selected according to the selected photoresist, and the temperature is preferably selected. The etching liquid used for the etching is not particularly limited, and an aqueous solution of ferric chloride or the like can be used. As the etching method, dry etching, wet etching, electrolytic etching, or the like can be used. The film antenna of the present invention can be effectively used for heat-melting a resin member or a metal member having a non-planar shape. In this case, the flexibility and pressure adhesion of the film antenna are utilized on one side of the film antenna. When the circuit is formed, it can be used, for example, as a film-shaped electronic circuit component inside a portable information terminal such as a mobile phone or a computer. In addition, when the circuit is formed on both sides, the range in which the function of the circuit is not hindered can be followed by other resin parts such as polycarbonate or polyphenylene sulfide resin parts, and if necessary, aluminum, Metal parts made of copper and stainless steel. -51 - 200925171 According to the present invention, it is possible to provide a film antenna which is excellent in bending resistance, cold resistance, flexibility, and heat repellency, and which can be thermally bonded to various resins. 5) As a fifth specific use, a conductive thin film or a sputtering target made of the unsaturated carboxylic acid grafted polyolefin of the present invention containing conductive fine particles will be described.

It was found that this was still firmly adhered to the metal, and the unsaturated carboxylic acid grafted polyolefin was effectively used as a medium in which the conductive fine particles were dispersed, and by grafting the unsaturated carboxylic acid-containing polyolefin containing conductive fine particles. The film is thinned and can be easily heated to the pair of target bodies and the back plate, and further, the conductivity between the pair of target bodies and the back plate can be ensured. The conductive film of the present invention is formed of an unsaturated carboxylic acid-grafted polyolefin containing conductive fine particles. The unsaturated carboxylic acid grafted polyolefin is unsaturated in order to maintain the uniformity of electrical conductivity and thermal conductivity of the film in the subsequent surface of the conductive film of the present invention in the subsequent bonding of the target body and the backing plate. The carboxylic acid grafted polyolefin is preferably one which does not contain a gel which is insoluble in xylene heated to 140 °C. The conductive fine particles contained in the unsaturated carboxylic acid-grafted polyolefin are not particularly limited as long as they are non-destructive and smooth on the surface of the film, and are not limited in any way, and examples thereof include gold and silver. , copper, molybdenum, nickel, carbon, tin, indium, palladium, rhodium, bismuth, antimony, bismuth, aluminum, iron, indium, magnesium, platinum, rhodium, tin, zinc, cobalt, chromium, titanium, molybdenum, tungsten, carbon Black, etc., preferably gold, silver, copper 'palladium, rhodium, ruthenium, osmium, uranium, cobalt, nickel, carbon black. The microparticles of the present invention are exemplified by one or more kinds of fine particles selected from the above particles, and the average particle diameter of the present invention is from 0.5 nm to 50 μm. -52- 200925171 The average particle diameter of the conductive fine particles is not particularly limited as long as it is appropriately selected depending on the application. When the conductivity is imparted, it is preferred to use nanoparticles, and the average particle diameter is preferably from 1 to 50 nm. It is possible to mix particles having different average particle diameters, and in particular, it is known that metal particles having an average particle diameter of a nanometer size cause spontaneous fusion due to a decrease in melting point, and metal particles having a small average particle diameter can be selected depending on the purpose. The content of the conductive fine particles in the unsaturated carboxylic acid-grafted polyolefin can be appropriately changed according to the purpose of Q, and the conductive fine particles are 30 parts by weight with respect to 100 parts by weight of the unsaturated carboxylic acid graft polyolefin in order to maintain conductivity and adhesion strength. It is preferably -99 parts by weight. The unsaturated carboxylic acid-grafted polyolefin may contain the above-mentioned other resin, elastomer or rubber component, and various additives for the purpose of improving the properties such as adhesion. Further, the conductive film of the present invention can improve the above-mentioned other resin, elastomer or rubber component, and various additives for the purpose of improving the properties such as adhesion. When the conductive film of the present invention contains the above-mentioned other resin, elastomer or rubber component, and various additives, it is contained in the range of non-destructiveness, conductivity, and adhesion, and is not particularly limited, but the content thereof is relative to More preferably, 0.1 to 10 parts by weight of the saturated citric acid-grafted polyolefin is 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and further, the content is 0.13 to 20.9 parts by weight based on 100 parts by weight of the conductive film of the invention. Preferably, 0.13 to 10.45 parts by weight is more preferred. Separation of the unsaturated carboxylic acid grafted polyolefin formed by the grafting reaction with a solvent, separation of the unsaturated carboxylic acid grafted polyolefin and the solvent in the reaction step - 53 - 200925171, and further, by a drum dryer Recovery of volatilized 1,1,2-trichloroethane, time required to remove solvent from the polymer solution by a drum dryer, processing of the isolated polymer, as described above. Various methods can be used for the production of the unsaturated carboxylic acid graft polyolefin containing the conductive fine particles used for the conductive film of the present invention. That is, a method in which the unsaturated carboxylic acid grafted polyolefin and the conductive fine particles are used, for example, a method of melt-kneading using a 2-axis extruder, may be used, and the polyolefin is dissolved in the solvent described above. The conductive fine particles are added to the obtained solution, and the solution is stirred and dispersed in a temperature range of room temperature or lower, preferably at a temperature equal to or lower than the boiling point of the solvent. The unsaturated carboxylic acid-grafted polyolefin containing conductive fine particles can be produced by removing the solvent from the obtained solution by the aforementioned method. In the conductive film of the present invention, the particles of the unsaturated carboxylic acid-grafted polyolefin containing the conductive fine particles are formed by a melt extrusion method in which a film is formed by melt-molding in a molten state, and a method such as blow molding. The film formation can be carried out by hot pressurization or the like, and the particles can be dissolved in the organic solvent described above and then thinned by a solution casting method. In this case, the solution preparation may be carried out using a reactor equipped with a stirrer or the like, but it may be carried out using a machine such as a homogenizer. In this case, the dissolution temperature is not particularly limited, but it is usually preferably from room temperature to the boiling point of the solvent to be used. The conductive fine particles are added to the obtained polyolefin solution, and the conductive fine particles are dispersed by using an ultrasonic cleaner or a homogenizer. The temperature at this time is not particularly limited as long as it is a temperature at which the solvent is not volatilized. From room temperature to below the boiling point of the solvent. Further, it is possible to use a pressure-resistant container to conduct conductivity at a temperature equal to or higher than the boiling point of the solvent. -54 - 200925171 Dispersion of fine particles. The sputtering target of the present invention is obtained by using the conductive film of the present invention and then pairing the target body and the back sheet.

The ammonium splash target of the present invention can be produced by using the conductive film of the present invention in conjunction with the pair of target bodies and the back sheet. The method of attaching the pair of target bodies and the back sheet is not limited as long as it can ensure electrical conductivity of both, and an example of the following method is used, and the back sheet and the conductive film of the present invention are used. And the paired target bodies are laminated in this order, and if necessary, placed in a heating chamber under pressure and melted. The temperature at this time may be followed by the back plate and the pair of target bodies, and is not particularly limited, and is usually 90 to 300 ° C, more preferably 120 to 250 ° C, which can be used according to the temperature. The melting point of the conductive film is appropriately changed, but it is preferably at least the melting temperature of the film, and more preferably at least the thermal decomposition temperature of the film. In order to ensure sufficient adhesion strength, for example, it is preferable to add a melting point of the temperature-based film to a temperature of 1 〇〇 ° C or less, and then the time is as long as the back plate and the pair of target bodies are uniform and practically sufficient. The strength is not particularly limited and is usually from 1 to 60 minutes, preferably from 1 to 30 minutes, and more preferably from 1 to 10 minutes. When subsequently, the backing plate and the pair of target bodies can be heated in advance to the subsequent temperature standby, in which case the bonding time can be shortened; the subsequent pressure is as long as the backing plate and the paired target body have uniform and practically sufficient bonding strength. There is no particular limitation, and it is usually 0.2 to 10 MPa, preferably 0 to 2 MPa, more preferably 0.2 to 3 MPa. In order to obtain sufficient sputtering performance, it is preferable to carry out the above-described pressure conditions which do not flow out to the outside of the surface when the conductive film of the present invention is melted. -55- 200925171 According to the present invention, it is possible to provide a conductive film, in particular, a conductive film which can be electrically connected to a target body and a back sheet in a simple manner, and which can impart electrical conductivity therebetween, and the back sheet is excellent in economical efficiency. Sputter target, and its manufacturing method. The unsaturated carboxylic acid grafted polyolefin of the present invention may be in this state as it is, but may also contain the inorganic fine particle dispersion liquid of the unsaturated carboxylic acid grafted polyolefin, inorganic fine particles and solvent of the present invention. Ο

It has been found that as a vehicle for dispersing inorganic fine particles, it is effective to dissolve a polymer solution in which an unsaturated carboxylic acid grafted polyolefin is dissolved in an organic solvent, and a solution in which inorganic fine particles are dispersed in the solution is applied in an appropriate manner. After the base material of metal or plastic, the solvent is volatilized, and a film formed of the polymer and the inorganic fine particles is formed by heat treatment, and the film is firmly adhered to a substrate such as metal or plastic. The inorganic fine particle dispersion liquid of the present invention contains the unsaturated carboxylic acid graft polyolefin of the present invention, inorganic fine particles and a solvent, and inorganic fine particles are dispersed in a polymer solution in which an unsaturated carboxylic acid grafted polyolefin is dissolved in a solvent. The unsaturated carboxylic acid-grafted polyolefin is obtained by coating or printing the inorganic fine particle dispersion of the present invention on a substrate, and then forming a film in a state in which the solvent is volatilized in a state in which the solvent is volatilized. In order to improve electrical conductivity when forming a circuit, it is preferred that the gel is not contained in xylene heated to 140 ° C. In the inorganic fine particle dispersion liquid of the present invention, as the inorganic fine particles, the film formed by the inorganic fine particles and the unsaturated carboxylic acid grafted polyolefin which is formed when the solvent is volatilized from the inorganic fine particle dispersion liquid may be smooth, and there is no - 56- 200925171 Specific restrictions include, for example, gold, silver, copper, palladium, rhodium, samarium, bismuth, antimony, aluminum, iron, indium, magnesium, platinum, rhodium, tin, zinc, cobalt, nickel, chromium, titanium, Examples of the ruthenium, tungsten, carbon black, and the like include fine particles selected from at least one of these particles. The term "microparticles" as used in the present invention means an average particle diameter of 1 nm to 5 Ομιη. When conductivity is imparted, fine particles such as gold, silver, or copper are preferably used, and fine particles such as aluminum, copper, and silver are preferably used for decorative purposes. The average particle diameter of the zero-particle-free fine particles can be appropriately selected depending on the use, and is not particularly limited. It is preferable to use a nanoparticle for imparting conductivity, and it is preferably used as an average particle diameter of 1 to 50 nm, and in addition, for decorative use, The average particle diameter of 50 ηηι to 50 μιη is preferably used, and in any application, if necessary, particles having different average particle diameters may be mixed and used. In particular, it is known that metal particles having an average particle diameter of a nanometer size cause spontaneous fusion due to a decrease in melting point. From the viewpoint of the use of a circuit, the use of metal particles having a small average particle diameter is used as much as possible. good. In the present invention, the content of the inorganic fine particles may be appropriately changed depending on the purpose, but in order to exhibit the function of conductivity or surface protection, and to prevent the decrease in the strength of the film, 1 part by weight of the unsaturated carboxylic acid grafted polyolefin is inorganic. The fine particles are preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight. The solvent for the inorganic fine particle dispersion of the present invention is not particularly limited as long as it is a solvent which does not saturate the carboxylic acid grafted polyolefin, and is appropriately selected depending on the type of the unsaturated carboxylic acid grafted polyolefin. Examples of the solvent include a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, an aromatic hydrocarbon such as benzene, toluene or xylene, or pentane, hexane or cyclohexane-57-200925171. An aliphatic hydrocarbon such as heptane, an alcohol such as cyclohexanol or onion alcohol, i1-dichloroethane, 1,2-dichloroethane, dichloromethane, chloroform, hydrazine, hydrazine, and tri-chloro a chlorine solvent such as ethane, 1,1,2-trichloroethane, carbon tetrachloride, trichloroethylene or perchloroethylene, a bromine solvent such as brominated ethane, monofluorobenzene or 1,4- Fluorine-based solvents such as difluorobenzene, perfluoroheptane, perfluorooctane, dichloropentafluoropropane, bromochloromethane, 1,2-dibromo-1,1-difluoroethane, etc. In order to suppress the change in the viscosity of the dispersion due to the volatilization of the solvent, the boiling point of the solvent of 0 is preferably 1 〇〇 ° C or more. These solvents may be used singly or in combination with a plurality of solvents if necessary. The viscosity of the inorganic fine particle dispersion of the present invention can be appropriately selected according to the method of coating and printing the dispersion, but the inkjet printing system has a viscosity of 1 to 50 mPa·s, and is suitable for gravure printing, offset printing, In the case of screen printing, it is suitable for a range of 1 to 500 Pa·s. The inorganic fine particle dispersion of the present invention may contain the above-mentioned other resin, elastomer or rubber component, and various additives. The other resin, elastomer or rubber component, and various additives may be contained in a range that does not impair the function of the conductive film or surface protective film provided by the present invention, and the content thereof is relative to the unsaturated carboxylic acid. The amount of the polyolefin of the branched polyolefin is preferably 0.1 to 10 parts by weight, more preferably 0 part by weight. The separation of the unsaturated carboxylic acid grafted polyolefin formed in the grafting reaction from the solvent can be carried out by using a drum dryer, steam distillation, an extruder equipped with a vent, etc. The dryer is particularly advantageous from the economical use surface. On the other hand, when the solvent used in the production of the inorganic fine particles of the present invention is the same as the solvent for the above grafting reaction, it is not necessary to isolate the unsaturated carboxylic acid grafted polyolefin from the reaction solution by The concentration of the unsaturated carboxylic acid grafted polyolefin is adjusted by adding a reaction solvent or a method of concentrating the reaction solution, etc., and is used in the production of the inorganic fine particle dispersion. Separation of the unsaturated carboxylic acid grafted polyolefin formed by the grafting reaction with a solvent, recovery of 1,1,2-trichloroethane which is volatilized by a drum dryer, and 0 by a drum dryer The time required for the polymer solution to remove the solvent, the processing of the isolated polymer, as described above. Examples of the substrate to be coated or printed with the inorganic fine particle dispersion of the present invention include polycarbonate, polyolefin, cyclic polyolefin, polyethylene terephthalate, and polyethylenenaphtalate. ), acrylonitrile-styrene copolymer, polymethyl methacrylate, polymethylpentene-1, polyphenylene sulfide, polyimide, polyvinyl chloride, etc., resin molded body, aluminum, copper, stainless steel Such as a metal molded body, a molded body of glass, a twinned Q circle, or the like. As a method for producing the inorganic fine particle dispersion of the present invention, various methods can be used, and an example thereof can be cited. The produced unsaturated carboxylic acid-grafted polyolefin is dissolved in the above-mentioned organic solvent to prepare a polyolefin solution. The solution can be prepared by using a reactor equipped with a stirrer or the like, but it can also be carried out using a machine such as a homogenizer. In this case, the dissolution temperature is not particularly limited, but it is usually preferably from room temperature to the boiling point of the solvent to be used. The inorganic fine particles are added to the obtained polyolefin solution. The inorganic fine particles are dispersed by using an ultrasonic cleaner or a homogenizer. The temperature at this time is not particularly limited as long as the temperature at which the solvent does not volatilize. It is from room temperature to below the boiling point of the solvent. Further, the pressure-resistant container can be used to disperse the inorganic fine particles at a temperature equal to or higher than the boiling point of the solvent. The inorganic fine particle dispersion of the present invention is formed into a plastic in a simple, economical, and high-productivity by existing technologies such as gravure printing, offset printing, screen printing, inkjet printing, impregnation, spin coating, and the like. A surface protective film for forming a conductive circuit on various substrates such as metal, glass, germanium wafer, or the like, or can be used to impart patterning on the surface of the molded body using the various substrates described above. According to the present invention, a film can be formed in a solid state on a substrate of various plastics, glass, germanium wafers, metals, etc., and an inorganic fine particle dispersion capable of forming a stable film by a short-time heat treatment can be provided. . [Embodiment]

The invention is described in detail below based on the embodiments, but these examples are examples of the understanding of the invention, and the invention is not limited by the examples. Further, the oxime used in the examples is obtained by the following measurement method. <Materials> The examples of the present invention use the raw materials described below. -60- 200925171

(1) EVA ethylene/vinyl acetate copolymer: Ulutou Laxian (registered trademark) 751 manufactured by Tosoh Corporation (vinyl acetate content = 28% by weight, MFR = 5.7g/10 minutes, density = 952kg/ M3)

(2) L-LDPE

Ethylene/hexene-1 copolymer: manufactured by Tosoh Corporation NIPOLON-Z (registered trademark) ZF230 (MFR = 2.0g/10 min, density = 920kg/m3)

(3) PP homopolypropylene: CHISSO POLYPRO XF181 1 manufactured by CHISSO Petrochemical Co., Ltd. (MFR = 2.5g/10 min, density = 900kg/m3)

(4) HDPE high-density polyethylene: manufactured by Tosoh Corporation, NIPOLON HARD (registered trademark) 4000 (MFR = 5.0g/10 minutes, density

(5) alkalized EVA (alkaline of ethylene/vinyl acetate copolymer)

1) Alkaline EVA-1: H-6410M manufactured by Tosoh Corporation

2) Alkali EVA-2: H-605 1 K manufactured by Tosoh Corporation 3) Alkaline EVA-3: H-6960 (6) Benzoyl peroxide (BPO) manufactured by Tosoh Corporation

NYPER B (7) bis(2-t-butylperoxypropyl)benzene (DBPIB) -61 - 200925171

PERBUTYL P (8) 2,6-di-tert-butyl-p-cresol (ΒΗΤ) Co., Ltd. API YOSHINOX ΒΗΤ (9) Maleic anhydride, acrylic acid, ethyl acrylate, acrylic acid Butyl ester, 1,1,2-trichloroethane, xylene, methanol, dimethylformamide, hydrazine, tetrahydrofuran (THF), phenylimidazole, 26% aqueous sulfuric acid, thymol blue indicator, Ν/ The hydrazine solution of 20 and the methyl hexahydrophthalic anhydride 0 were used as the first-stage reagents manufactured by Kanto Chemical Co., Ltd. (10) Aluminum plate Toyo Aluminum Co., Ltd. Count: Α1Ν30Η-Η18 Thickness: 1 0 0 μπι (11) Stainless steel (share) NILACO SUS304 753 5 1 3 (1 2 ) Wood FLOWER ART Dream ebony flakes, Papaya flakes, bird's eye maple leaf flakes, oak flakes, porphyra tree flakes thickness: 0.3mm

(1 3 ) Epoxy resin A

曰本 epoxy resin (share) jER (registered trademark) 807 (1 4) epoxy resin B Japan epoxy resin (share) jER (registered trademark) 191P (1 5) epoxy resin hardener Minghe Chemical Co., Ltd. phenol phenolic Varnish type hardener Η-1 (1 6 ) Polyimide film UPILEX (registered trademark) 755 -62- 200925171 (17) Polycarbonate film Teijin Chemical Co., Ltd. made panlite (Login trademark ) PC- 21 5 1 (1 8 ) Polyphenylene sulfide sheet SULTEEL (registered trademark) G10 (19) Poly-(styrene-butadiene-styrene) block copolymer Shell chemistry ( Co., Ltd., trade name TR-1150 (20) CU-113253 Manufactured by NILACO, Copper Foil Co., Ltd. Thickness: 40μιη (2 1 ) Polyimide Tape Polyurethane Tape 5412 (22) Developed by Sumitomo 3 Co., Ltd. liquid

ROHM&HAAS Μ IC R Ο Ρ 0 SIΤ (phosphate developer) DEVELOPPER (23) conductive microparticles

1) Copper microparticles: (stock) High purity chemical research institute CUE0 8PB Average particle size 1 μ m

2) Carbon black: manufactured by Mitsubishi Chemical Corporation KETJENBLACK

EC (24) Inorganic fine particles 1) Silver particles: (Stock) High-purity chemical research institute Reduced silver particles AGE08PB Average particle size Ιμιη 2) Aluminum particles: (Shares) High-purity chemical research institute ALE 11ΡΒ Average particle size 3μ -63- 200925171 3) Copper particles: (C) high-purity chemical research institute CUE08PB average particle size 1 μηι 4) Gold particles: (stock) high-purity chemical research institute average particle size 1 μηι 5) Acidification second Ferro-iron particles: FEO02PB average particle size 1 μιη produced by the High Purity Chemical Research Institute 6) Silver Nano Paste: Flattened by ULVAC Materials Co., Ltd.

7) Carbon black: KETJENBLACK EC manufactured by Mitsubishi Chemical Co., Ltd. (2 5 ) Onion alcohol (unsaturated aliphatic cyclic phenol) 曰本萜烯化学股份有限公司<Next test> Next, the test system uses the following resin ,metal.

(1) UP ILEX (registered trademark) 75 5 (2) Polycarbonate film manufactured by Teijin Chemicals Co., Ltd. panlite (registered trademark) ΡΟΖ 1 5 1 (3) Polyphenylene Sulfide (PPS) SULTEEL (registered trademark) GS40 (4) Polyethylene terephthalate film manufactured by Toray Co., Ltd. RUMIRER #1 00 -64- 200925171 (5) Limited copper plate shares Company NILACO CU-113328 0.10m (6) Aluminum plate Toyo Aluminum Co., Ltd. Count: A1N30H-H18 Thickness: 1 0 0 μπι &lt;acid price&gt; 0 Weigh the polymer sample lg and heat it to dissolve in toluene After adding 100 ml of '100 ml of methanol, dimethylformamide i〇ml, hydrazine. 5 ml, then 'add thymol blue indicator lml, use N/2 0 KOH solution (n-propanol / The benzene solution was titrated, and the time point above which the blue-violet continuation was counted as the end point was calculated. &lt;Melt flow rate (MFR) &gt; Melt flow rate (MFR) based on polyethylene according to JIS K6 922-1, acetonitrile vinyl acetate copolymer according to JIS K6924-1, polypropylene according to JIS K6921-2 'Use Bao industry MELT INDEXER L244 'made by (stock) was measured under the conditions of a temperature of 19 Torr and a load of 2.1 6 kgf. <Measurement of gel fraction> 50 mg of the polymer was added to 50 ml of xylene to 140. (: After it was dissolved for 12 hours, 'this solution was filtered with a stainless steel mesh (75 μm) of 2 mesh mesh, and dried at 105 ° C for 5 hours. -65-200925171 Unmelted component. &lt;Measurement of yellow index (YI)&gt; According to Jis K71 05 (1 98 1st edition), the double-action compression molding machine WFA-50 manufactured by the company will be used to add 150°. C, a pressure of 10 MPa, 10 minutes, a cooling temperature of 30 ° C 1 OMPa, a condition of 5 minutes of pressure, and a film of thickness ΙΟΟμηη was measured by a SU color tester (s).

Shentan Gold Hot Temperature 'Pressure YI, using a device made of long device ( &lt;1,1,2-trichloroethane in 1-butanol and 1,2-epoxybutane amount> Take with a micro syringe GC-1, manufactured by Gas Chromatography Shimadzu Corporation, with 1,1,2-trichloroethane 0.5 μl, GC capillary column DB-1301 (Agilent Technologies, Inc., 30 m, inner diameter 〇.25 mm, film thickness 〇·25 μπι) 4 A ), measured with the following conditions &lt; Injection temperature: 40 ° C Injection temperature retention time: 4 minutes Heating program 1: 5 ° C / minute (40 ~ 90 ° C) Heating program 2: 10 ° C / minute (90~190°C) Final temperature: 190°C Final temperature retention time: 20 minutes carrier gas: 氦&lt;Next test&gt; Forming machine used (share) Shendu Metal Industry's double-acting compression-66 - 200925171

WFA-50 was used as a press molding machine to obtain a pressurized film having a thickness of 1 ΟΟμηι under heating conditions of a heating temperature of 15 (TC, a pressure of 10 MPa, a pressure of 30 ° C, a pressure of 10 ° C, and a pressure of 5 MPa for 5 minutes). The film formed into a thickness of ΙΟΟμηη and the adherend were heated by a Heat Seal TESTERTP-701 manufactured by TESTER Industries, Inc., and heated at 180 〇C, 60 sec '0.2 MPa. The Tensilon universal test using ORIENTEC was used. RTE-1210 was used as a tensile tester and its adhesion strength was evaluated by a T-peel test at a tensile speed (peeling speed) of 300 mm/min. &lt;Fused extrusion&gt; Using NAKATANI with a vent The number of sections made by the mechanical industry is 10 and 2 axis extruders (115 ιηιηφ, L/D = 50). &lt;Heat cycle test&gt; Using the hot and cold blasting apparatus TSA-7 1L-A manufactured by ESPEC Co., Ltd., 85 °C for 30 minutes, normal temperature for 5 minutes, and -40 °C for 30 minutes as one cycle, heat treatment was applied to the subsequent test piece, and peeling of the adhesive sheet was observed. <Rot Coating> A MIKASA spin coater 1H-360S was used. &lt;Bending resistance&gt; -67 - 200925171 Evaluation of bending resistance (MIT test), using the MIT tester manufactured by Mitutoyo Co., Ltd. according to JIS-C5016, using the jig of R = 〇.38 to evaluate the number of breaks or the number of peeling of the laminate. (Kneading of conductive fine particles) Using a laboroplastomill R30 manufactured by Toyo Seiki Co., Ltd., conductive 0 microparticles were added to the unsaturated carboxylic acid grafted polyolefin at a rotation number of 60 rpm, and kneaded in a molten state to obtain a conductive material. Unsaturated carboxylic acid grafted polyolefin of fine particles. &lt;Forming of film&gt; Using a double-action compression molding machine WFA-50 manufactured by Shinto Metal Industry as a press molding machine at a heating temperature of 150 ° C , pressure lOMPa, 10 minutes, cooling temperature 30 ° C 'pressure lOMPa, 5 minutes of pressurization conditions to obtain a pressure film of thickness 1 〇〇 μηι. 〇 &lt; Τ type peel test> Use (stock) ORIENTEC Tensilon versatile The test machine RTE-1210 was evaluated for its adhesion strength by a T-peel test using a tensile speed (peeling speed) of 300 mm/min. &lt; Tape peeling test&gt; by screen printing on a substrate 100 patterns of 5 mm X 5 mm squares were printed, and after drying, heat treatment was carried out at 210 °C. On this pattern, tape was attached to -68-200925171. When the tape was peeled off, the pattern was peeled off from the substrate. number. Example 1

5 000 parts by weight of trichloroethane manufactured by Kanto Chemical Co., Ltd. and 2500 parts by weight of a 26% aqueous sulfuric acid solution were placed in a 10-liter flask with a lower mouth and vigorously stirred, and after standing, the lower organic layer was taken out. The extracted organic layer and 5000 parts by weight of distilled water were placed in a 10-liter flask with a lower opening and vigorously stirred, and the operation of removing the organic layer of the lower layer was carried out after standing, and the 1-butanol of the impurity was removed by repeating three times. Further, 1,2-epoxybutane was further dehydrated by adding 150 parts by weight of molecular sieve 4A to the taken-out organic layer and stirring with a stirrer. 1 liter of glass reaction vessel was charged with 1,1,2-trichloroethane 1 -1,2-trichloroethane 1 -butoxyl and 1 ,2-epoxybutane removed by the above operation, and EVA 100 weight A portion and 2 to 0 parts by weight of maleic anhydride were uniformly dissolved in EVA by raising the temperature of the reactor to 80 ° C and then maintaining at 80 ° C for 3 hours. In addition, during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liters/min to remove the air mixed into the reactor, and then the reactor was heated from 80 ° C to ll 〇 ° C, which was used as a catalyst for the graft reaction. (Free Radical Generating Agent) 0.8 parts by weight of BPO is dissolved in a catalyst solution of 50 parts by weight of 1,1,2-trichloroethane from which 1-butanol and 1,2-epoxybutane are removed, The grafting reaction was carried out continuously continuously for 3 hours to the reactor, and then the reaction was continued at the same temperature for 2 hours, and the pressure of the reactor was maintained below 1 MPa through the reaction. After the reaction was completed, the reactor was returned to atmospheric pressure. The temperature was lowered to 70 ° C, and then 0.03 parts by weight of -69-200925171 BHT as a stabilizer was added, and then the solution was reprecipitated by methanol to separate the unsaturated carboxylic acid grafted from the solvent. EVA. It is known that the resultant product has a result of analysis of 1.8% by weight of non-ti ci, the gel is 〇% by weight, YI is 2 and the hue is excellent, and the subsequent strengths of yttrium aluminum, polyimine, and polycarbonate 'PPS are each The results for gel, hue, and strength of 52, 39, 35, and 3 6 N/15 mm, which are strongly adhered to various adhesive rotations, are shown in Table 1. For life and carboxy copper, 60, measured

〇-70- 200925171 ο Ο [Is Example 7 &amp; Ο νΜ ο ΟΝ Η 〇 (N 〇〇〇»Ti &lt;NT—^ Ο ο 00 ο in 〇 (Ν (Ν 〇&lt;N cn (N implementation Example 6 HDPE Ο Ό ΟΝ in 〇〇 2200 ο ο s ο ο 00 〇 tn as (N 〇 \ o inch embodiment 5 L-LDPE ο Ο &lt;Ν 〇\ (Ν 〇 (N 〇〇ο W-) ( S ο ο 00 ο iTi 〇CN m 00 CN 00 CN &lt;N Embodiment 4 EVA ο CN Ον 〇〇 〇〇 0 1 ο ο ν〇ο ο &lt;r! 〇Γ〇g 〇ON m Ο 实施 Example 3 EVA ο &lt;Ν κη 〇\ 卜〇 \ 〇〇o &lt;rj (N ο ο ο ΓΟ η 〇S v〇m cn 寸 实施 实施 实施 实施 实施 E E E E ο νο ο 〇 04 m P; iTi m CN Example 1 EVA ο (Ν ^Ti Ο 〇(N 〇〇o in cs ο ο 00 ο 00 〇CN) in § ON cn νο cn CN Barrier m曰丨g/io minute parts by weight parts by weight parts by weight parts by weight parts by weight _ ώπΐ] ΡΤη N/15mm N/15mm N/15mm N/15mm 1 N/15mm jm MFR Maleic anhydride butyl acrylate 1 , 1,2-trichloroethane 擀η οο CU CQ acid change Amount of gel 骠 polyimine polycarbonate GO (X 筠Μ 遐氍 K · your solvent radical generator modified polymer followed by strength YU tone) -71 - 200925171 Example 2 In addition to the free radical generator The reaction was carried out in the same manner as in Example 1 except that the amount of addition was changed to 0.16 parts by weight, and then the product was separated. The product was analyzed to have an unsaturated carboxylic acid having a content of 1 to 5% by weight, and the gel was 〇% by weight. YI is 2 and the hue is excellent. In addition, the adhesion strength to copper, aluminum, polyimine, polycarbonate, and PPS is 42, 53, 37, 37, 3 5 N/15 mm, and is firmly adhered to various types. The results of measuring the gel, hue, and subsequent strength are shown in Table 1. Example 3 Example 1 was changed 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. The reaction was carried out in the same manner, followed by separation of the product. It is known that the product analysis result is 2.1% by weight of an unsaturated carboxylic acid, the gel is 〇% by weight, YI is 4 and the hue is excellent, and further, with copper, aluminum, polyimine, polycarbonate, PPS The strengths were then 60, 66, 36, 35, 40 N/1 5 mm, and the results were as follows. The results of measuring the gel, hue, and strength of the various adherends are shown in Table 1. Example 4 The amount of addition of maleic anhydride was changed to 20 parts by weight, the amount of addition of 1,1,2-trichloroethane was changed to 2,000 parts by weight, and the amount of BPO added was changed to 0.16 parts by weight. The reaction was carried out in the same manner as in Example 1 -72 to 200925171, followed by separation of the product. It is known that the product analysis results in an unsaturated residual acid of 3.0% by weight, and the gel has a 〇% by weight 'YI of 4 and excellent hue, and 'with copper, aluminum, polyimine, polycarbonate, The adhesive strengths of pps were each 73, 80, 40, 39, 40 N/15 mm, and the results of measuring gel, hue, and subsequent strength in various adherends are shown in Table 1. 0 Examples 5 to 7 except that the first embodiment and the base polymer were changed from EVA to L-LDPE, HDPE, and PP, and the amount of maleic anhydride added was changed to 30 parts by weight, 1,1,2-trichloroethane. The reaction was carried out in the same manner as in Example 1 except that the amount of the added amount of the alkane was changed to 2,200 parts by weight and the amount of the BPO was changed to 0.03 part by weight (Example 6), and then the product was separated. The results of measuring gel, hue, and subsequent strength are shown in Table 1. No gel, excellent hue and strength. Example 8 to 1 1 In addition to the addition amount of 1,1,2-trichloroethane, unsaturated carboxylic acid, and βρο, the reaction was carried out by the same method as in Examples 4 to 7, and the product was measured to measure The results of gel, hue, and subsequent strength are shown in Table 2. No gel, excellent hue and strength. -73- 200925171

Example 17 900 in &lt;N 〇(N 〇rH 1195 〇〇〇m οό 〇(Ν cn Ο m Example 16 EVA CN in ON 〇 (N 〇1665 〇〇to rn ο σν 〇m MD Ο (Ν ^Τ) Inch CO Example 15 HDPE Ο 1—Η VO G\ 〇〇〇1250 〇〇ο CN 〇Ο 1-Η vn &lt;Ν CN tN &lt;N Example 14 &amp; Ο 900 CN 〇〇(N 〇1250 〇〇ο ▼—Η 〇 in in (Ν 〇\ CN &lt;N m cn Example 13 L-LDPE ο 920 CN o 〇CN 〇1250 〇〇ο ΟΟ 〇§ Ο m (N us m CN embodiment 12 EVA Ο 952 卜o 〇&lt;N 〇1250 〇〇ο α; 〇ON in % &lt;Ν mm ο (N Example 11 Ο Τ*-Η 900 ^T) &lt;N om 〇〇2200 〇〇οο ο &lt;Ν 00 〇沄 CNCN § Example 10 HDPE Ο r—Η ν〇ON 〇〇2200 〇〇οο ο ο 卜·· 〇CN VO οο in Example 9 L-LDPE Ο r-^ 〇 ( N as CN 〇〇2200 〇〇οο ο ι&gt; 〇in in (N Ό cn et al. 8 EVA Ο CN V% ON οο 〇〇 2200 〇〇οο ο ο 〇 &lt;N Ό ΟΟ jrj σ\ CN (N weight Parts 1 g / io minutes 1 part by weight parts by weight parts by weight parts by weight parts by weight % by weight % N / 15mm N / 15mm N / 15mm N / 15mm 丨 N / 15mm 丨 density MFR Maleic anhydride acrylic acid butyl Ester 1,1,2-trichloroethane 浒fi ll ΒΡΟ acid-modified gel tio7 瑕polyimine polycarbonate PPS raw material polyolefin unsaturated carboxylic acid solvent free radical generator modified polymer bonding strength 1 _______ one — ί YU tone) -74-

200925171 Examples 12-15

The results of gel, hue, and subsequent strength were measured by the same method as in Example 1 except that EVA, L-LDPE, PP, and HDPE olefin were used, and the maleic anhydride was changed to acrylic acid. The hue and the strength are excellent. Examples 16 to 17 Reactions were carried out in the same manner as in the examples except that the maleic anhydride was changed to maleic anhydride/propylene and the amount of BPO added was changed. The product was separated, and the gel, hue, and fruit were measured and shown in Table 2. No gel, hue, and subsequent strength. Example 1 8 parts by weight of Kanto Chemical Co., Ltd. and 2500 parts by weight of a 26% aqueous solution of sulfuric acid were placed in a 1 liter flask and stirred vigorously. After standing, the lower layer was taken out. The taken-out organic layer was vigorously stirred in a 10 liter flask of 5,000 parts by weight of distilled water, and after standing, the operation was repeated three times, and the organic layer of 1-butanol and 1,2-epoxy butyl was added and 150 was added. Part by weight of molecular sieve 4A, and dehydrated.

A 2 liter glass reaction vessel was charged with a polyBP hydrazine added as a raw material by using 1-butanol and 1,2-epoxybutane as a raw material. The product 'Table 2. The gel-free butyl ester mixture 1 was excellent in the same strength and the strength of the knot. The trichloroethane 5000 was fed with the organic layer of the lower mouth, and was placed in the organic layer with the lower layer. Alkane. More than the operation of agitating with a stirrer, de-alkane 1 250 wt-75- 200925171

The solution, EVA 100 parts by weight, and 2.0 parts by weight of maleic anhydride, the reactor was heated to 80 ° C, and then kept at 80 ° C for 3 hours to uniformly dissolve the EVA. In addition, during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liters/min to remove the air mixed into the reactor, and then the reactor was heated from 80 ° C to 110 ° C to serve as a catalyst for the graft reaction ( a free radical generator), wherein 1.0 part by weight of BPO is dissolved in a catalyst solution of 50 parts by weight of 1,1,2-trichloroethane from which 1-butanol and 1,2-epoxybutane are removed, The crucible is put into the reactor for grafting reaction. Then, the reaction was continued at the same temperature for 2 hours, and the pressure of the reactor was maintained at 1 MPa or less through the reaction. After the reaction was completed, the pressure was returned to normal pressure to lower the temperature of the reactor to 70 ° C, and then, as a stabilizer, it was added. After 3 parts by weight of BHT, the solution was reprecipitated by methanol, and the unsaturated carboxylic acid grafted EVA as a product was separated from the solvent. It is known that the resultant product has an analytical result of 1.8% by weight of an unsaturated carboxylic acid, a gel of 0.010% by weight, a YI of 3 and excellent hue, and further, with copper, aluminum, polyimine, polycarbonate, PPS. The strengths were then 48, 55, 33, 30, 30 N/15 mm, and were firmly adhered to various adherends. The results of measuring gel, hue, and subsequent strength are shown in Table 3. -76- 200925171 ο Ο

US Embodiment 24 Ο τ—^ Ο 04 〇cs 〇〇(S ν·Η 〇〇〇0.015 m ο m yn CN CN CN Example 23 HDPE Ο Η νο ΟΝ in 沄〇〇2200 〇〇〇ο 00 0.012 oo 00 S inch embodiment 22 L-LDPE Ο 1-Η 宕CN o CN 〇〇〇in cs — 〇〇〇rH 0.013 inch rH o cn (N &lt;S Example 21 EVA Ο CA νη α\ 卜tr! 〇 〇ο 1 〇〇〇00 0.014 〇oo 寸Ο] inch embodiment 20 EVA Τ Τ—Η CN ΟΝ 卜卜 OS 〇〇ο vi CN 〇〇〇rn ο ΓΟ 0.011 § 〇00 cn 00 m inch Example 19 EVA Ο (Ν ΙΤ) ΟΝ o (N 〇〇(N r-~&lt; 〇〇〇yn 0.016 〇〇m 00 r^ m ο (N Example 18 EVA ο (Ν 〇\ 卜o CN 〇〇ο Ό ( Ν 〇〇P r—Η 00 0.010 κη ο cn m Parts by weight m day g/io minutes parts by weight parts by weight parts by weight parts by weight parts by weight parts by weight % by weight N/15mm N/15mm N/15mm N /15mm N/15mm MFR Maleic anhydride acrylic acid butyl acrylate U,2-trichloroethane paste fr Π ο Oh 03 acid modified amount gel i Πρ7 &lt;Μ Imine polycarbonate X/l CL, Μ铋 · · your solvent radical generator modified polymer adhesion strength _____-__1 YU tone) -77- 200925171 Example 1 9 In addition to the addition of free radical generator The reaction was carried out in the same manner as in Example 18 except that the amount was changed to 0.16 parts by weight, and then the product was separated. The product was analyzed to be 1.5% by weight of an unsaturated carboxylic acid, and the gel was 0.016% by weight, and YI was 2 and excellent hue, in addition, the bonding strength with copper, aluminum, polyimine, polycarbonate, PPS is 38, 48, 38, 37, 4 ON / 15 mm 'strongly followed by various adherends The results of measuring gel, hue, and subsequent strength are shown in Table 3. Example 20 Example 18 was changed 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. The reaction was carried out in the same manner, followed by separation of the product.

It is known that the product analysis result is 3.0% by weight of an unsaturated carboxylic acid, the gel is 0.011% by weight, the YI is 4, and the hue is excellent, and further, with copper, aluminum, polyimine, polycarbonate, PPS. The strengths were then 60, 64, 40, 38, 38 N/15 mm, and were firmly adhered to various adherends. The results of measuring gel, hue, and subsequent strength are shown in Table 3. Example 2 1 The amount of addition of 1,1,2-trichloroethane was changed to 2000 parts by weight, and the amount of addition of BPO was changed to 1.0 part by weight, except that the amount of maleic anhydride added was changed to 20 parts by weight. In the same manner, the reaction was carried out, and then the product was separated from -78 to 200925171. It is known that the resultant has an analytical result of 1.8% by weight of unsaturated carboxylic acid, and the gel has a 〇_〇14 weight °/. YI is 4 and the hue is excellent. In addition, the bonding strength with copper, aluminum, polyimine, polycarbonate, and PPS is 70, 78, 42, 43, and 42 N/15 mm, respectively, and is firmly adhered to various adhesives. The results of the measurement of gel, hue, and subsequent strength are shown in Table 3. 0 Examples 22 to 24 The example 18 and the base polymer were changed from EVA to L-LDPE, HDPE, and PP', and the amount of maleic anhydride added was changed to 3 parts by weight, 1,1,2-trichloroethane. The reaction was carried out in the same manner as in Example 18 except that the amount of the alkane added was changed to 2200 parts by weight (Example 23), and the product was separated. The results of measuring gel, hue, and subsequent strength are shown in Table 3. It contains a gel but its content is less than 0.02% by weight, and the hue and the strength are excellent.实施 Examples 25 to 2 8 The reaction was carried out in the same manner as in Examples 21 to 24 except that the amounts of 1,1,2-trichloroethane, unsaturated carboxylic acid and BPO were changed. Separation of the product The results of measuring the gel, hue, and subsequent strength are shown in Table 4. It contains a gel but its content is less than 0.02% by weight, and is excellent in hue and strength. -79- 200925171

Example 34 &amp; 900 in oi Ο oi 〇 1195 〇〇〇cn 〇6 0.013 〇m 3 00 m Ο Ο mm Example 33 EVA g 952 ο ri 〇 1665 〇〇m&quot; On 0.013 in ο οο mm 丨Example 32 lHDPE Ο νο ο 〇 (Ν 〇1250 〇〇〇CN ν—Η 0.012 00 卜 (N 丨Example 31 ο Η 900 in Η ο 〇 (Ν 〇1250 〇〇〇rH 0.010 (Ν ο m cn implementation Example 30 L-LDPE 920 920 CN ο 〇 (Ν 〇1250 〇〇1—Η 00 0.012 〇m ο cn (N Example 29 EVA ο 952 ο 〇CN 〇1250 〇〇r—Η Ο O) 0.016 m &lt; N Example 28 &amp; ο Τ-Η Ο Ο oi 〇〇 2200 〇〇 00 ο (N oo 0.014 in ΟΟ ίη § (N Example 27, HDPE Ο in νο Os 〇〇2200 〇〇00 ο O 0.012 (N m in m \〇Example 26 L-LDPE Ο 920 (Ν 〇〇 2200 〇〇οο 0.011 m S Example 25 EVA ο fN 卜 ΓΛ 〇〇 2200 〇〇οο ο o \〇0.013 s JO 3 inch 00 ( Ν (N parts by weight Ϊ g / io minutes by weight parts by weight parts by weight parts by weight parts by weight Quantity % Weight % N/15mm N/15mm N/15mm N/15mm N/15mm Density MFR Maleic anhydride butyl acrylate 1,1,2-trichloroethane xylene 1 ΒΡΟ Acid modified gel TTp7 box Polyimide Polycarbonate PPS Raw Material Polyolefin Unsaturated Carboxylic Acid Solvent Free Radical Producer Modified Polymer Strength YI (Hue) -80- 200925171 Examples 29~32 In addition to using EVA, L-LDPE, PP, HDPE The polyolefin was used as a raw material, and the reaction was carried out in the same manner as in Example 18 except that the maleic anhydride was changed to acrylic acid, and the amount of the BPO was changed. The product was separated, and the results of measuring the gel, the hue, and the subsequent strength were shown in the table. 4. It contains a gel but its content is less than 0.02% by weight, and is excellent in hue and strength.

Examples 33 to 34 Reactions were carried out in the same manner as in Example 18 except that the maleic anhydride was changed to a maleic anhydride/butyl acrylate mixture and the amount of BPO added was changed. The results of separating the product and measuring the gel, hue, and subsequent strength are shown in Table 4. It contains a gel but its content is less than 0.02% by weight, and is excellent in hue and subsequent strength. Comparative Example 1 In a state in which 100 parts by weight of EVA, 4.0 parts by weight of maleic anhydride, and 0.03 parts by weight of DBPIB were uniformly mixed in advance using a Henschel mixer, the product was supplied to a two-axis extruder (Toyo Seiki, laboroplastomill L/). D = 25 ' &lt;i&gt;=20mm), the first barrel is reacted at 140 ° C, the second barrel is 200 ° C, and the third barrel is 20 ° ° C at a rotation number of 30 rpm. Maleic anhydride modified EVA. The analysis result of the product was that the gel was present in an amount of 0.1% by weight, the YI was also as high as 15, and the yellowness was also high. Further, the adhesion strength to copper, aluminum, polyimine, polycarbonate, and PPS was significantly inferior to that of the polymer obtained in the examples, and the results of measuring gel, hue, and subsequent strength are shown in Table 5. . -81 - 200925171

-82-200925171 Comparative Example 2 Maleic anhydride-modified L-LDPE was obtained by the same method as in Comparative Example 1, except that the resin used for the modification was changed from EVA to L-LDPE.

The analysis result of the product was 0.08% by weight of the gel, YI was also as high as 13, and the yellowness was also high. Further, the adhesion strength to copper, aluminum, polyimine, polycarbonate, and PPS was significantly inferior to that of the polymer obtained in the examples, and the results of measuring gel, hue, and subsequent strength are shown in the table comparison. Example 3 Maleic anhydride-modified PP was obtained by the same method as Comparative Example 1, except that the resin used for the modification was changed from EVA to PP. The analysis result of the product was that the gel was present in 凝胶·〇 4% by weight, 'YI was also as high as 11, and the yellowness was also high. Further, the adhesion strength to copper, aluminum, polyimine, polycarbonate, and PPS was significantly inferior to that of the polymer obtained in the examples, and the results of measuring gel, hue, and subsequent strength are shown in Table Comparative Example 4 Maleic anhydride-modified HDPE was obtained by the same method as in Comparative Example 1, except that the resin used for the modification was changed from EVA to HDPE. The analysis result of the product was that the gel was present in an amount of 重量·〇6 wt%, YI was also as high as 11, and yellowness was also high. Further, the adhesion strength to copper, aluminum, polyimine, polycarb-83-200925171 acid ester, and PPS was significantly inferior to that of the polymer obtained in the examples, and the results of measuring gel, hue, and strength were measured. Listed in Table Comparative Examples 5 to 8

Grafting is not obtained by the same method as in Example 1 except that the reaction solvent was changed from 1,1,2-trichloroethane to xylene, and the amount of maleic anhydride added and the amount of BPO added were changed. a polymer of carboxylic acid. The amount of the unsaturated carboxylic acid introduced into the base polymer was small, and the hue was also excellent, but the adhesion was remarkably inferior to the polymer obtained in the examples. The results of measuring gel, hue, and subsequent strength are shown in Table 5. Comparative Examples 9 to 12 A polymer of grafted acrylic acid was obtained by the same method as Comparative Examples 1 to 4 except that maleic anhydride was changed to acrylic acid. The resultant contained a Q-gel, and the both sides of the hue and the adhesion were remarkably inferior to the polymer obtained by the examples. The results of measuring gel, hue, and subsequent strength are shown in Table 6. -84- 200925171

Comparative Example 19 EVA Ο (Ν On in in 〇(N 〇〇〇tr&gt; CN 〇〇〇00 ο ο 〇vn 卜mm CN cn (N Comparative Example 18 EVA ο (Ν 〇\r- 〇(N 〇〇〇 CN 1—Η 〇〇〇οο ο ο S ο 〇Η m H CN &lt;N Comparative Example 17 EVA ο 1—Η CS ΟΝ 卜 in 〇 (N 〇〇〇〇VO (Ν 〇〇00 ο ο 〇〇οο (Ν m Os (N om vo (N Comparative Example 16 HOPE ο ΙΤί νο Ον IT) &lt;N 〇〇〇〇〇〇〇κη (Ν S ο ο ο 〇ο oo &lt; N mm inch Comparative Example 15 g: ο 1-^ Ο Ui rN c&gt; 〇〇〇〇〇ο CN S ο ο g CD 〇ο oo to oo mm Comparative Example 14 L-LDPE ο Ο CS Ον &lt;N &lt;N 〇〇〇〇〇〇ο (Ν S ο ο s ο 〇ο inch inch m Comparative Example 13 EVA ο CS 〇\ r- iri CN 〇〇〇〇〇〇ο *Τ) &lt;Ν S ο ο ο 〇V£) oo VO 卜 m Comparative example HOPE ο os o P — 〇〇〇〇ο ο S ο (Ν ο S 〇o § o Comparative Example 11 ο 1—^ ο as to oi o P 〇〇〇〇ο ο S ο ΠΊ ο S 〇 os Comparison Example L-LDPE ο 宕Os o P 〇 〇〇〇ο ο S ο V-) ο S 〇On 1—H Comparative Example 9 EVA ο cs IT) Os r- tr! o 〇 inch · 〇〇〇〇ο ο S ο ν〇ο 〇〇Ρ 〇ο ON CN to os On 丨 by weight m 4 g/l 〇 min parts by weight parts by weight parts by weight parts by weight parts by weight parts by weight parts by weight % by weight N/15mm N/15mm N/15mm N/15mm N /15mm 俟MFR Maleic anhydride butyl acrylate 1,1,2_trichloroethane (purified) 1,1,2-trichloroethane (unpurified) 浒fi ll £ ο 〇Η PQ DBPIB acid modification Amount of gel m Polyimine polycarbonate Oh 蚝 Imprinted unsaturated carboxylic acid 1 Free radical generator Modified polymer Strength | yu tone) -85- 200925171 Comparative Example 1 3 ~ 1 6 In addition to the reaction solvent by 1 The 1,2-trichloroethane was changed to toluene, and the maleic anhydride was changed to a mixture of maleic anhydride and butyl acrylate, and the addition amount was changed, and the same method as in Examples 1 to 4 was used. A polymer of a branched unsaturated carboxylic acid. The amount of the unsaturated carboxylic acid introduced into the base polymer was small, and the adhesion was remarkably inferior to the polymer obtained in the examples. The results of measuring gel, hue, and subsequent strength are shown in Table 6. 〇Comparative Example 1 7 The same procedure as in Example 1 was carried out except that the reaction solvent was changed from the purified 1,1,2-trichloroethane to unpurified 1,1,2-trichloroethane. Maleic anhydride is grafted to EVA. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 6. The resulting product contained a gel, YI was also high, coloration was observed, and the appearance of the product was poor. Q Comparative Example 18 Maleic anhydride was grafted to EVA by the same method as in Example 1 except that the reaction temperature was lowered from 110 ° C to 35 t. The reaction temperature was low, EVA was not completely dissolved in the solvent, and the entire reaction solution became jelly-like, and the reaction could not be performed uniformly. In addition, since the solution after the reaction is jelly-like and has low fluidity, it cannot be treated with a drum dryer, and after it is precipitated in methanol, it is washed with methanol and dried, and then dried at 40 ° C for one day and one night under reduced pressure. The polymer was isolated, and the analysis results of the obtained polymer and the results of subsequent tests are shown in Table 6', which is the difference in strength. -86-200925171 Comparative Example 1 9 Maleic anhydride was grafted to EVA by the same method as in Example 1 except that the reaction temperature was raised from 110 °C to 135 °C. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 6. The resulting product contained a gel, Y1 was also high, coloration was observed, and the appearance of the product was poor.

Comparative Examples 20 to 23 The same procedure as in Example 18 except that the reaction solvent was changed from 1,1,2-trichloroethane to xylene, and the amount of maleic anhydride added and the amount of BPO added were changed. A polymer obtained by grafting an unsaturated carboxylic acid is obtained by a method. Although the hue is excellent, the amount of the unsaturated carboxylic acid introduced into the base polymer is small, and the gel is present in a large amount, which is remarkably inferior to the polymer obtained in the examples, and the gel, hue, and subsequent strength are measured. The results are shown in Table 7.

-87- 200925171

US Comparative Example 30 EVA ο CN Ον 〇 〇 &lt;N 〇〇1250 〇Ο ο οο ο ο 'Ο 0.05 〇Ό (N (N Comparative Example 29 ί EVA ο &lt;Ν 〇\ 卜tri 〇 (N 〇〇1250 〇ο ο 00 ο ο 0.02 0.09 〇〇&lt;N Comparative Example 28 EVA Ο 1 952 卜 in 〇oi 〇〇〇1250 ο ο 00 ο ο 0.05 VO (N 艺 v〇CN Comparative Example 27 HDPE ο ν〇OS CN o 〇〇〇〇ο 1250 0.03 ο 0.06 0.11 Ο VO ί—^ Inch Comparative Example 26 g: ο 1 900 &lt;N &lt;N o 〇〇〇〇ο 1250 0.03 ο 0.06 〇ο m ν〇Comparative Example 25 L-LDPE ο ο CS ΟΝ (N (N 〇〇〇〇〇ο 1250 0.03 ο 0.05 0.09 ο (N 00 CN (N m Comparative Example 24 EVA ο 1 952 卜&lt;ri (N 〇〇〇〇〇ο 1250 0.03 ο 0.07 〇 inch 比较 Comparative Example 23 HDPE ο «&quot;Η ιη ν〇〇\ iTi o 〇〇〇〇1250 Ο 0.03 ο 0.01 0.06 ο 卜 CN rN m Comparative Example 22 ο ί—^ ο § CN In c&gt; 〇〇〇〇1250 Ο 0.03 ο 0.02 0.06 ο m cn (N inch Comparative Example 21 L-LDPE ο 1 920 &lt;N 〇〇〇〇〇1250 ο 0.03 ο 0.04 0.08 ο ΓΟ 卜 比较 20 20 E E E E E E E E E E E E E E E E E E E E 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 景 景 景 景 景 景 景Parts by weight parts by weight _% by weight parts by weight parts by weight _ _ N/15mm N/15mm N/15mm N/15mm N/15mm Μ Β MFR Maleic anhydride butyl acrylate|1,1, 2-trichloroethane (purification) $ m 遁K1 U Π1 (N-xylene ΒΡΟ ΡΒΡΙΒ acid modified amount of gel polyimine polycarbonate PPS raw material polyolefin unsaturated carboxylic acid solvent free radical generator modification Polymer strength γι (hue) -88- 200925171 Comparative Example 24~27

In addition to changing the reaction solvent from 1,1,2-trichloroethane to toluene', and changing the maleic anhydride to a mixture of maleic anhydride and butyl acrylate, the amount of addition was changed, and Example 18~ 21 The same procedure was used to obtain a polymer grafted with an unsaturated carboxylic acid. The amount of the unsaturated carboxylic acid introduced into the base polymer was small, and the gel was present in a large amount, and the adhesion was remarkably inferior to the polymer obtained in the examples. The results of measuring the gel, the hue, and the subsequent strength are shown in Table 7. Comparative Example 2 8 The same procedure as in Example 18 was carried out except that the reaction solvent was changed from purified 1,1,2-trichloroethane to unpurified 1,1,2-trichloroethane. Maleic anhydride is grafted to EVA. The analysis results of the obtained polymer and the results of subsequent tests are shown in Table 7. The resulting product contained a gel, and the YI 値 was also high, and the coloration was observed, and the appearance of the product was poor. Comparative Example 2 9 Maleic anhydride was grafted to EVA by the same procedure as in Example 18 except that the reaction temperature was lowered from ll 〇 °C to 35 Torr. The reaction temperature was low, EVA was not completely dissolved in the solvent, and the entire reaction solution became jelly-like, and the reaction could not be performed uniformly. In addition, since the solution after the reaction is jelly-like and has low fluidity, it cannot be treated with a drum dryer, precipitated in methanol, washed with methanol, filtered, and then dried at 40 ° C for one day and one night under reduced pressure. The polymer, the analysis results of the obtained polymer, and the subsequent test results are shown in Table 7, which was followed by the difference in strength. -89-200925171 Comparative Example 3 0 Maleic anhydride was grafted to EVA by the same procedure as in Example 18 except that the reaction temperature was raised from 110 °C to 135 °C. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 7. The resulting product contained a gel, and the YI was also high, and the coloration was observed, and the appearance of the product was poor.

❹ Production Example 1: Production Example of Chlorinated Polypropylene (CPP) In a 10 L separable flask equipped with a stirrer, a UV irradiation device, and a reflux condenser, polypropylene having MFR 2.5 and a density of 9000 kg/m 3 was charged. 500 parts by weight, 8 L of ion-exchanged water, and 0.23 part by weight of sodium alkyl sulfonate, and a suspension was prepared, and while the suspension was irradiated with UV, chlorine gas was continuously introduced, and the reaction was carried out at 100 ° C for 6 hours. A chlorinated polypropylene (CPP) having a chlorine content of 20% was obtained. Production Example 2: Production Example of Chlorinated Polyethylene (CPE) A chlorinated polymer having a chlorine content of 16% was obtained by the same method as in Production Example 1 except that the polypropylene was changed to MFR2 and ΙΕDPE having a density of 920 kg/m3. Ethylene (CPE). Example 3 5 10000 parts by weight of 1,1,2-trichloroethane manufactured by Kanto Chemical Co., Ltd. and 500 parts by weight of a 20% aqueous sulfuric acid solution were placed in a 20-liter flask with a lower opening. Stir vigorously' After standing, remove the lower organic layer. Next, 10,000 parts by weight of the taken-out organic layer and distilled water were placed in a 20-liter flask equipped with a lower mouth of -90-200925171, stirred vigorously, and the operation of removing the organic layer of the lower layer was repeated three times after the standing, to remove 1-butanol. And 1,2-epoxybutane' was added to the taken-out organic layer, and 40 parts by weight of molecular sieve 4A' was added and stirred with a stirrer to dehydrate. A 5 liter glass reaction vessel was charged with 25 parts by weight of 1,1,2-trichloroethane of 1-butanol and 1,2-epoxybutane by the above operation, and EVA20 0 Parts by weight and 4 parts by weight of maleic anhydride.

❹ The reactor was heated to 80 ° C, then kept at 80 ° C for 3 hours to uniformly dissolve the EVA, and during this time, nitrogen was introduced into the reactor at a flow rate of 5 liter / minute to remove the air mixed into the reactor. Next, the reactor was heated from 80 ° C to 1 l ° ° C, and 1.6 parts by weight of BPO was dissolved as a catalyst for the graft reaction to remove 1-butanol and 1,2-epoxybutane. 100 parts by weight of the 1,1,2-trichloroethane catalyst solution was continuously added to the reactor for 3 hours for grafting reaction, and then continued at the same temperature for 2 hours, during which time The pressure of the reactor was kept below IMPa. After the completion of the reaction, after the pressure of the reactor was returned to normal pressure, the temperature of the reactor was lowered to 70 ° C, 0.06 parts by weight of BHT as a stabilizer was added, and the solution was heated to a drum of 16 〇t. In the dryer, the modified EVA of the product is separated from the solvent. It is known that the product analysis results are 1.3% by weight of maleic anhydride, no gel, YI of 2, and excellent hue. Further, it is strongly adhered to copper, aluminum, polyimide, polycarbonate, PET, and PPS, and exhibits excellent characteristics as a secondary polymer. The analysis results of the obtained polymer and the results of subsequent tests are shown in Table 8. -91 - 200925171 Qο [8撇] Example 42 CPP 200 1 p inch 2500 I 0.16 I 〇〇in CN cn inch embodiment 41 EVA 200 952 〇 inch ' 2500 0.16 〇〇 (NO m as (Ν VO (Ν ΓΟ Example 40 EVA 200 1 L-952 .1 2 2500 1 0.16 CN 〇〇m 卜 (N CN m Example 39 EVA 200 CN ON Ο 2500 1 0.16 &lt;Ti 〇c&gt; CN ON &lt;N CM (N (N m embodiment 38 HDPE 200 965 ο 2500 〇ΓΠ CN (N CNκη m (N m CN m embodiment 37 200 900 ο — 2500 〇〇〇〇T-Η cn ΓΛ CN m ΓΝΪ m embodiment 36 L-LDPE 200 920 ο ¥ [2500 00 〇〇〇 (Ν 00 CN &lt;N (N Example 35 EVA 200 952 ο inch · "2500 1 [0.16 cn 〇〇 (Ν Ο cn o CO CN (N weight Parts m day|g/i〇minute 1 ! parts by weight parts by weight parts by weight: parts by weight parts by weight parts by weight parts by weight% by weight Brother/15mm S/15mni1 N/15mm ^/15mni| S/15mm 1 density maleic anhydride acrylic acid butyl acrylate ethyl 1,1,2-trichloro Alkanol chloroform monochlorobenzene monofluorobenzene 1,2-dibromo-1,1-difluoroethane benzoic acid modified amount gel 骠polyimine polycarbonate PPS raw material polyolefin unsaturated carboxylic acid Acid solvent free radical generator modified polymer followed by strength YI (color shift -92- 200925171 Example 36. In addition to using purified 1,1,2-trichloroethane, EVA was changed to L-LDPE, borrowed The grafting reaction of maleic anhydride grafted to L-LDPE was carried out in the same manner as in Example 35. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 8. Example 37

The grafting reaction of maleic anhydride grafted to pp was carried out in the same manner as in Example 35 except that the purified 1,1,2-trichloroethane was changed to PP. The analysis results of the polymer and the results of the subsequent tests are shown in Table 8. Example 3 8 Grafting of maleic anhydride grafted to 〇HDPE was carried out by the same method as in Example 35 except that purified 1,1,2-trichloroethane was used and EVA was changed to HDPE. reaction. The analysis results of the obtained polymer and the results of subsequent tests are shown in Table 8. Example 39 Maleic anhydride was grafted to EVA by the same procedure as in Example 35 except that the reaction solvent was changed from purified 1,1,2-trichloroethane to chloroform. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 8. -93-200925171 Example 40 Acrylic acid was grafted to EVA by the same method as in Example 35 except that the reaction solvent was changed from purified 1,1,2-trichloroethane to carbon tetrachloride. The analysis results of the obtained polymer and the results of subsequent tests are shown in Table 8. Example 4 1 Butyl acrylate was grafted to EVA by the same procedure as in Example 35 except that the reaction solvent was changed from purified 1,1,2-trichloroethane to monofluorobenzene. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 8. Example 42 except that the reaction solvent was changed from purified 1,1,2-trichloroethane to 1,2-dibromo-1,1-difluoromethane, and the modified polyolefin was changed from EVA to a production example. Maleic anhydride was grafted to CPP in the same manner as in Example 35 except for the chlorinated polypropylene (CPP) produced. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 8 ° Example 43 except that the modified polyolefin was changed from EVA to chlorinated polyethylene (CPE) produced in Production Example 2, Maleic anhydride was grafted to CPE in the same manner as in Example 35. The results of the classification of the obtained polymer and the results of the subsequent tests are shown in Table 9. -94- 200925171 [6S Example 48 CPE 200 1 〇 (N 〇 oi 2500 0.16 〇〇 ON (N (N m CN Example 47 CPP 200 &gt; 〇 inch _ 2500 0.16 ΓΟ 〇〇00 (N m 〇o ( N 00 (N Example 46 HDPE 200 ON 〇CN 〇 (N 2500 0.16 00 t-η 〇〇in inch 卜V V 〇 Example 45 &amp; 200 900 〇 (N 〇CN 2500 0.16 〇 (N 〇〇rH 〇 CN oo cn Example 44 LDPE 1 200 〇&lt;N On 〇-2500 0.16 \〇〇&lt;d&gt; 宕Ό m &lt;N m Example 1__43 — CPE 200 1 inch · 2500 0.16 in 〇〇 (N m 00 (N inch 丨 part by weight m day | g / i 〇 minute 重量 parts by weight parts by weight parts by weight parts by weight parts by weight _ tlrml paste weight % | N / 15mm , N / 15mm | S / 15mm N/15mm N/15mm j side maleic anhydride acrylic acid butyl acrylate ethyl acrylate U, 2-trichloroethane chloroform carbon tetrachloride monofluorobenzene 1,2-dibromo-1,1-difluoroethane Benzoyl phthalate modified amount gel polyimine polycarbonate PPS raw material polyolefin unsaturated carboxylic acid Agent free radical generator modified polymer strength YU tone) -95- 200925171 Example 44 In addition to changing the modified polyolefin from EVA to LDPE, and changing the unsaturated carboxylic acid from maleic anhydride to acrylic acid, In the same manner as in Example 35, acrylic acid was grafted to LDPE. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 9. Example 45

The unsaturated carboxylic acid was grafted in the same manner as in Example 35 except that the modified polyolefin was changed from EVA to PP and the unsaturated carboxylic acid was changed from maleic anhydride to a mixture of maleic anhydride and butyl acrylate. Branched in PP. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 9. Example 4 6 except that the modified polyolefin was changed from EVA to HDPE, and the unsaturated hydrazine carboxylic acid was changed from maleic anhydride to maleic anhydride. The unsaturated carboxylic acid was grafted to HDPE by the same method as in Example 35 except that a mixture of ethyl acrylate was used. The analysis results of the obtained polymer and the results of subsequent tests are shown in Table 9. Example 47 The same procedure as in Example 35 except that the modified polyolefin was changed from EVA to chlorinated polypropylene (CPP) produced in Production Example 1, and the unsaturated carboxylic acid was changed from maleic anhydride to acrylic acid. The graft is grafted with acrylic acid -96-200925171 in CPP. The analysis results of the obtained polymer and the results of subsequent tests are shown in Table 9. Example 4 8

In addition to changing the modified polyolefin from EVA to chlorinated polyethylene (CPE) manufactured in Production Example 2, and changing the unsaturated residual acid from maleic anhydride to a mixture of maleic anhydride and butyl citrate, Maleic anhydride was grafted to the CPE by the same procedure as in Example 35. The analysis results of the obtained polymer and the results of subsequent tests are shown in Table 9. Comparative Example 3 1 The same procedure as in Example 35 was carried out except that the reaction solvent was changed from purified 1,1,2-trichloroethane to monochlorobenzene having a boiling point of 132 ° C under normal pressure. Maleic anhydride is grafted to EVA. The polymer solution after the reaction was introduced into a drum dryer, and the segregation of the test polymer was tasted by the same method as in Example 35, but the polymer film adhered to the drum, the film could not be peeled off, and the continuous separation could not be performed. polymer. Therefore, the polymer solution could not be isolated by re-precipitation with methanol. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 1, and the strength was lowered. -97- 200925171 οο [01 撇] Comparative Example 33 EVA 200 I 952 〇—2500 0.16 (N 〇〇νο 3 in (N Comparative Example: “J2— _ EVA 200 952 〇τί- 2500 0.16 inch· 〇〇00 ( CM CM m CN (N Comparative Example 31 EVA 200 (N in ON q — 2500 0.16 p 〇CN (Ν 00 (Ν N (N inch 1 part by weight m 丨 g/10 minutes 丨 parts by weight parts by weight | parts by weight | weight Parts by weight ιΐτπΐΐ _ N/15mm N/15mm N/15mm N/15mm N/15mm Maleic anhydride 1,1,2-trichloroethane monochlorobenzene 1 benzoic acid modified gel germination醯imine polycarbonate PPS raw material polyolefin unsaturated carboxylic acid solvent free radical generator modified polymer strength YU color tone) -98-

〇 200925171 Comparative Example 3 2 Maleic anhydride EVA was obtained by the method shown in Example 35 except that the polymer after the graft reaction of the unsaturated carboxylic acid was changed. After the completion of the reaction, after the pressure of the reactor was returned to normal pressure, the temperature of 5 was lowered to 70 ° C, and BHT 0.06 I as a stabilizer was added, and water was supplied to the reaction system to carry the temperature of the reactor again. 〇°C, the water is azeotroped with 1,1,2-trichloroethane, and 1,1,2-trichloroz is removed to the outside of the reactor, and 200 parts by weight of water is supplied to the reaction heat. A suspension of the high concentration polymer solution dispersed in water. This was held in a pulverizer which circulated 300 ml of methanol to obtain a slurry which was pulverized at the same time as the polymerization. The slurry was filtered, and 5 L of methanol was used, and then dried under reduced pressure at 40 ° C overnight. And get a dried game. As described above, this method is compared with the method represented by the embodiment, and the method of economical cost and cost is lacking. The analysis results of the obtained polymer and the subsequent test results are shown in Table 10, but the strength was subsequently lowered. Comparative Example 33 A horse was prepared by a method similar to that of the example except that the reaction solvent was purified from 1,1,2-trichloroethane and a toluene having a boiling point of 1 l〇.6 ° C under normal pressure. The anhydride is grafted to EVA. Because the E solution after the reaction is introduced into the drum dryer 'different from the non-combustible three: the volatilized toluene vapor may have a risk of igniting and exploding, although the operation branch is high in the hospital, the liquid is obtained. The precipitated washing compound was mixed and shown in: more homopolymerized, ethane: the polymer was isolated by the same method as in Comparative Example 31 by -99-200925171' but it was very complicated and time consuming and costly. Lack of economics. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 1 and the strength was lowered. Example 49 &lt;Production of Unsaturated Carboxylic Acid-Grafted Polyolefin&gt; 0 5000 parts by weight of 1,1,2-trichloroethane and 2500 parts by weight of a 26% aqueous sulfuric acid solution were placed in the lower mouth. The 1 liter flask was vigorously stirred, and after standing, the lower organic layer was taken out. Then, 'the extracted organic layer and 5 kg of distilled water were placed in a 1-liter flask equipped with a lower mouth and stirred vigorously'. The operation of removing the organic layer of the lower layer was repeated 3 times to remove the butanol and 1,2- Epoxy butane. Further, by adding 150 parts by weight of the molecular sieve 4A to the taken-out organic layer and dehydrating by stirring with a stirrer, purified 1,1,2-trichloroethane (hereinafter referred to as purified TCE) was obtained. Purifying 2480 parts by weight of TCE and 200 parts by weight of EVA, and 4.1 parts by weight of maleic anhydride in a 4 liter glass reaction vessel, heating the reactor to 80 ° C, and then by 80 ° C The EVA was uniformly dissolved for 4 hours, and during this time, nitrogen gas was introduced into the reactor at a flow rate of 5 liters/min to remove the air mixed into the reactor, and 1.5 parts by weight of BPO was used as a catalyst for the graft reaction. The solution was dissolved in 100 parts by weight of purified TCE, and this solution was continuously continuously added to the reactor, and the pressure of the reactor was maintained at 1 MPa, and grafting reaction was carried out for 3 hours. After the completion of the reaction, the pressure was returned to normal pressure, the temperature of the reactor was raised to 70 ° C, and 0.06 part by weight of BHT as a stabilizer was added to add -100 to 200925171, and this solution was poured into a large amount of methanol to make The product of maleic anhydride grafted EVA was separated from the solvent. The result of the analysis of the product was found to be 1.5% by weight of an unsaturated carboxylic acid (maleic anhydride), the gel was 〇% by weight, the YI was 2, and the hue was excellent. &lt;Production of unsaturated carboxylic acid grafted polyolefin film&gt;

By using the double-action compression molding machine WFA-50, the above-mentioned unsaturated carboxylic acid grafted EVA is heated at a temperature of 150 ° C, a pressure of 10 MPa, a heating time of 1 〇 minutes, a cooling temperature of 30 ° C, Pressure molding was carried out under the conditions of a pressure of 10 MPa and a cooling time of 5 minutes to obtain a film (film 1) having a size of 5 Omm X 1 00 mm and a thickness of 100 μm, and the obtained film was excellent in appearance and properties, and no fisheye or the like was observed. Disadvantages. &lt;Insulation coating of copper flakes&gt; Q A film (film 1) having a size of 50 mm x 10 mm, a thickness of 100 μm, a size of 100 mm x 100 mm of a surface which is not subjected to lamp treatment, a copper sheet having a thickness of 0.5 mm (sheet 1), and a size of 100 mm x 100 mm A polyimide film (film 2) having a thickness of 100 μm was laminated by the composition of the sheet 1 / film 1 / film 2 to obtain a copper sheet under the conditions of a pressure of 2 MPa, a temperature of 180 ° C, and a time of 1 minute. And half of the area of the polyimide film is passed through the subsequent composition. A thin rectangular sample having a length of 100 mm and a width of 15111111 was cut out from the obtained laminate so that half of the area was followed, and half of the area was not followed, at a stretching speed of -101 - 200925171 〇

As a result of the T-peel test under conditions of 30,000 mm/min, the laminate exhibited excellent peel strength of 4 Å / 15 mm. In addition, it can be confirmed that the test piece has undergone 200 thermal cycle tests between the materials constituting the laminate.

No peeling or breakage occurred, and it was a laminate which was strong for hot stamping, and the results are shown in Table 11. Q -102- 200925171 ο Ο [11¥ Example 56 LDPE maleic anhydride 1 (N 〇 inch copper flakes maleic anhydride grafted EVA ^ m crocodile m 1 1 1 200 or more Example 55 EVA maleic anhydride 1 00 〇 Aluminum flakes Maleic anhydride grafted EVA PPS flakes 1 1 1 200 Above Example 54 EVA Maleic anhydride 1 〇cn Aluminum flakes Maleic anhydride grafted EVA Polycarbonate film 1 1 1 200 Above Example 53 EVA Acrylic acid 1 〇 aluminum Sheet acrylic graft EVA salt tender m 1 1 1 200 or more Example 52 EVA Maleic anhydride ethyl acrylate cncn aluminum sheet ^ K! w long i Zhao sleeping PPS sheet _1 maleic anhydride / ethyl acrylate graft EVA Copper flakes 1 - Η 200 Above Example 51 EVA Maleic anhydride butyl acrylate N (N 〇m copper flakes via fc ω ^ f t &lt; polycarbonate film maleic anhydride / butyl acrylate graft EVA copper flakes Ό ro 200 Example 50 above EVA acrylic acid 1 〇〇〇 (N copper foil acrylic grafted EVA aluminum foil 1 1 00 1 200 or more Example 49 EVA maleic anhydride 1 〇CN copper foil maleic anhydride graft EVA crocodile tender embedded 1 1 ο More than 1,200 polyolefins Unsaturated Carboxylic Acid 1 Unsaturated Carboxylic Acid 2% by Weight Weight % 1 幽CN 幽m 寸幽yri 幽 N/15mm 1 N/15mm ι Acid Modified Gel YI (Hue) Layer 1 / Layer 3 Layer 3 Layer 5 The number of times of peeling of the raw material-modified polymer was adhered to the strength and thermal cycle test. -103 - 200925171. Example 5 EVA of grafted acrylic acid was produced by the same method as in Example 49, followed by thinning and subsequent tests. The laminate was obtained by the same method as that of Example 49 except that the adhesive was a copper foil and an aluminum foil. The result of the peeling test of the laminate was carried out. 'The laminate showed 3 8 N/1 5 mm. The peeling strength was very strong, and it was confirmed that the test piece passed through 200 heat cycle tests, and the laminates were not peeled or broken between the materials constituting the laminate, and were strong laminates for hot stamping. Shown in Table 1 1. Example 5 1

The EVA grafted with maleic anhydride and butyl acrylate was produced by the same method as in Example 49, and thinned and then tested. An EVA film/polycarbonate film/grafted maleic anhydride and butyl acrylate EVA film/copper obtained from copper flakes/grafted maleic anhydride and butyl acrylate was obtained by the same method as in Example 49. The laminate of the five layers formed by the sheet was subjected to the peeling test of the laminate, and the laminate layer 1 / layer 3 had a peel strength of 4 2 N /1 5 mm, and the layer 3 / layer 5 The peel strength between the sheets was 3 6 N/1 5 mm, showing a very strong peel strength. Further, it was confirmed that the test piece was subjected to a heat cycle test for 200 times, and the material constituting the laminate did not cause peeling or breakage of the stomach, and was a strong laminate for hot stamping. The results are shown in Table 11. Example 52 -104-200925171 EVA grafted with maleic anhydride and ethyl acrylate was produced by the same procedure as in Example 49, followed by thinning and subsequent tests. By the same method as in Example 49, an EVA film/PPS sheet/grafted maleic anhydride and an ethyl acrylate-based EVA film/copper sheet of aluminum flakes/grafted maleic anhydride and ethyl acrylate were obtained. A 5-layer laminate. As a result of performing the peeling test of this laminate, the present laminate showed a peel strength between layer 1 / layer 3 of 50 N / 15 mm, and a peel strength between layer 3 / layer 5 of 4 1 N / 15 mm Very strong peeling strength, and it was confirmed that the test piece passed through 200 thermal cycle tests, and the laminates were not peeled or broken between the materials, and the laminates were strong laminates. Shown in Table 11. Example 5 3 EVA of grafted acrylic acid was produced by the same method as in Example 49, followed by thinning and subsequent tests. A laminate was obtained by the same method as in Example 49 except that Example 49 and an aluminum foil having a thickness of 〇5 mm and a polyimide film having a thickness of 1 μm were used. As a result of performing the peeling test of this laminate, the present laminate exhibited a very strong peel strength of 5 1 Ν / 15 mm, and further, it was confirmed that the test piece was subjected to 200 thermal cycle tests 'constituting the laminate. There was no peeling or breakage between the materials, and it was a strong laminate for hot stamping, and the results are shown in Table 11. Example 54 - 105-

200925171 A grafted maleic acid EVA was prepared by the same method as in Example 49, followed by thinning and subsequent tests. Lamination was carried out in the same manner as in Example 49 except that the Example 49 and the adhesive were an aluminum flake having a thickness of 0.5 mm and a polyacrylate film having a thickness of 1 μm. As a result of performing the peeling test of this laminate, the present laminate exhibited a very strong peel strength of 53 Å / 15 mm, and it was confirmed that the test was conducted between the materials of the laminate through 200 heat cycle tests. It is not peeled or broken, and is a strong laminate for hot stamping. The results are shown in Table 11. Example 5 5 Grafted maleic anhydride EVA was produced by the same procedure as in Example 49, followed by thinning and subsequent tests. A laminate was obtained in the same manner as in Example 49 except that Example 49 and an aluminum foil having a thickness of 〇5 mm and a PPS having a thickness of 1 mm were used. As a result of the peeling test of this compound, the present laminate exhibited a very strong peel strength of 55 N/15 mm, and it was confirmed that the test piece was subjected to 200 heat cycle tests to constitute a laminate material. There is no peeling or breaking, and it is a laminate which is strong for hot stamping, and the results are shown in Table 11. Example 5 6 A LDPE grafted with maleic anhydride was produced by the same method as in the Example except that the polyolefin was changed to LDPE, and the film was further subjected to a test, and the results are shown in Table i i. The bad layer of the carbonaceous material produced by the layer 4-9-106-200925171 Example 5 7 The grafted horse was produced by the same method as in Example 49 except that the polyolefin was changed to HD PE. The HDPE of the anhydride was subjected to a subsequent test after the film formation, and the laminate was obtained by the same method as in Example 49 except that the polyimide film was made of an aluminum foil having a thickness of 55 mm. The results of the tests are shown in Table 12. 〇-107 200925171 ο〇 [(Nls Example 63 EVA 1 Maleic anhydride 1 00 Ο m Aluminum flakes Maleic anhydride grafted EVA Copper flakes Maleic anhydride grafted EVA 1 1 1 Film rupture 200 or more Example 62 EVA Acrylic acid 1 〇m aluminum foil acrylic graft EVA 1 1 1 1 film cracking 1 1 200 or more Example 61 maleic anhydride 1 〇ΓΟ aluminum flake maleic anhydride graft PP polyimine film maleic anhydride graft PP 1 1 〇〇 1 1 1 200 or more 1 Example 60 L-LDPE Maleic anhydride butyl acrylate 〇m Aluminum sheet 11 s 1^3 With ® Polyimine film | 1 a Iap3 Aluminum sheet 〇 1 1 1 - Η 200 or more Examples 56 CPP maleic anhydride 1 beryllium copper flakes maleic anhydride grafted CPP polyimine film maleic anhydride grafted CPP copper flakes 1 1 200 above Example 55 L-LDPE maleic anhydride acrylic acid bismuth copper bismuth copper maleate / Acrylic acid grafted L-LDPE polycarbonate film maleic anhydride / decanoic acid grafted L-LDPE 1 ο 1 1 1 200 above Example 57 HDPE maleic anhydride 1 〇 inch copper flake maleic anhydride graft HDPE 1 aluminum Sheet 1 1 1 1 1 200 or more polyolefin is not full Carboxylic acid 1 ! Unsaturated carboxylic acid 2 Thunder %! Weight 0 / 〇 * 幽 (N 13^ inch 幽 N / 15mm N / 15mm N / 15mm N / 15mm acid modified amount 丨 gel YI (hue) Layer 1 /layer 3 layer 1 / layer 2 layer 3 / layer 4 layer 3 / layer 5 peeling times raw material modified polymer adherent strength thermal cycle test -108- 200925171 Example 5 8 In addition to changing the polyolefin to L-LDPE A graft of maleic anhydride and L-LDPE of acrylic acid was produced by the same method as in Example 49, and the film was subjected to a subsequent test. The same procedure as in Example 49 was carried out to obtain a copper flake/graft. A four-layer laminate of maleic anhydride and acrylic acid L-LDPE film/polycarbonate film/grafted maleic anhydride and acrylic acid L-LDPE film, and the peeling test of the laminate was carried out, and the result was as follows. Column

Example 59 In a 10 L separable flask equipped with a stirrer, a UV irradiation apparatus, and a reflux cooler, 500 parts by weight of polypropylene having MFR 2.5, density of 900 kg/m 3 , ion-exchanged water of 8 L, and 〇·23 parts by weight were charged. The sodium alkylsulfonate was prepared, and the suspension was irradiated with UV gas, and chlorine gas was continuously introduced thereto, and the mixture was reacted at 1 ° C for 6 hours to obtain a chlorinated polypropylene having a chlorine content of 20%. Using the obtained chlorinated P P, a CPP obtained by grafting maleic anhydride was obtained by the same method as in Example 49, and then subjected to a subsequent test after film formation. By the same method as in Example 49, a 5-layer layer of a copper foil/grafted maleic anhydride CPP film/polyimine film/grafted maleic anhydride CPP film/copper sheet was obtained. The laminate and the peel test for carrying out the laminate were shown in Table 12. Example 60 -109- 200925171

L-LDPE grafted with maleic anhydride and butyl acrylate was produced by the same method as in Example 49 except that LFR was changed to MFR2 and had a density of 920 kg/m3. Further, the obtained modified L- The LDPE was subjected to the same method as in Example 49 to carry out a subsequent test. L-LDPE film/polyimine film/grafted maleic anhydride and butyl acrylate L-LDPE obtained from aluminum flakes/grafted maleic anhydride and butyl acrylate were obtained by the same method as in Example 49. A peel test of the laminate was carried out on the laminate of the five layers of the film/Ming sheet, and the results are shown in Table 12. Example 6 1 PP which was grafted with maleic anhydride was produced by the same method as in Example 49 except that the polyolefin was changed to PP, and the film was subjected to a subsequent test. A four-layer laminate of a copper foil/grafted maleic anhydride PP film/polyimine film/grafted maleic anhydride PP film was obtained by the same method as in Example 49. A peel test of this laminate was carried out, and the Q results thereof are shown in Table 12. Example 62 An EVA film grafted with acrylic acid was produced by the same method as in Example 49, followed by grafting an acrylic EVA film on one side of an aluminum foil having a thickness of 0.5 mm, at which time, it was followed by an aluminum foil. The film of the acrylic grafted EVA protected with a polyethylene terephthalate film on the opposite side was obtained by the same method as in Example 49. As a result of the peeling test of this laminate, since the EVA film and the aluminum foil were strong in strength from -110 to 200925171, the EVA film was first broken, and further, it was confirmed that the test piece was subjected to thermal cycling test for 200 times to constitute lamination. No peeling occurred between the materials of the material, which was a strong laminate for hot stamping, and the results are shown in Table 12. Example 63 An aluminum flake/maleic anhydride was obtained by the same procedure as in Example 49, from an aluminum flake having a thickness of 〇5 mm, a copper flake having a thickness of 55 mm, and a maleic anhydride grafted EVA film having a thickness of ΙΟΟμηη. A four-layer laminate composed of a grafted EVA film/copper sheet/maleic anhydride grafted EVA film. The results of the subsequent tests for carrying out this laminate are shown in Table 12. Example 64 &lt;Production of Unsaturated Carboxylic Acid-Grafted Polyolefin&gt;

5 000 parts by weight of 1,1,2-trichloroethane and 2500 parts by weight of a 26% aqueous solution of sulfuric acid were placed in a 10-liter flask with a lower mouth and stirred vigorously, and after standing, the lower organic layer was taken out, followed by The removed organic layer and 5 kg of distilled water were placed in a 10-liter flask with a lower mouth and vigorously stirred. After standing, the operation of taking out the lower organic layer was repeated three times to remove 1-butanol and 1,2-epoxy. Butane, by adding 150 parts by weight of molecular sieve 4A to the extracted organic layer, and dehydrating with a stirrer to obtain purified 1,1,2-trichloroethane (hereinafter, referred to as purification 1) ). A 4 liter glass reaction vessel was charged with 2480 parts by weight of purified TCE and 200 parts by weight of EVA, and 4.1 parts by weight of maleic anhydride, and the -111 - 200925171 reactor was heated to 80 ° C, and then EVA was uniformly dissolved at 80 ° C for 4 hours. Further, during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liters / minute to remove air mixed into the reactor, and 1.5 parts by weight as a catalyst for the graft reaction was used. BPO was dissolved in 100 parts by weight of purified TCE. After adding this solution to the reactor for 1 hour, the grafting reaction was carried out for 3 hours while the pressure of the reactor was maintained at 1 MPa. After the reaction was completed, the pressure was returned to normal. Pressurize, increase the temperature of the reactor to 70 ° C, add 6 parts by weight of BHT as a stabilizer, and inject this solution into a large amount of methanol to form a product of maleic anhydride grafted EVA from the solvent. Separated. The result of the analysis of the product was found to be 1.5% by weight of an unsaturated carboxylic acid (maleic anhydride), the gel was 0.011% by weight, the YI was 2, and the hue was excellent. &lt;Production of unsaturated carboxylic acid grafted polyolefin film&gt;

The above-mentioned unsaturated carboxylic acid was grafted with EVA by using a double-action compression molding machine WFA-50 at a heating temperature of 150 ° C, a pressure of 10 MPa, a heating time of 1 Torr, a cooling temperature of 30 ° C, and a pressure of 10 MPa. The film was formed by press molding under the conditions of a cooling time of 5 minutes to obtain a film (film 1) having a size of 50 mm x 100 mm and a thickness of 100 μm. The obtained film was excellent in appearance and properties, and the defects such as fish eyes were not observed. &lt;Insulation coating of copper sheet&gt; Film of the obtained size 50 mm x 100 mm 'thickness ΙΟΟμηη-112-200925171 (film 1), copper sheet (sheet 1) having a surface treatment size of 1 OO mm x 100 mm and a thickness of 0.5 mm, A polyimine film (film 2) having a size of loommxlOOmm and a thickness of 100 μm was laminated by a composition of a sheet w film w film 2, and a copper sheet was obtained under the conditions of a pressure of M2 Mpa and a temperature of 18 (TC, time of 1 minute). Half of the area of the polyimide film was passed through the laminate. A thin rectangular sample having a length of 100 mm and a width of 15 mm was cut out from the obtained laminate, so that the area of the half was followed by half of the area. As a result of performing a T-type peeling test under the conditions of a tensile speed of 300 mm/min, the present laminate exhibited excellent peel strength of 42 N/15 mm. Further, it was confirmed that the test piece was heated by 200 times. In the cycle test, no peeling or breakage was observed between the materials constituting the laminate, and the results were shown in Table 13.

-113- 200925171 ο Ο [Π撇] Example 71 LDPE Maleic Anhydride 1 (N 0.010 inch copper flake maleic anhydride grafted EVA polyimine film 1 1 5 1 200 or more Example 70 EVA maleic anhydride 1 00 0.014 Aluminum flakes Maleic anhydride grafted EVA PPS flakes 1 1 CN 1 200 Above Example 69 EVA Maleic anhydride 诵 0.011 m Aluminum flakes Maleic anhydride grafted EVA Feeding mm ϋ 嵌 1 1 1 200 200 Above E 68 Acrylic acid 1 ! 0.011 m Aluminium foil Acrylic grafted EVA crocodile 1 1 1 200 or more Example 67 EVA Maleic anhydride ethyl acrylate Η 0.014 m Aluminum flakes Κ ω g 怒 uf SI PPS flakes Maleic anhydride / ethyl acrylate Grafted EVA copper flakes 〇 200 above Example 66 EVA Maleic anhydride butyl acrylate 〇 0.013 m Copper flakes tw Protected by your polycarbonate film Maleic anhydride butyl acrylate graft EVA Copper flakes 〇 m 200 or more Example 65 EVA Acrylic acid 1 oo 0.013 fN Copper flakes Acrylic grafted EVA Aluminum flakes 1 1 〇 1 200 Above Example 64 丨 EVA Maleic anhydride 1 0.011 (N copper flake maleic anhydride grafted EVA) 3⁄4 m 磐 tender m 1 1 1 200 or more I polyolefin! Unsaturated carboxylic acid 1 Unsaturated carboxylic acid 2 1% by weight % by weight 1 幽&lt;N cn is inch _ N/15mm N/15mm acid-modified gel YU tone) Layer 1 / layer 3 layer 3/layer 5 peeling times raw material modified polymer adherend followed by strength heat cycle test-114-200925171 Example 65 by grafting acrylic acid-containing EVA' in the same manner as in Example 64, after thinning Next, a laminate was obtained by the same method as in Example 64 except that the adherend was a copper foil and an aluminum foil. As a result of performing the peeling test of the laminate, the laminate exhibited a very strong peel strength of 40 N/15 mm, and further, it was confirmed that the test piece was subjected to a thermal cycle test of 200 times to constitute a laminate material. There is no peeling or damage, and it is a strong laminate for hot stamping, and the results are shown in Table 13. Example 66 EVA obtained by grafting maleic anhydride and butyl acrylate was produced by the same method as in Example 64, followed by film formation and subsequent test, and the same procedure as in Example 64 was carried out to obtain a copper foil/wafer. EVA film/polycarbonate film grafted with maleic anhydride and butyl acrylate/5 layer laminate of grafted maleic anhydride and Q-butyl acrylate EVA film/copper sheet. As a result of performing the peeling test of this laminate, the present laminate showed a very strong peel strength of a peel strength of 40 Å/15 5 mm between layers 3 and 5 and a peel strength of 35 N/15 mm between layers 3 and 5. In addition, it was confirmed that the test piece was subjected to 200 thermal cycle tests, and the laminates were not peeled or broken between the materials constituting the laminate, and the laminates were strong for thermal pulverization. The results are shown in Table 13. Example 67 -115- 200925171

The EVA grafted with maleic anhydride and ethyl acrylate was produced in the same manner as in Example 64, and subjected to film formation followed by a test. By the same method as in Example 64, an EVA film/PPS sheet/grafted maleic anhydride and an ethyl acrylate-based EVA film/copper sheet of aluminum flake/grafted maleic anhydride and ethyl acrylate were obtained. A 5-layer laminate. As a result of performing the peeling test of this laminate, the present laminate showed a peel strength between layer 1/layer 3 of 48 N/15 5 mm, and a peel strength between layer 3/layer 5 of very strong 40 N/1 5 mm. In addition, it was confirmed that the test piece was subjected to a thermal cycle test of 200 times, and no peeling or breakage occurred between the materials constituting the laminate, and it was a strong laminate for hot stamping, and the result was 7K. In Table 13. Example 6 8 EVA of grafted acrylic acid was produced by the same method as in Example 64, followed by thinning and subsequent tests. A laminate was obtained in the same manner as in Example 64 except that the Example 64 and the adherend were an aluminum flake having a thickness of 〇5 mm and a polyimide film having a thickness of Ι00 μm. As a result of the peeling test of this laminate, the laminate exhibited a very strong peel strength of 54 Å / 15 mm. Further, it was confirmed that the test piece passed through the thermal cycle test for 200 times, and the laminates were not peeled or broken between the materials constituting the laminate, and were strong laminates for hot stamping. The results 歹IJ are shown in Table 13. Example 69 - 116 - 200925171 EVA of grafted maleic anhydride was produced by the same procedure as in Example 64, followed by thinning and subsequent tests. A laminate was obtained in the same manner as in Example 64 except that the Example 64 and the adherend were an aluminum foil having a thickness of 〇5 mm and a polycarbonate film having a thickness of ΙΟΟμηη. As a result of performing the peeling test of the laminate, the laminate exhibited a very strong peel strength of 50 N/15 mm, and further, it was confirmed that the test piece was subjected to 200 heat cycle tests to constitute a laminate material. There is no peeling or damage, and it is a strong laminate for hot stamping, and the results are shown in Table 13. Example 70 An EVA grafted with maleic anhydride was produced by the same procedure as in Example 64, followed by thinning and subsequent tests. A laminate was obtained in the same manner as in Example 64 except that the Example 64 and the adherend were an aluminum foil having a thickness of 55 mm and a PPS having a thickness of 1 mm. As a result of the peeling test of this layer of the composition, the laminate exhibited a very strong peel strength of 52 N/1 5 mm, and it was confirmed that the test piece was subjected to 200 cycles of heat cycle test to constitute each of the laminates. There was no peeling or breakage between the materials, and it was a strong laminate for hot stamping, and the results are shown in Table 13. Example 7 1 A LDPE grafted with maleic anhydride was produced by the same procedure as in Example 64 except that the polyolefin was changed to LDPE, and the film was subjected to a subsequent test. The results are shown in Table 13. 117- 200925171

Example 72 In addition to the modification of the polyolefin to HDPE, HDPE grafted with maleic anhydride was produced by the method of the sample of Example 64, and the film was subjected to the subsequent test. A laminate test was conducted in the same manner as in Example 64 except that the polyimide film was made of an aluminum foil having a thickness of 55 mm, and the peel test of the composition was carried out. The results are shown in Table 14. -118- 200925171 [Inch 1 ¥ Example 78 EVA Maleic anhydride 1 〇〇 0.015 m Aluminum flakes Maleic anhydride grafted EVA Copper flakes Maleic anhydride grafted EVA 1 1 1 Film rupture 200 or more Example 77 EVA Acrylic acid 1 0.011 m Aluminium foil acrylic grafted EVA 1 1 1 1 Film cracked 1 1 200 or more Example 76 &amp; Maleic anhydride 1 inch · 0.012 m Copper flakes Maleic anhydride grafted PP Polyimine film Maleic anhydride grafted PP 1 〇1 1 1 200 or more Example 75 L-LDPE Maleic anhydride butyl acrylate 0.015 m Aluminum flakes 1^3 Polyimide film 1^3 Aluminum flakes 1 1 〇200 or more Example 74 Ah P-. ο Malay Anhydride I m fN 0.016 m Copper flakes &amp; 氍 ^ HU 醯 醯 醯 薄膜 薄膜 & & 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- Copper flake maleic anhydride / acrylic acid grafted L-LDPE polycarbonate film maleic anhydride / acrylic acid grafted L-LDPE 1 1 1 1 200 or more Example 72 HDPE maleic anhydride 1 (N 0.011 inch copper flake maleic anhydride Branch HDPE aluminum sheet 1 1 1 1 1 200 or more polyolefin Unsaturated Carboxylic Acid 1 Unsaturated Carboxylic Acid 2 Thunder Amount % |% by Weight 隹(N _ m 寸i; 幽N/15mm N/15mm N/15mm N/15mm Acid Modified Gel YU Tone) Layer 1 Layer 3 Layer 1 / Layer 2 Layer 3 / Layer 4 Layer 3 / Layer 5 Stripping Times Raw Material Modified Polymer Adhesive Next Strength Thermal Cycle Test 119 - 200925171 Example 73 In addition to changing the polyolefin to L-LDPE, L-LDPE grafted with maleic anhydride and acrylic acid was produced in the same manner as in Example 64, and the film was subjected to a subsequent test. The same procedure as in Example 64 was carried out to obtain a copper flake/grafted maleic anhydride. And a laminate of four layers of an L-LDPE film/polycarbonate film/grafted maleic anhydride and an L-LDPE film of acrylic acid, and a peeling test of the laminate was carried out, and the results are shown in the table. Example 74 In a 10 L separable flask equipped with a stirrer, a UV irradiation apparatus, and a reflux cooler, 500 parts by weight of polypropylene having MFR 2.5, density of 900 kg/m 3 , 8 L of ion-exchanged water, and 0.23 parts by weight of an alkyl group were charged. Sodium sulfonate, a suspension is prepared, and the suspension is continuously introduced with chlorine while irradiating UV to the suspension. In the reaction for 6 hours l〇〇 ° C, a chlorine content of chlorinated Q 2〇% polypropylene. Using the obtained chlorinated PP, a CPP obtained by grafting maleic anhydride was obtained by the same method as in Example 64, and then a film was formed and subjected to a subsequent test. By the same method as in Example 64, a 5-layer layer of a copper foil/grafted maleic anhydride CPP film/polyimine film/grafted maleic anhydride CPP film/copper sheet was obtained. The laminate was subjected to a peel test of this laminate, and the results are shown in Table 14. Example 75 - 120 - 200925171 L-LDPE 'addition' of grafted maleic anhydride and butyl acrylate was produced by the same procedure as in Example 64 except that LFR was changed to MFR 2 and a density of 920 kg/m 3 . The obtained modified L-LDPE was thinned by the same method as in Example 64, and the subsequent test was carried out. An L-LDPE film/polyimine film/a grafted maleic anhydride and butyl acrylate L_LDPE film obtained from aluminum flakes/grafted maleic anhydride and butyl acrylate was obtained by the same method as in Example 64. The laminate of the five layers of the aluminum foil was subjected to a peel test of the laminate, and the results are shown in Table 14. Example 7 6 PP which was grafted with maleic anhydride was produced by the same method as in Example 64 except that the polyolefin was changed to PP, and the film was subjected to a subsequent test. A four-layer laminate of a copper foil/grafted maleic anhydride PP film/polyimine film/grafted maleic anhydride PP film was obtained by the same method as in Example 64. The peel test of this laminate was carried out, and the results are shown in Table 14. Example 7 7 EVA of grafted acrylic acid was produced by the same method as in Example 64 on one side of an aluminum foil having a thickness of 0.5 mm, followed by grafting an EVA film of acrylic acid, at this time, with an aluminum foil A laminate of acrylic acid-grafted EVA film protected with a polyethylene terephthalate film on the opposite side of the surface was obtained in the same manner as in Example 64. As a result of the peeling test of this laminate, since the EVA film and the aluminum thin-121 - 200925171 sheet had strong adhesive strength, the EVA film was first broken, and further, it was confirmed that the test piece was subjected to 200 thermal cycle tests to form a layer. The peeling of each material of the compound did not occur, and it was a strong laminate for hot stamping, and the results are shown in Table 14. Example 78

Aluminum flake/maleic anhydride grafted EVA film/copper formed by aluminum flakes having a thickness of 0.5 mm, copper flakes having a thickness of 55 mm, and a maleic anhydride grafted EVA film having a thickness of ΙΟΟμηη by the same method as in Example 64. A four-layer laminate of a sheet/maleic anhydride grafted EVA film. The results of the subsequent tests for carrying out this laminate are shown in Table 14. Comparative Example 3 4 Sections Cl, C2, and C3 were set at 150, 180, and 200 ° C using a two-axis extruder of 115 mechanical industry mm φ and L/D = 5 制 manufactured by NAKATANI, and the section C4 was CIO, A, and D were set at 220 ° C, and the unreacted unsaturated carboxylic acid was removed from the exhaust port between C6 and C7 at a number of revolutions of 1 1 O rpm to carry out a graft reaction. That is, in a ratio of EVA1 〇〇 by weight, 4 parts by weight of maleic anhydride, and BP02 parts by weight, a preblend uniformly mixed using a Henschel mixer is supplied to a two-axis extruder for grafting reaction. An EVA grafted with maleic anhydride was obtained. It was confirmed that the obtained EVA-containing analysis analysis contained 0.6% by weight of maleic anhydride and contained 0.15% by weight of coagulum.

-122- 200925171 &lt;Production of Unsaturated Carboxylic Acid-Grafted Polyolefin Film&gt; Using the double-action compression molding machine WFA-50, the obtained maleic anhydride was grafted with EVA at a heating temperature of 15 ° C, pressure Pressurization molding was carried out under the conditions of 〇 MPa, heating time of 10 minutes, cooling temperature of 30 ° C, pressure of 10 MPa, and cooling time of 5 minutes to obtain a film having a thickness of 1 μm. The obtained film appeared fish eyes, and the appearance was remarkably inferior to that of the film obtained in the examples.

薄膜 The obtained film (film 3) having a size of 50 mm×100 mm and a thickness of ΙΟΟμη, a copper foil (sheet 1) having a surface treatment size of 100 mm×100 mm and a thickness of 0.5 mm, and a polyimide film (film 2) having a thickness of 100 μm and a thickness of 100 μm Lamination was carried out in the form of sheet 1 / film 3 / film 2, and a layer of half area of the foil 1 and the polyimide film was obtained under the conditions of a pressure of 2 MPa, a temperature of 180 ° C, and a time of 1 minute. Compound. A thin rectangular sample having a length of 1 mm and a width of 15 mm was cut out from the obtained laminate so that half of the area was followed, and half of the area was not followed, at a stretching speed of 300 mm/min. As a result of the T-peel test, the laminate exhibited a ruthenium having a low peel strength of 13 N/15 mm, and the test piece was peeled off between the materials constituting the laminate through 20 thermal cycle tests. Compared with the laminate obtained in the examples, it was a laminate which was weak for hot stamping, and the results are shown in Table 15. -123- 200925171 Q o [SIS Comparative Example 42 Ρη 〇 Maleic anhydride 1 m Ο I Copper flakes 1 Maleic anhydride grafted CPP Hall &&amp; m ^ Long υ | 逝 1 00 t Comparative Example 41 Ah Oh u Maleic anhydride 1 ο c5 m Beryllium copper sheet I Maleic anhydride grafted CPP mm Maleic anhydride grafted CPP 1 00 v〇1 Comparative Example 40 EVA Maleic anhydride 1 inch ο S o rH l aluminum sheet” Maleic anhydride Branch EVA PPS sheet Maleic anhydride graft EVA 1 00 Bu 1 Comparative Example 39 EVA Maleic anhydride 1 inch ο go 1 Aluminum sheet 1 Maleic anhydride grafted EVA polycarbonate film Maleic anhydride grafted EVA 1 〇〇 ( N CO 匕 匕 38 EVA maleic anhydride 1 rn so rs 1 aluminum flakes I maleic anhydride graft EVA 跬 crane mm maleic anhydride graft EVA 1 ON 卜 1 沄 Comparative Example 37 EVA maleic anhydride 1_ 1 Οί o ' so 1 aluminum flakes Ί maleic anhydride graft EVA PPS flakes maleic anhydride graft EVA 1 copper flakes Ί 1 m Comparative Example 36 EVA maleic anhydride butyl acrylate 〇 so ON 1 copper flakes 1 maleic anhydride / acrylic acid Butyl Ester Grafted EVA Polycarbonate Film Maleic Anhydride / Butyl Acrylate Graft EVA "Copper Sheet I 1 CN oo rH Comparative Example 35 EVA Maleic Anhydride Acrylic Acid 1_ osoo 1-H 1 Copper Sheet I Maleic Anhydride / Acrylic Graft EVA Aluminum Sheet 1 1 1 1 Comparative Example 34 EVA Maleic Anhydride 1 o c5 CN 1 Copper Sheet I Maleic anhydride grafted EVA polyimine film 1 1 ΓΛ 1 1 I polyolefin i unsaturated carboxylic acid 1 unsaturated carboxylic acid 2 _ \Μ\ wt% 1 幽 (N m _ inch 幽|N/15mm| N /15mm N/15mm acid modified gel | yu tone) 1 layer 1 / layer 3 J 丨 layer 3 / layer 4 | layer 3 / layer 5 J stripping times raw material modified polymer is adhered ... . 1 Intensity Thermal Cycling Test - 124 - 200925171 Comparative Example 3 5 The adhesive of Comparative Example 34 was made into a copper foil, and the EVA of the grafted maleic anhydride and acrylic acid was produced by the same method as that of Comparative Example 34. A laminate was obtained by the same method as in Example 49 except for the aluminum foil. As a result of the peeling test of the laminate, the laminate exhibited a low peel strength of 15 N/15 mm, and further, the test piece was passed through 50. The second thermal cycle test, the peeling occurred between the materials constituting the laminate, compared with the laminate obtained in the examples, For laminates which are weakly hot, the results are shown in Table 15. Comparative Example 3 6 The EVA of the grafted maleic anhydride and butyl acrylate was produced by the same method as that of Comparative Example 34, and the adherend of Comparative Example 34 was a copper foil (layer 1) and a polycarbonate film (layer 3). The laminate was obtained in the same manner as in Example 49 except for the structure of the copper foil (layer 5). As a result of performing the peeling test of the Q laminate, the laminate showed a peel strength of 10 N/15 mm between the layers 1 and 3 and a peel strength of 12 N/15 mm between the layers 3 and 5. Further, this test piece was peeled off between the respective materials constituting the laminate by the thermal cycle test of 18 times, and was a laminate which was weak against thermal pulverization as compared with the laminate obtained in the examples. The results are shown in Table 15 » Comparative Example 3 7 A grafted maleic acid was produced by the same method as Comparative Example 34 -125-200925171

The EVA of the anhydride was such that the adherend of Comparative Example 34 was an aluminum foil (layer i), a PPS sheet (layer 2), and a copper sheet (layer 3), and the same method as in Example 49 was carried out. . As a result of the peeling test of the laminate, the laminate showed a peel strength of 1 ON/1 5 mm between the layers 1 and 3, and a peel strength of 1 1 N/1 5 mm between the layers 3 and 5. In addition, this test piece was peeled off between the materials constituting the laminate through 35 heat cycle tests, and compared with the laminate obtained in the example, the laminate was weak to heat, and the result was as follows. Listed in Table 15. Comparative Example 38 An EVA of the grafted maleic anhydride was produced by the same method as that of Comparative Example 34, and the adherend of Comparative Example 34 was an aluminum flake and a polyimide film, and Example 49 was used. The same method was used to obtain a four-layer laminate represented by Table 5. As a result of the peeling test of the laminate, the laminate showed a peel strength of 〇' layer 3/layer 4 having a peel strength of 9 N/1 5 mm between layer 1 and layer 3 of 7 N. /1 5 mm low enthalpy, in addition, the test piece was peeled off between the materials constituting the laminate through 30 thermal cycle tests, and compared with the laminate obtained in the example, it was The weak laminates are shown in Table 15. Comparative Example 3 9 The same procedure as in Comparative Example 34 was carried out to produce EVA grafted with maleic anhydride, and the adherend of Comparative Example 34 was an aluminum flake and polycarbonate, and the same as in Example 49. The four-layer laminate of -126-200925171 represented by Table 15 was obtained. As a result of performing the peeling test of the laminate, the laminate showed a peel strength of 1 1 n /1 5 mm between the layers 1 / 3 and a peel strength between the layers 3 / 4 8N/1 5mm low enthalpy, in addition, this test piece was peeled off between the materials constituting the laminate through 32 heat cycle tests, compared with the laminate obtained in the example, The weak laminates are shown in Table 15.

Comparative Example 40 The EVA of the grafted maleic anhydride was produced by the same method as that of Comparative Example 34, and the adherend of Comparative Example 34 was an aluminum flake and the same as PPS, by the same as Example 49. The four layer laminates shown in Table 15 were obtained by the method. As a result of performing the peeling test of this laminate, the laminate showed a peel strength of 8 N/15 mm between layers 1/layer 3, and a peel strength between layer 3/layer 4 of 7 N/l 5 mm. In addition, the test piece was peeled off between the materials constituting the laminate by the 26th thermal cycle test, and was a weak laminate for hot stamping as compared with the laminate obtained in the example. The results are shown in Table 15. Comparative Example 4 1 Using the CPP obtained in Example 59, CPP of grafted maleic anhydride was produced by the same method as Comparative Example 34, and the obtained polymer was thinned to prepare a copper flake/grafted horse. The results of the subsequent tests of the CPP film of the anhydride anhydride/the polyamidide film/the four-layered layer of the CPP film grafted with maleic anhydride are shown in Table 15. As a result of the test, the -127-200925171 laminate was inferior to any of the properties of the subsequent strength, hue, and hot stamping, and the results are shown in Table 15. Comparative Example 42

Using the CPP obtained in Example 74, CPP of grafted maleic anhydride was produced by the same method as Comparative Example 34, and the obtained polymer was thinned to prepare a copper flake/CPP of grafted maleic anhydride. A laminate of a film/polyimine film/a four-layer laminate of a CPP film grafted with maleic anhydride was subjected to the subsequent test, and is shown in Table 15. As a result of the test, the laminate was inferior to any of the properties of the subsequent strength, hue, and hot stamping, and the results are shown in Table 15. Example 79 &lt;Production of Unsaturated Carboxylic Acid-Grafted Polyolefin&gt; 5000 parts by weight of 1,1,2-trichloroethane and 2500 parts by weight of a Q 26% sulfuric acid aqueous solution were placed in the lower mouth 1 The stirred flask was vigorously stirred, and after standing, the lower organic layer was taken out. Next, the taken-out organic layer and 5 kg of distilled water were placed in a 1-liter flask equipped with a lower mouth and vigorously stirred, and the operation of removing the organic layer of the lower layer was repeated 3 times to remove 1-butanol and 1,2. - Epoxybutane. Further, 15 parts by weight of molecular sieve 4A was added to the extracted organic layer, and the mixture was stirred and dehydrated to obtain purified 1,1,2-trichloroethane (hereinafter referred to as purified TCE). A 4 liter glass reaction vessel was charged with 3 parts by weight of purified TCE and 200 parts by weight of EVA, and 5 parts by weight of maleic anhydride, and -128-200925171

The reactor was heated to a temperature, and then EVA was uniformly dissolved by maintaining at 80 ° C for 4 hours. Further, during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liter / minute to remove air mixed into the reactor as a graft reaction. The catalyst was dissolved in 1.55 parts by weight of BPO in 100 parts by weight of purified TCE, and this solution was continuously continuously added to the reactor, and the graft reaction was carried out for 3 hours while maintaining the pressure of the reactor at 1 MPa. After the completion of the reaction, the pressure was returned to normal pressure, the temperature of the reactor was raised to 70 ° C, 0.06 parts by weight of BHT as a stabilizer was added, and the solution was poured into a large amount of methanol to form a product of Malay. The acid anhydride-grafted EVA was separated from the solvent by a known product system and found to have 1.6% by weight of an unsaturated carboxylic acid (maleic anhydride) and the gel was 〇% by weight. &lt;Production of unsaturated carboxylic acid grafted polyolefin film&gt; The above-obtained unsaturated carboxylic acid was grafted with EVA at a heating temperature of 15 (TC, pressure 10 MPa, heating using a double-action compression molding machine WFA-50) The film was subjected to press molding under the conditions of a time of 10 minutes, a cooling temperature of 30° C., a pressure of 10 MPa, and a cooling time of 5 minutes to obtain a film having a size of 100 mm×100 mm and a thickness of ΙΟΟμπι, and the obtained film was excellent in appearance and properties, and no fisheye or the like was observed. Disadvantages. &lt;Manufacturing of Multilayer Laminate&gt; The obtained film having a size of 1 OOmm x 1 00 mm and a thickness of 1 ΟΟμπι and a ebony sheet having a thickness of 0.3 mm in the reinforced paper were pressed at a pressure of -129 to 200925171 O. IMPa, temperature and temperature of 180 ° C, 1 minute conditions were heated and pressure-bonded to obtain a blister sheet having heat fusibility. The obtained ebony sheet was superposed on a non-surface-treated sheet of a size of 100 mm x 100 mm and a thickness of 1 mm. The mixture was heated and pressure-bonded under the conditions of a pressure of 0.1 MPa and a temperature of 180 ° C for 1 minute to obtain a multilayer laminate. The layers of the obtained laminate were firmly followed by heating to 40 to 80 ° C, but not Seeing peeling The release test piece having the same structure as the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was excellent at 50 N/15 mm.値, the peeling strength between the wood and the adhesive layer exceeded the breaking strength of the wood itself. Further, it was confirmed that the laminate was not peeled off at -40 ° C, and the low-temperature characteristics were excellent. The compound did not show peeling after 200 cycles of thermal cycling, and was a laminate having high strength. Example 8 0

The film having a size of 100 mm×100 mm and a thickness of ΙΟΟμηη obtained in Example 79 and a papaya sheet having a thickness of 3.3 mm reinforced with a paper were heated and pressure-bonded under the conditions of a pressure of 0.1 MPa and a temperature of 180 ° C for 1 minute to obtain Hot-melt papaya flakes. The obtained papaya sheet was overlaid on an aluminum plate having a size of 10 mm×100 mm and a thickness of 1 mm which was not subjected to surface treatment, and was pressure-bonded under the conditions of a pressure of 0.1 MPa and a temperature of 180 ° C for 1 minute to obtain a multilayer laminate. The layers of the obtained laminate were firmly adhered to each other, and although it was heated to 40 to 80 ° C, no peeling test piece was formed which was formed into the same composition as the laminate to obtain a tensile speed of 3 0. 0mm/ -130- 200925171 minutes As a result of the τ-type peeling test, the peel strength between the metal layer and the adhesive layer was excellent at 55 Ν / 15 mm, and the peel strength between the wood and the adhesive layer exceeded the rupture of the wood itself. In addition, it was confirmed that the laminate was not peeled off at -40 ° C, and the low-temperature characteristics were excellent. Further, the laminate did not show peeling after the thermal cycle test of 200 times. It is a laminate with high strength.

Example 8 1 A 3 liter glass reaction vessel was charged with 3,000 parts by weight of purified TCE and 200 parts by weight of L-LDPE, and 6 parts by weight of acrylic acid, and the reactor was heated to 80 ° C, and then by The L-LDPE was dissolved uniformly at 80 ° C for 4 hours. Further, during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liter / minute to exclude air mixed into the reactor, and 1.4 parts by weight of BPO was dissolved as 100 parts by weight of the purified TCE as a catalyst for the graft reaction. This solution was continuously continuously added to the reactor, and the graft reaction was carried out for 3 hours while maintaining the pressure of the reactor at 1 MPa. After the completion of the reaction, the pressure was returned to normal pressure, and the temperature of the reactor was raised to 70 ° C, and 0.06 part by weight of BHT as a stabilizer was added. This solution was poured into a large amount of methanol, and the resultant acrylic grafted L-LDPE was separated from the solvent. It is known that the result of the analysis of the product system was 1.8% by weight of acrylic acid, and the gel was 〇% by weight. The obtained acrylic grafted L-LDPE was thinned by the same method as in Example 79, and then heat-pressed with a bird's eye maple leaf under the conditions of pressure 〇 IMPa, temperature of 180 ° C, and 1 minute. , superimposed on the -131 - 200925171 surface treatment size lOOmmxlOOmm, thickness lmm of the nameplate, pressure 0.1 MPa, temperature 180 ° C, 4 〇 second conditions of heating and pressure bonding, to obtain a multilayer laminate. A peeling test piece having the same structure as the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was excellent at 52 N/15 mm. The peeling strength between the wood and the adhesive layer exceeded the breaking strength of the wood itself. Further, it was confirmed that the laminate was not peeled off at -40 ° C, and the low-temperature characteristics were excellent. Further, the laminate was passed through 200. No peeling was observed after the secondary heat cycle test, and the laminate was high in strength. Example 82

A 4 liter glass reaction vessel was charged with 3,000 parts by weight of purified TCE and 200 parts by weight of L-LDPE, and 5 parts by weight of maleic anhydride, and the reactor was heated to 80 ° C, and then by 80 The L-LDPE was uniformly dissolved at °C for 4 hours. Further, during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liters/min to remove air mixed into the reactor, and 1.8 parts by weight of BPO was dissolved in 100 parts by weight of purified TCE as a catalyst for the graft reaction. The solution was continuously continuously added to the reactor, and the graft reaction was carried out for 3 hours while the pressure of the reactor was maintained at 1 MPa. After the completion of the reaction, the pressure was returned to normal pressure, the temperature of the reactor was raised to 7 ° C, and 6 parts by weight of BHT as a stabilizer was added. This solution was poured into a large amount of methanol, and the product of maleic anhydride grafted L-LDPE was separated from the solvent, and it was known that the product analysis result was 1.4% by weight of Malay-132-200925171 anhydride, gel. It is % by weight. The obtained lanthanum maleate grafted L-LDPE was thinned by the same method as in Example 79, and then heated and pressed with the plaque wood sheet under the conditions of pressure 〇1 MPa, temperature 15 (TC, 30 seconds). Further, a stainless steel sheet having a thickness of 1 mm was heated and pressure-bonded under the conditions of a pressure of 0.1 MPa, a temperature of 180 ° C, and a temperature of 60 seconds to obtain a multilayer laminate.

A peeling test piece having the same structure as that of the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was excellent at 47 N/15 mm. 'The peel strength between the wood and the adhesive layer exceeds the crack strength of the wood itself. In addition, it is confirmed that the laminate is bent at -4 ° C and no peeling is observed. The low temperature property is also excellent. In addition, the laminate is excellent. No peeling was observed after 200 cycles of the heat cycle test, and the laminate was high in strength. Example 83 The film of the acrylic acid grafted L-LDPE obtained in Example 81 and the oak sheet having a thickness of 0.3 mm were heat-pressed under the conditions of a pressure of 0.15 MPa, a temperature of 160 ° C, and a temperature of 30 seconds, and a thickness of 1 mm. The stainless steel sheet was heat-pressed under the conditions of pressure 〇 IMPa, temperature of 1 70 ° C, and 7 〇 second to obtain a multilayer laminate. A peeling test piece having the same structure as that of the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was excellent at 45 N/1 5 mm. The peel strength between the wood and the adhesive layer exceeds the fracture strength of the wood itself. In addition, it is confirmed that the laminate is not peeled off at -40 ° C, and the low temperature characteristics are excellent. The laminate did not show peeling after 200 cycles of heat cycle test, and was a laminate having high strength. Example 84 &lt;Production of Unsaturated Carboxylic Acid-Grafted Polyolefin&gt;

5000 parts by weight of 1,1,2-trichloroethane and 260 parts by weight of a 26% aqueous sulfuric acid solution were placed in a 10-liter flask with a lower opening and vigorously stirred, and after standing, the lower organic layer was taken out. Next, the taken-out organic layer and 5 kg of distilled water were placed in a 10-liter flask with a lower mouth and vigorously stirred. After standing, the operation of taking out the lower organic layer was repeated three times to remove 1-butanol and 1,2. - Epoxybutane. Further, 150 parts by weight of molecular sieve 4A was added to the taken-out organic layer, and the mixture was stirred and dehydrated to obtain purified 1,1,2-trichloroethane (hereinafter referred to as purified TCE). A 4 liter glass reaction vessel was charged with 3000 parts by weight of purified TCE and 200 parts by weight of EVA, and 5 parts by weight of maleic anhydride, and the reactor was heated to 80 ° C ' and then maintained at 80 ° C. EVA was uniformly dissolved in 4 hours, and during this period, nitrogen was introduced into the reactor at a flow rate of 5 liters/min to exclude air mixed into the reactor. As a catalyst for the grafting reaction, 1.55 parts by weight of BPO was dissolved in the purification. TCE 100 parts by weight 'After adding this solution to the reactor', the grafting reaction was carried out for 3 hours while the pressure of the reactor was maintained at 1 MPa. After the completion of the reaction, the pressure was returned to normal pressure, and the temperature of the reactor was raised to 70. 5% by weight of BHT was added as a stabilizer. This solution was poured into a large amount of -134-200925171 methanol. The maleic anhydride grafted EVA of the product was separated from the solvent. The resulting product analysis was found to have 1.6% by weight of an unsaturated carboxylic acid (maleic anhydride) and a gel of 0.012% by weight. &lt;Production of unsaturated carboxylic acid grafted polyolefin film&gt;

Using the double-action compression molding machine WFA-50, the unsaturated carboxylic acid obtained above was grafted with EVA at a heating temperature of 150 ° C, a pressure of 10 MPa, a heating time of 10 minutes, a cooling temperature of 30 ° C, The pressure of 10 0 MP a and the cooling time of 5 minutes were subjected to press molding to obtain a film having a size of 100 mm x 100 mm and a thickness of 1 μm, and the obtained film was excellent in appearance and properties, and the defects such as fish eyes were not observed. &lt;Production of Multilayer Laminate&gt; The obtained film having a size of 100 mm x 100 mm and a thickness of ΙΟΟμπι and a ebony sheet having a thickness of 〇.3 mm reinforced with paper and paper were subjected to a pressure of O.IMPa and a temperature of 180 ° C for 1 minute. The conditions were heat-pressed to obtain a blister sheet having heat fusion properties. The obtained ebony flakes were superposed on a nameplate having a surface treatment size of 100 mm x 100 mm and a thickness of 1 mm, and pressed at a pressure of O.IMPa 'temperature of 180 ° C for 1 minute to obtain a multilayer laminate. The layers of the obtained laminate were firmly adhered, and although peeling was not carried out at 40 to 80 ° C, peeling test pieces having the same constitution as the laminate were prepared at a tensile speed of 300 mm/min. As a result of the T-peel test, the peel strength between the metal layer and the adhesive layer was excellent at 45 N/15 mm, and the peel strength between the wood and the adhesive layer exceeded the fracture strength of the wood from -135 to 200925171, and It was confirmed that the laminate was not peeled off at -40 ° C, and the low-temperature characteristics were excellent. Further, the laminate did not show peeling after the thermal cycle test of 200 times, and was a layer having a high strength. Compound. Example 8 5 A film having a size of 100 mm X 100 mm and a thickness of 0 ΙΟΟμη obtained in Example 84 and a papaya sheet having a thickness of 0.3 mm in the same manner as the paper were subjected to a pressure of 0.1 MPa and a temperature of 180 ° C for 1 minute. Heat-pressed to obtain papaya flakes with heat solubility. The obtained papaya sheet was superposed on an aluminum plate having a size of 100 mm x 100 mm and a thickness of 1 mm which was not subjected to surface treatment, and was pressure-bonded under the conditions of a pressure of 0.1 MPa and a temperature of 180 ° C for 1 minute to obtain a multilayer laminate. The layers of the obtained laminate were firmly adhered to each other, and although peeling was not observed at 40 to 80 ° C, a peeling test piece having the same constitution as that of the laminate was prepared at a stretching speed of 300 mm/min. As a result of the τ-type peeling test, the peel strength between the metal layer and the adhesive layer was excellent at 50 N/15 mm, and the peel strength between the wood and the adhesive layer exceeded the crack strength of the wood itself. The laminate was not peeled off at -40 ° C, and was excellent in low-temperature characteristics. Further, the laminate did not show peeling after 200 cycles of heat cycle test, and was a laminate having high strength. Example 8 6 3 000 parts by weight of a 4 liter glass reaction vessel was charged -136-200925171 Ο

TCE and 200 parts by weight of L-LDPE, and 6 parts by weight of acrylic acid, the reactor was heated to 80 ° C, and then L-LDPE was uniformly dissolved by maintaining at 80 ° C for 4 hours, and in addition, during the reaction Nitrogen gas was introduced at a flow rate of 5 liters/min to exclude air mixed into the reactor, and 1.4 parts by weight of BPO was dissolved as 100 parts by weight of purified TCE as a catalyst for the graft reaction. After the solution was added to the reactor at a time, the grafting reaction was carried out for 3 hours while maintaining the pressure of the reactor at 1 MPa. After the completion of the reaction, the pressure was returned to normal pressure, and the temperature of the reactor was raised to 70 ° C, and 0.06 part by weight of BHT as a stabilizer was added. This solution was poured into a large amount of methanol, and the resultant acrylic grafted L-LDPE was separated from the solvent. The resulting product analysis was found to have 1.8% by weight of acrylic acid and a gel of 0.012% by weight. The obtained acrylic grafted L-LDPE was thinned by the same method as in Example 84, and then heated and pressure-bonded with a bird's eye maple leaf under the conditions of a pressure of 0.1 MPa and a temperature of 180 ° C for 1 minute. The nameplate having a surface treatment size of 100 mm×100 mm and a thickness of 1 mm was heat-press-bonded under the conditions of a pressure of 0.1 MPa, a temperature of 180 ° C, and a temperature of 40 seconds to obtain a multilayer laminate. A peeling test piece having the same structure as that of the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was excellent at 50 N/15 mm.値, the peel strength between the wood and the adhesive layer exceeds the crack strength of the wood itself, and further, it is confirmed that the laminate is not peeled off at -40 ° C, and the low-temperature property is also excellent, and further, the laminate After the thermal cycle test of 200 times, no peeling-137-200925171 was observed, which was followed by a high strength laminate. Example 8 7

G was charged with 300 parts by weight of purified TCE and 200 parts by weight of L-LDPE, and 5 parts by weight of maleic anhydride in a 4 liter glass reaction vessel, and the reactor was heated to 80 ° C, and then borrowed. The L-LDPE was uniformly dissolved by maintaining at 80 ° C for 4 hours, and during this time, nitrogen gas was introduced into the reactor at a flow rate of 5 liter / minute to remove the air mixed into the reactor as a catalyst for the graft reaction. 1.8 parts by weight of BPO was dissolved in 100 parts by weight of purified TCE, and this solution was added to the reactor once, and the graft reaction was carried out for 3 hours while maintaining the pressure of the reactor at 1 MPa. After the completion of the reaction, the pressure was returned to normal pressure, the temperature of the reactor was raised to 70 ° C, and 0.06 part by weight of BHT as a stabilizer was added. This solution was poured into a large amount of methanol, and the product of maleic anhydride grafted L-LDPE was separated from the solvent, and it was found that the product analysis result was that the maleic anhydride 'gel having 1.4% by weight was 0.014% by weight. . The obtained maleic anhydride-grafted L-LDPE was thinned by the same method as in Example 84, and then heated and pressure-bonded with the porphyra tree flakes under the conditions of pressure 11 MPa, temperature 150 ° C, and 30 seconds. Further, a stainless steel sheet having a thickness of 1 mm was heated and pressure-bonded under the conditions of a pressure of 0.1 MPa, a temperature of 180 ° C, and a temperature of 60 seconds to obtain a multilayer laminate. A peeling test piece having the same structure as that of the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was excellent at 45 N/15 mm. Wood and joint -138- 200925171 The peel strength between the layers exceeds the crack strength of the wood itself. In addition, it is confirmed that the laminate is not peeled at -40 ° C, and the low-temperature characteristics are also excellent. The laminate did not show peeling after the thermal cycle test of 200 times, and was a laminate having high strength. Example 8 8 The film of the acrylic acid grafted L-LDPE obtained in Example 86, φ and the thickness of 橡3 mm of the oak sheet were heated and pressure-bonded under the conditions of a pressure of 0.15 MPa, a temperature of 160 ° C, and 30 seconds, and The stainless steel sheet having a thickness of 1 mm was heat-press-bonded under the conditions of a pressure of 0.1 MPa, a temperature of 170 ° C, and 70 seconds to obtain a multilayer laminate. A peeling test piece having the same constitution as that of the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was excellent at 44 N/15 mm. 'The peel strength between the wood and the adhesive layer exceeds the crack strength of the wood itself. In addition, it is confirmed that the laminate is not peeled off at -40 ° C, and the low temperature characteristics are also excellent. The compound did not show peeling after 200 cycles of heat cycle test, and was a laminate having high strength. Comparative Example 4 3 Sections Cl, C2, and C3 were set at 150, 180, and 200 ° C using a 1 1 5 mm φ, L/D = 50 2-axis extruder manufactured by NAKATANI Machinery Co., Ltd., and the section C4 was CIO, A, and D are set at 220 ° C, and the unreacted unsaturated carboxylic acid -139 - 200925171 is removed from the exhaust port between C6 and C7 at a number of revolutions of 10 rpm to carry out a graft reaction, that is, 100 parts by weight of EVA. The ratio of 3.6 parts by weight of maleic anhydride and 2 parts by weight of DBPIB is supplied to the two-axis extruder by a Hensley blender through a uniformly mixed pre-blend, and grafting reaction is carried out to obtain a grafted maleic anhydride. EVA. The obtained EVA contained 0.6% by weight of maleic anhydride and contained 0.10% by weight of a gel.

The obtained maleic anhydride was grafted with EVA by using a double-action compression molding machine WFA-50 at a heating temperature of 160 ° C, a pressure of 10 MPa, a heating time of 1 minute, a cooling temperature of 30 ° C, a pressure of 10 MPa, and cooling. Press forming was carried out under the conditions of a time of 5 minutes to obtain a film having a thickness of 1 1 〇μηη. The obtained EVA of the grafted maleic anhydride was thinned by the same method as in Example 79, and then heat-pressed with the ebony flakes under the conditions of a pressure of 0.1 MPa, a temperature of 1,50 ° C, and 30 seconds, and The aluminum plate having a thickness of 1 mm was superposed on the aluminum plate having a thickness of 1 mm, and heated and pressure-bonded under the conditions of a pressure of 0.1 MPa and a temperature of 180 ° C for 1 minute to obtain a multilayer laminate. A peeling test piece having the same structure as that of the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was excellent at 50 N/15 mm. The peel strength between the wood and the adhesive layer exceeds the fracture strength of the wood itself. 'When the laminate is bent at -4 ° C, a part of the peeling 'in addition' of the laminate is seen through 50 times. The thermal cycle test, a part of the peeling of the aluminum plate was significantly inferior to the example. Comparative Example 44 -140-200925171 L-LDPE grafted with maleic anhydride was obtained by the same procedure as in Comparative Example 43, that is, 100 parts by weight of L-LDPE, maleic anhydride 4.0.

The ratio of parts by weight and DBPIB of 2.2 parts by weight is supplied to the two-axis extruder by the Hensley blender through the uniformly mixed pre-blend, and the sections C1, C2, C3 are set at 150, 180, 200°. C' set the sections C4 to CIO, A, and D at 220 ° C, and carry out a graft reaction by removing unreacted maleic anhydride from the exhaust port between C6 and C7 by a number of revolutions of 10 rpm. The L-LDPE grafted with maleic anhydride contained 0.4% by weight of maleic anhydride and contained 0.13% by weight of a gel. The obtained maleic anhydride was grafted with L-LDPE by a double-acting compression molding machine WFA-50 at a heating temperature of 170 ° C, a pressure of 10 MPa, a heating time of 10 minutes, a cooling temperature of 3 (TC, a pressure of 10 MPa, and cooling). The film was formed by press molding under the conditions of a time of 5 minutes to obtain a film having a thickness of 1 μm. The obtained grafted maleic anhydride L-LDPE was thinned by the same method as in Comparative Example 43 and then with the bird's eye. The maple flakes were heated and pressure-bonded under the conditions of a pressure of 0.1 MPa and a temperature of 15 (TC, 30 seconds), and were superposed on an aluminum plate having a thickness of 1 mm, and subjected to heating and pressure bonding under the conditions of a pressure of 0.1 MPa and a temperature of 180 ° C for 1 minute. A multilayer test piece was prepared. The peeling test piece having the same constitution as the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was 43 N/ The excellent 値 of 15mm, the peeling strength between the wood and the adhesive layer exceeds the breaking strength of the wood itself, but the laminate is made to a part of the peeling of the laminate by -4 (TC bending, the laminate is passed through 1 00 thermal cycle test, part of the aluminum strip The adhesion was significantly inferior to the examples. -141 - 200925171 Example 8 9 &lt;Production of Unsaturated Carboxylic Acid-Grafted Polyolefin&gt; 5000 parts by weight of 1,1,2-trichloroethane and 2500 A part by weight of a 26% aqueous sulfuric acid solution was placed in a 10-liter flask with a lower mouth and vigorously stirred, and after standing, the lower organic layer was taken out. Then, the removed organic layer and 5 kg of distilled water were placed in the lower mouth. The 10-liter flask was vigorously stirred, and the operation of taking out the lower organic layer was repeated three times to remove 1-butanol and 1,2-epoxybutane (confirmed by a gas chromatography apparatus). Further, 150 parts by weight of the molecular sieve 4A was added to the taken-out organic layer, and the mixture was dehydrated by stirring with a stirrer to obtain purified 1,1,2-trichloroethane (hereinafter, referred to as purified TCE). The glass reaction vessel was charged with 2480 parts by weight of purified TCE and 200 parts by weight of EVA, and 4.1 parts by weight of maleic anhydride, and the reactor was heated to 80 ° C, and then uniformly maintained at 80 ° C for 4 hours. Q dissolves EVA, and during this time, nitrogen is introduced into the reactor at a flow rate of 5 liters/min. The air mixed into the reactor was excluded, and 1.5 parts by weight of BPO was dissolved in 100 parts by weight of purified TCE as a catalyst for the graft reaction. This solution was continuously continuously added to the reactor, and the pressure at the reactor was maintained at 1 MPa. In the state, the grafting reaction was carried out for 3 hours. After the reaction was completed, the pressure of the reactor was returned to normal pressure, the temperature of the reactor was lowered to 7 CTC, and 6 parts by weight of BHT was added as a stabilizer. The solution was fed into a drum dryer heated to 160 ° C, and the modified EVA of the product was separated from the solvent. From -142 to 200925171, it was found that the result of the analysis of the product was 5% by weight of unsaturated citric acid (maleic anhydride), and the gel had a weight % of ’ of 2 and a good hue. &lt;Production of Unsaturated Carboxylic Acid-Grafted Polyolefin Film&gt; The above-obtained unsaturated carboxylic acid was grafted with EVA using a double-acting compression molding machine WFA-50' at a heating temperature of 150 ° C and a pressure of 10 MPa. The film was heated under the conditions of a heating time of 10 minutes, a cooling temperature of 30° C., a pressure of 10 MPa, and a cooling time of 0 5 minutes to obtain a film (film 1) having a size of i〇〇mm×l〇〇mm and a thickness of 13 μm. The appearance and properties of the film are excellent, and the disadvantages such as fish eyes are not observed. &lt;Lamination of Copper Foil&gt; A film (film 1) having a size of 1 OO mm x 100 mm and a thickness of 130 μm and a copper foil (foil 1) having a surface treatment size of 100 mm x 100 mm and a thickness of 40 μm were subjected to a pressure of O. IMpa, temperature 180. (:, 〇# stomach laminated for 1 minute, to obtain a laminate of polyolefin and copper foil (hereinafter referred to as "copper foil laminated polyolefin film"). The clean room will be laminated according to the obtained copper foil. The olefin film and the circuit diagram were fixed on a circular quartz glass substrate by using a polyimide tape. Then, the above-mentioned quartz glass substrate having the fixed copper foil laminated polyolefin film was placed on a spin coater to make a photoresist. The liquid 61111 is cast on the copper foil laminated poly-smoke film, 'rotating the spin coater at a rotation of 3 00 rpm for 10 seconds' and then increasing the number of rotations to 15 rpm for 5 seconds, thereby rotating the liquid The number of rotations was 20 seconds to obtain a photoresist-coated copper foil-laminated-143-200925171 polyolefin film. The copper foil-laminated polyolefin film was fixed to a circular quartz glass substrate at a wavelength of 3 The phosphor light of 65 nm is exposed for 15 seconds, and then the developer is cast in a state where the above-mentioned glass substrate is rotated, and development is carried out, followed by washing with water, and drying while blowing nitrogen gas.

The obtained copper box-laminated dense hydrocarbon film obtained by development was treated with an etching solution for 30 minutes at room temperature, washed with water, and the photoresist layer was peeled off with acetone to obtain a flexible wiring film having a circuit pattern. It was confirmed that the wiring film was subjected to a thermal cycle test of 200 times, and the copper foil was not peeled off, and the cold resistance and the heat-resistant punching property were excellent. Further, the obtained wiring film was bonded to the polyolefin side of the unsaturated carboxylic acid. The laminate was heated and pressure-bonded to a polycarbonate film at a pressure of 0.1 MPa at 100 ° C to obtain a laminate. It was confirmed that the laminate was subjected to a thermal cycle test of 200 times, the wiring film was not peeled off from the polycarbonate, a strong laminate was obtained for hot stamping, and the peel strength of the obtained laminate was measured, and copper was measured. Then, the strength showed an extremely high enthalpy of 60 N/mm, and as a result of the MIT test, the laminate was subjected to a bending test of 150 times, the copper foil was not peeled off, and the film was broken at the same time, and the bending resistance and flexibility were obtained. Excellent sex. Example 90 LDPE grafted with maleic anhydride was produced by the same procedure as in Example 89, and after lamination, lamination was carried out under the same conditions as in Example 89, and a layer of a copper foil which was pressure-bonded by heating was applied. In the order of photoresist coating, exposure, etching, and photoresist peeling, a circuit pattern of copper was formed on the LDPE to obtain a flexible wiring film of -144 to 200925171. It was confirmed that the wiring film was excellent in cold resistance and heat resistance, and the peeling strength of the wire film was extremely high at 55 N/mm. Further, the film was subjected to a bending test of 150 times, and the copper crack was excellent in bending resistance and flexibility. Example 9 1 After the film was formed by the same hand LDPE as in Example 89, a three-layer laminate of LDPE/copper foil was obtained by laminating a copper foil on both sides of the seed film. The one side of the composition was coated with a photoresist liquid by a spin coater on the surface of Example 89, and the surface of the other side was subjected to development, water washing, and then grafted. A double-sided flexible wiring film of maleic anhydride LDPE. It was confirmed that the wiring film was excellent in the peeling strength of the wiring film by the peeling, the cold resistance and the heat-resistant squeezing property, and the extremely high enthalpy of 56 N/mm, and the film was subjected to a bending test of 150 times, copper: In the thermal cycle test, the copper foil was not peeled off. The measured bond strength of the copper and the copper showed the results of the MIT test. The wire 丨 foil was not peeled off, and the film was finally broken to produce grafted maleic anhydride. Example 8 9 The same conditions, the thin copper foil / grafted maleic anhydride, first, the resulting layer is protected by the same method of lamination, coating, exposure, and then coated with photoresist After exposure. Then, etching treatment and water washing were carried out to obtain a thermal cycle test of the circuit pattern on which copper was formed, and the copper foil was not. Further, the measured adhesion strength between the copper and the copper showed the result of the MIT test, and the wiring foil was not peeled off, and the film was also broken at -145 to 200925171, and the bending resistance and flexibility were excellent. Example 92

The grafted acrylic acid LDPE was produced by the same method as in Example 91 except that Example 91 and the unsaturated carboxylic acid were changed from maleic anhydride to acrylic acid, and the same conditions as in Example 89 were carried out after thinning. The copper foil was laminated on both sides of the film to obtain a three-layer laminate of copper foil/grafted maleic anhydride LDPE/copper foil. First, the one side of the obtained laminate was protected. The photoresist was coated on one side of the laminate by a spin coater in the same manner as in Example 89, coated, exposed, and then coated on the exposed side, and coated on the other side. Light resistance, exposed. Then, development and washing with water were carried out, followed by etching treatment and water washing to obtain a flexible wiring film of a circuit pattern in which copper was formed on both sides of LDPE grafted with maleic anhydride. It was confirmed that the wiring film was subjected to a thermal cycle test for 200 times, and the copper foil was not peeled off, and was excellent in cold resistance and heat resistance. Further, as a result of measuring the peel strength of the obtained wiring film, the adhesion strength to copper showed an extremely high enthalpy of 5 4 N/mm, and as a result of the MIT test, the wiring film was subjected to a bending test of 150 times. The copper foil is not peeled off, and the film is also broken at the end, and is excellent in bending resistance and flexibility. Example 93 Using a 115 mm 0, L/D = 50 2-axis extruder manufactured by NAKATANI Machinery Co., Ltd., the sections C1, C2, and C3 were set at 150, 180, -146 - 200925171 2 00 ° C, and the section C4 was used. ~CIO, A, D are set at 220 ° C, and the unreacted unsaturated carboxylic acid is removed from the exhaust port between C6 and C7 at a rotation number of 1 lO rpm for grafting reaction, that is, 100 parts by weight of EVA, horse The ratio of 4.1 parts by weight of the anhydride to 2 parts by weight of DBPIB was supplied to the two-axis extruder by a Henkelly kneader through a uniformly mixed preblend, and grafting reaction was carried out to obtain EVA grafted with maleic anhydride. The obtained EVA contained 0.5% by weight of maleic anhydride and contained 0.13 % by weight of a gel.

Using the double-action compression molding machine WFA-50, the obtained maleic anhydride was grafted with EVA at a heating temperature of 150 ° C, a pressure of 10 MPa, a heating time of 1 〇 minutes, a cooling temperature of 30 ° C, a pressure of 10 MPa, and a cooling time of 5 The film was formed by press molding under the conditions of a minute to obtain a film having a thickness of 1 μm. A two-layer laminate of a copper foil/maleic anhydride grafted polyolefin was obtained by heating a pressure-bonded copper foil by the same method as in Example 89 on the obtained film. A circuit is formed by lithography to obtain a flexible wiring film. This wiring film was subjected to a heat cycle test of 150 times, and the copper foil was not peeled off. Although the peeling of the copper foil was slightly observed after 200 tests, the cold resistance and the heat-resistant punching property which were practically problem-free were exhibited. Further, as a result of measuring the peel strength of the obtained wiring film, the adhesion strength with copper showed an extremely high enthalpy of 57 N/mm, and as a result of the enthalpy test, the wiring film was subjected to a bending test of 150 times, copper. The foil is not peeled off, and the film is also broken at the end, and is excellent in bending resistance and flexibility. Comparative Example 4 5 - 147 - 200925171 The poly-(styrene-butadiene-styrene) block copolymer was dissolved in dichloromethane to prepare a solution having a polymer concentration of 15% by weight, and the solution was applied to the polyfluorene. The imine film is formed into a film of poly-(styrene-butadiene-styrene) block copolymer having a thickness of 40 μm, and the solvent is allowed to stand at room temperature for one day and one night to evaporate and then removed at a normal pressure of 40 ° C. It was dried for 4 hours, and dried at room temperature under reduced pressure for 1 day and 1 night. Then, while avoiding the incorporation of the copper foil and the bubbles, the layer was pressed. 'The film side of the polyimide film with the copper foil attached thereto. A Cudrow-type electron-line accelerating device (manufactured by Thermal Energy Scientific Co., Ltd.) irradiates the electron beam 'cross-linking treatment under conditions of an acceleration voltage of 168 kV and an irradiation amount of 1 OMrad. Hereinafter, a wiring pattern was obtained by lithography on a copper foil-attached polyimide film by the same method as in Example 89, and a copper foil and a polyimide layer were compared with the examples. The pressure required a large amount of time and the number of steps, and the obtained wiring film was partially peeled off by the thermal cycle test of one turn, and the cold resistance and the heat-resistant punching property were inferior to those of the wiring film obtained in the example. As a result of the T-type Q peeling test, the interface between the copper and the adhesive layer was peeled off in the peeling test, and the strength at the time of peeling was a low enthalpy of 5 N/15 mm, and as a result of the MIT test, the wiring film was passed through 15 〇. In the secondary bending test, although the crack of the polyimide layer was not observed, the copper foil was peeled off and the bending resistance was poor. Comparative Example 46 8.0 mol of p-phenylenediamine (manufactured by DuPont) and 2.0 mol of 4,4,-diaminophenyl ether (manufactured by Wakayama Seika Co., Ltd.) were dissolved in N-methyl-2-pyrrolidone (BASF). Made in Japan) After 24kg, cool the system to 1〇, -148-

200925171 Slowly added 3,3',4,4,-biphenyltetracarboxylic anhydride (Ube Hiroshi Co., Ltd. 9 · 9 moles and reacted it to 25. (: It was shown to show 26,000 centipoise quinone imine The precursor solution was applied to a copper mold having a thickness of 40 μm and a size of 5 cm×5 cm in a thickness of 25 μm, and the air drying oven was dried at 120 ° C for 1 〇 minutes. The obtained substrate coated with the imine precursor was heated to 350 ° C in a state where the degree of vacuum was ltorr, and then naturally cooled by 18 hours to obtain a copper foil. On the polyimide film, the wiring film was obtained by the lithography pattern, and the lamination of the copper foil and the polysilicon required a large amount of time and steps compared with the example, and the obtained wiring film 2〇〇 In the secondary heat cycle test, although the peeling of the copper foil was not observed, the film was subjected to the T-peel test, and the interface between the copper and the joint was peeled off in the peeling test, and the strength at the time of peeling was 9 N/1 5 mm, The wiring film obtained by the example is inferior, and the result of MIT is The wiring film was subjected to a bending test of 150 times, and although the polyimide film was not broken, the copper foil was peeled off, cracks occurred in the adhesive layer, and the resistance was poor. Comparative Example 4 7 11.6 g of epoxy resin A, 3.9 g of epoxy Resin B, 7 g of an oxygen resin curing agent, and phenyl. phenyl imidazole were dissolved in THF (80 ml) to adjust the curable resin solution. The obtained thermosetting resin solution was applied to a thickness of 40 μm by a doctor blade so as to have a hard thickness of 20 μm. The condensed side of the system is heated by a poly-pyrene. The electro-imine is laminated to the polyamine film of the 5Cmx5Cm after the bending of the loop through the wiring layer. On, 5 (TC heating for 20 minutes to dry 0

The obtained polyimide film forming a thermosetting resin layer and a copper foil having a thickness of 40 μm were heated by using a roll heated to 130° C., and then the obtained laminate was completely cured in order to completely cure the adhesive. The laminate was cured by heating at 1 〇〇 ° C for 1 hour, 120 ° C for 1 hour, and 180 ° C for 5 hours to form a laminate, and a circuit pattern was formed by lithography on the obtained laminate. The wiring film requires a large amount of time and number of steps for lamination of the copper foil and the polyimide under comparison with the examples. Further, the obtained wiring film was subjected to a heat cycle test for 200 times, and the copper foil was partially peeled off. Further, as a result of the T-type peeling test of the wiring film, the interface between the copper and the adhesive layer was peeled off during the peeling test, and the peeling was performed. The enthalpy having a low strength of 10 N/1 5 mm was inferior to the wiring film obtained in the examples, and as a result of the MIT test, the wiring film was subjected to a bending test of 150 times, although no aggregation was observed. The bismuth imide layer is broken, the copper foil is peeled off, the subsequent layer is cracked, and the bending resistance is poor. Example 94 &lt;Production of Unsaturated Carboxylic Acid-Grafted Polyolefin&gt; 5000 parts by weight of 1,1,2-trichloroethane and 2500 parts by weight of a 26% aqueous sulfuric acid solution were placed in the lower mouth with 10 liters. The flask was vigorously stirred, and after standing, the lower organic layer was taken out. Next, the taken-out organic layer and 5 kg of distilled water were placed in a 10-liter flask with a lower opening and vigorously stirred. The operation of removing the organic layer of the lower layer was repeated three times to remove 1-butanol and -150- 200925171 1,2-Epoxybutane (confirmed by gas chromatography apparatus). Further, 150 parts by weight of molecular sieve 4A was added to the taken-out organic layer, and the mixture was dehydrated by stirring with a stirrer to obtain purified 1,1,2-trichloroethane (hereinafter referred to as purified TCE). 〇

A 4 liter glass reaction vessel was charged with 2480 parts by weight of purified TCE and 200 parts by weight of L-LDPE, and 2.0 parts by weight of maleic anhydride, and the reactor was heated to 80 ° C, and then by 80 °. C was uniformly dissolved in L-LDPE for 4 hours. Further, during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liter / minute to exclude air mixed into the reactor, and 1.5 parts by weight of BPO was dissolved as a catalyst for the graft reaction in 100 parts by weight of the purified TCE. This solution was continuously continuously added to the reactor, and a graft reaction was carried out for 3 hours while maintaining the pressure of the reactor at 1 MPa. After the reaction is completed, the pressure of the reactor is returned to normal pressure, the temperature of the reactor is lowered to 70 ° C, and 6 parts by weight of BHT as a stabilizer is added, and the solution is heated to 1 60 °. In the drum dryer of C, the modified L-LDPE of the product was separated from the solvent. It is known that the product analysis result is 1.5% by weight of unsaturated carboxylic acid (maleic anhydride), the gel is 〇% by weight, 丫1 is 2, and the hue is excellent. &lt;Production of a film formed of an unsaturated carboxylic acid grafted polyolefin&gt;

The above-mentioned unsaturated carboxylic acid was grafted with L-LDPE by using a double-action compression molding machine WFA-50 at a heating temperature of 180 ° C, a pressure of 10 MPa, a force and heat time of 10 minutes, and a cooling temperature of 30 ° C. Pressure molding was carried out under the conditions of a pressure of 10 MPa and a cooling time of 5 minutes to obtain a film (film 1) having a size of 100 mm X 200925171 100 mm and a thickness of ΙΟΟμηη. The obtained film was excellent in appearance and properties, and no fisheye or the like was observed. Disadvantages. &lt;Lamination of copper boxes&gt;

The obtained film (film 1) having a size of 100 mm×100 mm and a thickness of ΙΟΟμη, and a copper foil (foil 1) having a surface-treated size of 100 mm×100 mm and a thickness of 40 μm were subjected to a pressure of 0.1 Mpa, a temperature of 180° C., and a time of 1 minute. A laminate of an unsaturated carboxylic acid grafted L-LDPE and a copper foil (hereinafter referred to as a copper foil-laminated polyolefin film) was obtained by lamination. &lt;Production of Film Antenna&gt; In a clean room, a copper foil-laminated polyolefin film and an antenna circuit pattern are fixed on a circular quartz glass substrate by using a polyimide tape, and then the above-mentioned A quartz glass substrate device with a fixed copper foil laminated polyolefin film was applied to a spin coater, and 6 ml of the photoresist liquid was cast on the copper foil laminated polyolefin film, and the spin coater was rotated at a rotation number of 300 rpm. Secondly, the number of rotations was increased to 1500 rpm in 5 seconds, and the number of rotations was rotated for 20 seconds to obtain a photoresist-coated copper foil-laminated polyolefin film. In the state in which the copper foil-laminated polyolefin film is fixed to a circular quartz glass substrate, it is exposed to UV light having a wavelength of 35 5 nm for 15 seconds, and then cast and developed in a state where the above-mentioned glass substrate is rotated. The solution was developed, and then washed with water and dried while blowing nitrogen gas. The obtained developed copper foil-laminated polyolefin film was treated with an -152-200925171 etching solution at room temperature for 30 minutes, washed with water, and the photoresist layer was peeled off with acetone to obtain a film antenna having a conductive circuit pattern. &lt;Test of film antenna&gt; The film antenna was excellent in cold cycle test, copper foil peeling, cold resistance and heat resistance, and the obtained film antenna was grafted with unsaturated carboxylic acid. The olefin side was bonded to a polycarbonate film at 100 ° C 0 and a pressure of OL MPa to obtain a laminate. In the film antenna, the antenna circuit was not peeled off even after 200 thermal cycle tests, and the peeling with the polycarbonate was not observed, and the cold resistance and the heat-resistant punchability which were practically problem-free were exhibited. Further, as a result of the MIT test, the film antenna was subjected to a bending test of 150 times, the copper foil was not peeled off, and the film was finally broken, and the bending resistance and the flexibility were excellent. The maximum benefit of the film antenna at 135 kHz is -2 DBic, which shows practical characteristics. Example 95 An EV A grafted with maleic anhydride was obtained by the same procedure as in Example 94 except that the L-LDPE was changed to EVA, and the product was analyzed to have an unsaturated carboxyl group of 1.8% by weight. Acid (maleic anhydride), the gel is % by weight, YI is 1 and the hue is excellent. The unsaturated carboxylic acid grafted EVA was pressure-molded under the same conditions as in Example 94 to obtain a film having a size of 100 mm x 100 mm and a thickness of Ι 20 μm, and the obtained film was excellent in appearance and properties, and no fisheye or the like was observed. Disadvantages. -153- 200925171 The obtained film and the copper foil having a surface-treated size of 100 mm x 100 mm and a thickness of 40 μm were laminated at a pressure of 0.1 Mpa, a temperature of 180 ° C, and a time of 1 minute to obtain an unsaturated carboxylic acid bond. A laminate of a branch EVA and a copper foil (hereinafter, also a copper foil laminated polyolefin film). &lt;Production of Film Antenna&gt; In a clean room, a copper foil-laminated polyolefin film and an antenna circuit pattern 0 are sequentially fixed on a circular quartz glass substrate using a polyimide tape, and then the above-mentioned A quartz glass substrate device with a fixed copper foil laminated polyolefin film was applied to a spin coater, and 6 ml of a photoresist liquid was cast on a copper foil laminated polyolefin film, and the spin coater was rotated at a number of revolutions of 30 rpm. After 1 second, the number of rotations was increased to 15 rpm for 5 seconds, and the number of rotations was rotated for 20 seconds to obtain a copper foil-laminated polyolefin film coated with a photoresist. In the state where the copper foil-laminated polyolefin film is fixed to a circular quartz glass base plate, exposure is performed for 15 seconds with UV light having a wavelength of 365 nm, and then the film is rotated and developed in a state where the glass substrate is rotated. The solution was developed, and then washed with water and dried while blowing nitrogen gas. The obtained developed copper foil-laminated polyolefin film was treated with a bathing solution at room temperature for 30 minutes, washed with water, and peeled off with a photoresist layer to obtain a film antenna having a conductive circuit pattern. &lt;Test of film antenna&gt; The film antenna was excellent in cold resistance and heat-resistant squeezing property through 200 heat cycle tests, copper foil not peeling, -154-200925171, and the obtained film antenna was made into unsaturated carboxylic acid. The grafted polyolefin side was pressure-bonded to a polyimide film at 120 ° C and a pressure of 0.1 MPa to obtain a laminate.

In the film antenna, the antenna circuit was not peeled off even after performing the thermal cycle test for 200 times, and the peeling of the polyimide film was not observed, but the cold resistance and the heat-resistant punching property which were practically problem-free were exhibited. Further, as a result of the MIT test, the film antenna was subjected to a bending test of 150 times, the copper foil was not peeled off, and the film was finally broken, and the bending resistance and the flexibility were excellent. The maximum benefit of this film antenna at an average benefit of 135 kHz is -1.8 DBic, indicating a practical level of characteristics. Example 96 An alkalized EVA grafted with acrylic acid was obtained by the same method as in Example 94 except that L-LDPE was changed to alkalized EVA-1 and maleic anhydride was changed to acrylic acid. The result was an unsaturated carboxylic acid (acrylic acid) having 1% by weight, a gel of 0% by weight, a YI of 1 and a good hue. The unsaturated carboxylic acid grafted alkalinized EVA was the same as that of Example 94. Under pressure, a film having a size of 10 mm×100 rnm and a thickness of 130 μm was obtained, and the obtained film was excellent in appearance and properties, and the defects such as fish eyes were not observed. The obtained film and the copper foil having a surface treatment size of 100 mm×100 mm and a thickness of 40 μm were laminated under the conditions of a pressure of 0.1 Mpa, a temperature of 180° C., and a time of 1 minute to obtain an unsaturated carboxylic acid graft alkalized EVA. Laminate with copper foil (hereinafter, also referred to as copper foil laminated polyolefin film-155-200925171 &lt;Manufacturing of film antenna&gt; in a clean room> in the order of copper foil laminated polyolefin film and antenna circuit pattern The film was fixed on a circular quartz glass substrate by using a polyimide tape, and then the above-mentioned quartz glass substrate having a fixed copper foil laminated polyolefin film was placed on a spin coater to flow a photoresist liquid of 6 m 1 . Extending on the copper foil laminated Q polyolefin film, 'rotating the spin coater at 300 rpm for 10 seconds, then 'reducing the number of rotations to 5500 seconds to I500 rpm, and rotating it for 20 seconds with this rotation number' A copper foil-laminated polyolefin film coated with a photoresist is applied. The copper foil-laminated polyolefin film is fixed to a circular quartz glass substrate, and exposed to UV light having a wavelength of 365 nm for 15 seconds. Then, in making the above glass The developing solution was cast in a state where the substrate was rotated, and development was carried out, followed by washing with water and drying while blowing nitrogen gas. 0 The obtained copper foil-laminated polyolefin film which was developed was treated with an etching solution at room temperature for 30 minutes. After washing with water, the photoresist layer was peeled off with acetone to obtain a film antenna having a conductive circuit pattern. <Test of film antenna> The film antenna was subjected to 200 heat cycle tests, and copper foil was not peeled off. Cold resistance and heat resistance. It is excellent in the squeezing property, and the obtained film antenna is heat-pressed and bonded to the polyimide film at 120 ° C and a pressure of 0.1 MPa on the side of the unsaturated carboxylic acid grafted polyolefin side to form a laminate. -156- 200925171 This film antenna has not been peeled off even after 200 cycles of thermal cycling test. In addition, no peeling from the polyimide film has been observed, but it shows a practically problem-free level of cold resistance. Thermal shock resistance. Moreover, as a result of the MIT test, the film antenna was subjected to a bending test of 150 times, the copper foil was not peeled off, and the film was broken at the same time, and the bending resistance and flexibility were resistant. The maximum benefit of the average benefit of the film antenna at 135 kHz is -1.9 DBic, which shows practical characteristics. ❹ Manufacturing Example 3 1 7500 parts by weight of 1,1,2-trichloroethane and 2500 weight a 26% aqueous solution of sulfuric acid was placed in a 10-liter flask with a lower mouth and stirred vigorously.

After standing, the lower organic layer was taken out. Next, the taken-out organic layer and 5 kg of distilled water were placed in a 1-liter flask equipped with a lower mouth and vigorously stirred. After standing, the operation of taking out the lower organic layer was repeated three times to remove 1-butanol and 1, 2-epoxybutane. Further, 150 parts by weight of molecular sieve 4A was added to the taken-out organic layer, and the mixture was dehydrated by stirring with a stirrer to obtain purified 1,1,2-trichloroethane (hereinafter referred to as purified TCE). A 4 liter glass reaction vessel was charged with 1 750 parts by weight of purified TCE and 100 parts by weight of EVA, and 5 parts by weight of maleic anhydride, and the reactor was heated to 80 ° C, and then by 80 °C was uniformly dissolved for 4 hours, and during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liters/min to exclude air mixed into the reactor, and 0.16 parts by weight of BPO was used as a catalyst for the graft reaction. The solution was dissolved in 100 parts by weight of purified TCE, and this solution was continuously continuously added to the reactor, and the grafting reaction was carried out for 3 hours while maintaining the pressure of the reactor at -157 to 200925171 at 1 MPa. After the reaction was completed, the pressure of the reactor was returned to normal pressure, the temperature of the reactor was lowered to 70 ° C, and 0.1 part by weight of BHT as a stabilizer was added, and the solution was fed to a drum heated to 160 ° C. In the dryer, the EVA grafted with maleic anhydride is separated from the solvent, and the amount of gel analysis in the product is 〇% by weight.

Production Example 4 Into a 4 liter glass reaction vessel, 1 750 parts by weight of purified TCE and 100 parts by weight of alkalized EVA-1 and 7 parts by weight of maleic anhydride were charged, and the reactor was heated to 80 ° C. The alkalized EVA-1 was then uniformly dissolved by holding at 80 ° C for 4 hours. Further, during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liters/min to remove air mixed into the reactor, and as a catalyst for the graft reaction, 0.2 part by weight of BPO was dissolved in 1 part by weight of the purified TCE. This solution was continuously continuously added to the reactor, and a graft reaction was carried out for 3 hours while the pressure of the reactor was maintained at 1 MPa. After the reaction is completed, the pressure of the reactor is returned to normal pressure, the temperature of the reactor is lowered to 70 ° C, and the stabilizer is added as a stabilizer. After 1 part by weight of B HT, the solution is heated to 160 °. In the drum dryer of C, the alkalized EVA-1 grafted with maleic anhydride was separated from the solvent, and the amount of gel analysis in the product was 〇% by weight. Production Example 5 The alkalinized eva-2 of the grafted maleic anhydride was obtained by the same method as in Production Example 4 of -158-200925171, except that the alkalized EVA-1 was changed to the alkalized EVA-2. The quantitative analysis results are the weight of 〇. /. . Production Example 6 The EVA of the grafted acrylic acid was obtained by the same method as in Production Example 3 except that the maleic anhydride was changed to acrylic acid, and the result of the gelation analysis in the product was 0% by weight. 〇Example 9 7 30 g of the grafted maleic anhydride obtained in Production Example 3 (hereinafter referred to as modified EVA) and 9 g of carbon black were melt-kneaded at 150 ° C for 1 〇 minutes using a laboplastomill. The modified EVA in which carbon black was dispersed was obtained by cooling, and the obtained resin was pressed at 180 ° C to obtain a film having a thickness of 100 μm, and the obtained film was used, followed by 60 mm x 13 mm x 5 mm as shown in FIG. The copper plate, at this time, the area of the area was © 10 mm x 13 mm, and the next part was clamped with two long tail clips, followed by the conditions shown in Table 16. Then, the results of measuring the electrical resistance between the copper plates by TESTER, all the samples were 0 Ω, showing excellent electrical conductivity. In addition, the tensile strength was measured by Autograph, and all the samples showed strengths of 500 ng or more. Shows excellent adhesion. -159- 200925171 [Table 16] Temperature Time [°c] [Minute] Condition - 1 200 60 Condition - 2 180 60 Condition - 3 160 60 Condition - 4 140 60 Condition 1 5 200 30 Condition 1 6 200 15

Example 9 8 The modified e VA 30 g obtained in Production Example 3 and 18 g of copper fine particles were melt-kneaded at 150 ° C for 10 minutes using a laboplastomill, and then the modified EVA in which copper fine particles were dispersed was obtained by cooling. A film having a thickness of 1 μm was obtained by pressurizing the obtained resin at 180 ° C, except that the film containing copper microparticles obtained by the above method was used instead of the film containing carbon black. 97. The test was carried out in the same manner, and the heat treatment conditions are shown in Table 16'. Then, the resistance between the copper plates was measured by TESTER. All the samples were 0 Ω, showing excellent electrical conductivity, and 'measuring tensile strength with Autograph. As a result, all the samples showed an intensity of 500 N or more, showing excellent adhesion. Example 9 9 A film containing carbon black was used for the subsequent test in the same manner as in Example 97. However, in this example, a one-sided copper plate was used for an ITO plate (Ten 203 containing 10% by weight of Sn02) and a ZAO plate (containing 2% by weight). Al2〇3

ZnO), heat treatment conditions were carried out at 200 ° C for 1 hour, and then, the resistance between the plates was measured with -160 - 200925171 TESTER, and the ITO plate/copper plate was then 5 Ω, and the ZAO plate/copper plate was then sampled. 1 Ω showed excellent electrical conductivity. Further, as a result of measuring the tensile strength by Autograph, both of the samples were not peeled off even when the test force of 500 N was observed, and it was confirmed to be excellent adhesion. Example 100

30 g of the modified EVA and 18 g of the copper fine particles obtained in Production Example 3 were melt-kneaded at 150 ° C for 1 minute using a laboplastomill, and then the modified EVA in which the copper fine particles were dispersed was obtained by cooling, and the obtained resin was 180. The film was pressed at a temperature of ° C to obtain a film having a thickness of 1 μm, and the film was subjected to the same procedure as in Example 97 except that the film containing the copper fine particles obtained by the above method was used instead of the film containing the carbon black. The results are shown in Table 16. Then, the results of the electrical resistance between the copper plates were measured by TESTER. All the samples were 0 Ω, showing excellent electrical conductivity. In addition, the tensile strength was measured by Autograph, and all the samples were displayed. The strength of 500 N or more showed excellent adhesion. Example 1 〇1 A film containing a Cu powder was used for the subsequent test in the same manner as in Example 98. However, in this example, a one-sided copper plate was used for an ITO plate (T 203 containing 1% by weight of Sn02) and a ZAO plate (containing 2). ZnO of weight %A12〇3, heat treatment conditions at 200 ° C for 1 time, and then, after measuring the resistance between the plates with TESTER, the ITO plate/copper plate was followed by a sample of 0 Ω, ZAO plate/copper plate followed by sample It was 1 Ω and showed excellent electrical conductivity. -161 - 200925171 In addition, the tensile strength was measured by Autograph, and even if the test force of the two samples was not peeled off, it was confirmed to be excellent adhesion. Example 102 The alkalized EVA-1 (hereinafter referred to as modified EVA-1), 30 g of copper microparticles obtained by grafting maleic anhydride obtained in Production Example 4, and 15 g of copper fine particles were mixed by laboplastmill for 15 minutes. Thereafter, a film having a thickness of 11 μm was obtained by cooling the obtained resin to a modified EVA-1 having copper fine particles dispersed thereon by pressurizing the obtained resin at 1800 ° C, and using the obtained copper-containing film. The film of the microparticles was subjected to a pressure of 2 MPa at a temperature of 1 mm, a width of 15 mm, and a length of 100 mm, which was applied at 180 ° C for 1 minute, and then, the results of electrical resistance between the copper plates were measured by TESTER, and all the samples were 0 Ω showed excellent electrical conductivity, and in addition, the T-peel strength measured by Autograph was 35 N/15 mm, showing excellent adhesion. 〇 Example 103 The grafted maleic anhydride obtained in Production Example 5 was obtained. The alkalized EVA-2 (hereinafter referred to as modified EVA-2), 30 g, and carbon black 20 g were melt-kneaded at 150 ° C for 10 minutes using a laboplastomill, and then the modified EVA-2 in which carbon black was dispersed was obtained by cooling. Thickness obtained by pressurizing the obtained resin at 180 ° C A 20 micron film was obtained by using a film containing carbon black obtained, and a copper sheet having a thickness of 1 mm, a width of 15 mm, and a length of 100 nm was applied at 180 ° C for 1 minute at a pressure of 0.2 MPa, and then, after -162 to 200925171, As a result of TESTER measuring the electrical resistance between the copper plates, all the samples were 0 Ω, showing excellent electrical conductivity. In addition, the T-peel strength measured by Autograph was 30 N/15 mm, showing excellent adhesion. Example 104 30 g of grafted acrylic acid EVA (hereinafter referred to as "modified EVA") and 16 g of copper fine particles obtained in Production Example 6 were melt-kneaded at 150 ° C for 1 minute using a laboplastomill 0, and then dispersed by cooling. The modified EVA having copper microparticles was obtained by pressurizing the obtained resin at 180 ° C to obtain a film having a thickness of 105 μm, and using the obtained film containing copper microparticles to have a thickness of 1 mm, a width of 15 mm, and a length. The 100 mm copper piece was applied at 180 ° C for 1 minute at a pressure of 〇 2 MPa and then 'afterwards, the resistance between the copper plates was measured by TESTER. All the samples were 〇 Ω, showing excellent electrical conductivity, in addition' Use Aut〇 The T-peel strength measured by graph was 30 N/15 mm', which showed excellent adhesion. From Examples 97 to 104, it was confirmed that the conductive film of the present invention is not only a metal but also a metal and a conductive acid. Excellent Example 1〇5 Using a blended carbon black followed by polymer sheet (carbon black content: 30% by weight), a circular pure A1 paired target body having a diameter of 76.2 mm and a thickness of 5 mm and a copper backing plate were used. Bonding.

A carbon black-containing film having a diameter of about 70 mm was placed between a pure A1 paired target body and a copper backing plate, and then heat-treated at 200 ° C -163 - 200925171 for 1 hour. Then, the device is used in a sputtering apparatus, and Ar is used as a sputtering gas, and sputtering discharge characteristics (current-voltage characteristics) are measured at a pressure of 0.5 Pa, and a film formation rate is measured, and a film formed by sputtering is measured. Resistivity. In comparison, the same measurement was performed for the subsequent pure A1 target using general indium soldering. Fig. 2 shows the measurement results of the discharge characteristics, and Table 17 shows the measurement results of the film formation rate and the sheet resistivity. [Table 17] Film formation rate [nm/min] Resistivity μΩοιη] Film thickness: 100 nm Film thickness: 300 nm Conductive film 58.1 3.59 3.18 Indium soldering 57.7 3.56 3.26 From Fig. 2 and Table 17, it is known that the conductivity of the present invention is used. The film has the same characteristics as the subsequent target by using a general indium soldering through the subsequent sputtering target, and it is confirmed that it can be used as a bonding material. Example 106 Using a post-polymer sheet of copper fine particles (copper particle content: 60% by weight), a pure A1 sputtering target having a diameter of 76.2 mm and a thickness of 5 mm was bonded to a copper backing body (bonding) ). A copper polymer microparticle-containing adhesive polymer sheet having a diameter of about 70 mm was placed between a pure A1 sputtering target and a copper backing plate, and fixed with a vise clamp - 164 - 200925171 '200 ° C, 1 hour heat treatment And proceed. Then, the device is placed on a sputtering apparatus, and Ar is used as a sputtering gas, and sputtering discharge characteristics (current-voltage characteristics) are measured at a pressure of Pa5 Pa, and a film formation rate is measured, and the resistance of the film formed by sputtering is measured. rate. The same measurement was also carried out for the subsequent pure A1 target using general indium soldering. Fig. 3 shows the measurement results of the discharge characteristics, and the table is a graph showing the measurement results of the film formation rate and the sheet resistivity. [Table 18] Film formation rate [nm/minl Electro-positive rate μΩοηι] Film thickness: lOOnm Film thickness: 300 nm Conductive film 58.4 3.47 3.18 Indium soldering 57.7 3.56 3.26

From Fig. 3 and Table 13, it is found that the use of the conductive film of the present invention through the subsequent sputtering target has the same characteristics as that of the subsequent target using general indium soldering, and it has been confirmed that it can be used as a bonding material. Production Example 7 1 7500 parts by weight of yttrium, iota, 2-trichloroethane and 2500 parts by weight of a 26% aqueous sulfuric acid solution were placed in a 1-liter flask equipped with a lower mouth and vigorously stirred, and the lower layer was taken out after standing. The organic layer was then vigorously stirred by placing the removed organic layer with 5 kg of distilled water in a 10-liter flask with a lower opening, and the operation of removing the organic layer of the lower layer after standing for 3 times was repeated to remove 1-butanol- 165- 200925171 and 1,2-epoxybutane. Further, 150 parts by weight of the molecular sieve 4A was added to the taken-out organic layer, and the mixture was dehydrated by stirring with a stirrer to obtain purified 1,1,2-trichloroethane (hereinafter referred to as purified TCE).

A 4 liter glass reaction vessel was charged with 1750 parts by weight of purified TCE and 100 parts by weight of alkalized EVA-1 (manufactured by Tosoh Co., Ltd., 11-641 0 M), and 9.7 parts by weight of maleic anhydride. The reactor was heated to 80 ° C, and then EVA was dissolved in both at 80 ° C for 4 hours, and during this time, nitrogen was introduced into the reactor at a flow rate of 5 liter / minute to remove the air mixed into the reactor. As a catalyst for the graft reaction, 0.16 parts by weight of BPO was dissolved in 100 parts by weight of the purified TCE, and this solution was continuously continuously added to the reactor, and the pressure of the reactor was maintained at 1 MPa for 3 hours. Branch reaction. After the reaction was completed, the pressure of the reactor was returned to normal pressure, the temperature of the reactor was lowered to 70 ° C, and 0.1 part by weight of BHT as a stabilizer was added, and the solution was fed to a drum heated to 160 ° C. In the dryer, the alkalized EVA grafted with maleic anhydride was separated from the solvent, and the amount of the gel in the product was analyzed by weight %. Production Example 8 Grafting was carried out by the same method as in Production Example 7, except that the modified polyolefin was changed from alkalized EVA-1 to alkalized EVA-2 (manufactured by Tosoh Corporation, H-6051K). In the alkalized EVA of maleic anhydride, the amount of gel analysis in the product was 〇% by weight. Production Example 9-166-200925171 The same method as in Production Example 7 except that the modified polyolefin was changed from alkalized EVA-1 to alkalized EVA-3 (manufactured by Tosoh Corporation, H-6960). The alkalized EVA obtained by grafting maleic anhydride was obtained, and the amount of gel analysis in the product was 〇% by weight. Manufacturing Example 10

The EVA of the grafted maleic anhydride was obtained by the same method as in Production Example 7, except that the modified polyolefin was changed from alkalized EVA-1 to EVA, and the gel amount analysis result in the product was 〇 weight. %. Production Example 1 1 L-LDPE grafted with maleic anhydride was obtained by the same method as in Production Example 7, except that the modified polyolefin was changed from alkalized EVA-1 to L-LDPE. The results of the analysis of the amount of glue were 〇% by weight. 0 Production Example 12 EVA of grafted acrylic acid was obtained by the same method as in Production Example 7, except that the modified polyolefin was changed from alkalized EVA-1 to EVA, and the grafted unsaturated carboxylic acid was changed to acrylic acid. The amount of gelation in the product was analyzed by the weight %. Production Example 13 In the same manner as in Production Example 7, except that the modified polyolefin was changed from alkalized EVA-1 to L-LDPE, and the grafted unsaturated residual acid was changed to acrylic acid, the same procedure as in Production Example 7-167-200925171 was used. The l-ldpe of the grafted acrylic acid was obtained, and the amount of gel analysis in the product was 0% by weight. Manufacturing Example 14

The EVA of the grafted acrylic acid was obtained by changing the modified polyolefin to the EVA from the alkalized EVA-1 to the EVA, and changing the grafted unsaturated carboxylic acid to methacrylic acid by the same methylation method as in Production Example 7. The amount of gel in the product was analyzed by 0% by weight. Production Example 1 5 The modified polyolefin was changed from the alkalized EVA-1 to L-LDPE, and the grafted unsaturated carboxylic acid was changed to methacrylic acid, and the same methyl group as in Production Example 7 was used. The amount of the gel in the product of the grafted acrylic acid L-LDPE was 0% by weight. 〇Production Example 16 A grafted methyl group was obtained by the same method as in Production Example 7, except that the modified polyolefin was changed from alkalized EVA-1 to PP, and the grafted unsaturated carboxylic acid was changed to methacrylic acid. The amount of gel in the PP of acrylic acid was analyzed by the amount of 〇% by weight. Example 1 0 7 The alkalized EvA 1.08 g of the grafted maleic anhydride obtained in Production Example 7 was dissolved in 1,1,2-trichloroethane to obtain 20 g of a polymer solution, and the solution was dissolved in -168- 200925171 20 g of silver particles were added to the solution, and silver particles were dispersed in an ultrasonic cleaner at room temperature to obtain a paste liquid in which silver particles were uniformly dispersed. Although the dispersion was allowed to stand at room temperature for one week, the dispersion state did not change. No precipitation of silver particles was observed. Further, this dispersion was used to print a circuit on a polyimide film by screen printing, and the solvent was volatilized at room temperature, followed by heat treatment at 220 °C. The obtained circuit had a resistivity of ΙΟμΩοηη, and showed excellent conductivity. Further, this circuit was completely peeled off by a peeling test using a tape, and showed excellent adhesion to the substrate. Example 108

1.08 g of alkalized EVA of grafted maleic anhydride obtained in Production Example 8 was dissolved in trichloroethane to obtain 20 g of a polymer solution, and 26 g of copper particles were added to the solution, and ultrasonic cleaning was performed at room temperature. The copper particles were dispersed to obtain a paste liquid in which copper particles were uniformly dispersed. Although the dispersion was allowed to stand at room temperature for one week, there was no change in the dispersion state, and no precipitation of copper particles was observed. Further, using this dispersion, a polyimine film was printed by a screen printing method, and the solvent was volatilized at room temperature, followed by heat treatment at 220 °C. The obtained circuit had a resistivity of 1 1 μΩ (; ηι, which showed excellent conductivity, and this circuit showed no peeling at all by a peeling test using a tape, and showed excellent adhesion to the substrate. 109. 1.08 g of the alkalized EVA of grafted maleic anhydride obtained in Production Example 9 was dissolved in 1,1,2-trichloroethane to obtain 20 g of a polymer solution, which was added to the solution -169-200925171 16 g of aluminum was dispersed in an ultrasonic cleaner at room temperature to obtain a paste liquid in which aluminum particles were uniformly dispersed. Although the dispersion was allowed to stand at room temperature for one week, there was no change in the dispersion state, and no aluminum particles were observed. Further, using this dispersion, a polyimine film was printed by a screen printing method, and the solvent was volatilized at room temperature, and then heat-treated at 220 ° C. Further, the circuit was peeled off by using a tape. The test, which was not peeled at all, showed excellent adhesion to the substrate. 〇 Example 1 1 〇

0.1 g of the grafted maleic anhydride-derived EVA obtained in Production Example 1 was dissolved in 1,1,2-trichloroethane to obtain 2 g of a polymer solution, and gold particles lg were added to the solution. In the ultrasonic cleaning device, the silver particles were dispersed to obtain a paste liquid in which the gold particles were uniformly dispersed. Although the dispersion was allowed to stand at room temperature for one week, the dispersion state did not change, and no precipitation of gold particles was observed. Using this dispersion, a circuit was printed on a polyphenylene sulfide sheet by screen printing, and the solvent was volatilized at room temperature, and then heat-treated at 23 ° C, and the obtained circuit had a resistivity of 6 μΩ cm ' Excellent electrical conductivity was obtained, and this circuit showed no peeling at all through the peeling test using a tape, and showed excellent adhesion to the substrate. Example 1 1 1 The alkalized EVA0·05 g of the grafted maleic anhydride obtained in Production Example 7 was dissolved in 1,1,2-trichloroethane to obtain a polymer solution of lg' added to this solution. Silver Nylon paste · 5 g 'Disperse silver particles -170- 200925171 at room temperature in an ultrasonic cleaner to obtain a paste-like liquid in which silver particles are uniformly dispersed, although the dispersion is allowed to stand at room temperature. Week, the dispersion state did not change, no precipitation of silver particles was observed, and in addition, the dispersion was printed on the polycarbonate film by screen printing using the dispersion, and the solvent was volatilized at room temperature at 23 ° C. The heat treatment was performed, and the obtained circuit had a specific resistance of 5 μΩ (^πι, which showed excellent electrical conductivity, and the circuit was completely peeled off by a peeling test using a tape, and showed excellent adhesion to the substrate. Example 1 1 2 L-LDPElg of the grafted maleic anhydride obtained in Production Example 11 was dissolved in 1,1,2-trichloroethane to obtain 20 g of a polymer solution, and silver particles 1 were added to the solution. 6g, dispersing silver particles in an ultrasonic cleaner at room temperature to obtain silver particles A uniformly dispersed paste-like liquid, although the dispersion was allowed to stand at room temperature for one week, the dispersion state did not change, and no precipitation of silver particles was observed, and further, the dispersion was printed by screen printing using the dispersion. The circuit was subjected to a Q polyimine film, and the solvent was volatilized at room temperature, and then heat-treated at 230 ° C. The obtained circuit had a resistivity of ΙΟμΩοπι, which showed excellent conductivity, and the circuit was peeled off by using a tape. The test was not peeled at all, and showed excellent adhesion to the substrate. Example 1 1 3 The grafted acrylic acid EVA lg obtained in Production Example 12 was dissolved in 1,1,2-trichloroethane to obtain 20 g of the polymer solution, 12 g of silver particles were added to the solution, and the silver particles were dispersed in an ultrasonic cleaner at room temperature to obtain a paste-like liquid in which the silver particles were uniformly dispersed, although at room temperature. The dispersion was allowed to stand for 1 week, the dispersion state was unchanged, and no precipitation of silver particles was observed. Further, the dispersion was printed on the polyimide film by screen printing using the dispersion, and the solvent was volatilized at room temperature. After, to 210 C was heat-treated, and the obtained circuit had a specific resistance of 9 μΩ, which showed excellent conductivity. Further, this circuit showed no peeling at all by a peeling test using a tape, and showed excellent adhesion to the substrate. Example 1 1 4

1.2 g of grafted acrylic acid L-LDPE obtained in Production Example 13 was dissolved in 1,1,2-trichloroethane to obtain 20 g of a polymer solution, and 14 g of copper particles were added to the solution at room temperature. The ultrasonic cleaner disperse the copper particles to obtain a paste liquid in which the copper particles were uniformly dispersed. Although the dispersion was allowed to stand at room temperature for one week, the dispersion state did not change, and no precipitation of copper particles was observed. Further, using this dispersion liquid, a polyimine film was printed by a screen printing method, and the solvent was volatilized at room temperature, and then heat-treated at 21 (TC), and the obtained circuit had a resistivity of 9 μΩ (ηη, This circuit showed excellent conductivity, and this circuit showed no adhesion at all through the peeling test using a tape, and showed excellent adhesion to the substrate. Example 1 1 5 The methyl group obtained in Production Example 14 was grafted. Acrylic EVA 0.8g is dissolved in 1,1,2-trichloroethane to obtain 20g of polymer solution, 14g of copper particles are added to the solution, and copper particles are dispersed by ultrasonic cleaning at room temperature -172- 200925171 While the paste liquid in which the copper particles were uniformly dispersed was obtained, the dispersion was allowed to stand at room temperature for one week, and the state of dispersion was not changed, and precipitation of copper particles was not observed. Further, the dispersion was printed by screen printing using the dispersion. The printed circuit is printed on a polyimide film, and the solvent is volatilized at room temperature, and then heat-treated at 1 90 ° C. The obtained circuit has a resistivity of 8 μΩ ε η, which exhibits excellent conductivity, and the circuit uses a tape. Peel test, No separation, displayed an excellent adhesive properties to the substrate.

Example 116

The methyl group obtained in Production Example 15 was dissolved in 1,1,2-trichloroethane by dissolving 1.4 g of L-LDPE of grafted acrylic acid to obtain 20 g of a polymer solution, and 15 g of aluminum particles were added to the solution. The aluminum particles were dispersed in the ultrasonic cleaner to obtain a paste liquid in which the aluminum particles were uniformly dispersed. Although the dispersion was allowed to stand at room temperature for one week, there was no change in the dispersion state. No precipitation of aluminum particles was observed. Further, using this dispersion, a PPS sheet was printed by a screen printing method, and the solvent was volatilized at room temperature, and then heat-treated at 23 ° C, and the obtained circuit had a resistivity of 12 μΩ ειη, which showed excellent Conductivity, in addition, this circuit showed excellent adhesion to the substrate via a peeling test using a tape, 'completely undivided'. Example 1 1 7 The methyl group obtained in Production Example 16 was dissolved in PP, 1.5 g of grafted acrylic acid, and dissolved in 1,1,2-trichloroethane to obtain 2 μg of a polymer solution. The iron particles were dispersed in the ultrasonic cleaner at room temperature by an ultrasonic cleaner-173-200925171 to obtain a paste liquid in which iron particles were uniformly dispersed. Although the dispersion was allowed to stand at room temperature for one week, the dispersion state did not change, and no Precipitation to iron particles. Further, using this dispersion liquid, a polyimine film was printed by a screen printing method, and the solvent was volatilized at room temperature, and then heat-treated at 230 ° C. The obtained circuit had a resistivity of 13 pQ Cm, which showed Excellent Conductivity' In addition, this circuit showed no peeling at all through a peeling test using a tape, and showed excellent adhesion to a substrate. 〇Comparative Example 4 8 After dissolving 6 g of dodecylamine in 75 g of onion alcohol, silver particles were added to obtain a silver particle dispersion, and 0.7 g of methylhexahydrophthalic anhydride was added to the solution. Silver paste, the silver paste is printed on a polyphenylene sulfide sheet by screen printing, and the solvent is volatilized at room temperature, and then heat treated at 230 ° C, although the resistivity of the obtained circuit is 8 μΩ (ίΐη ' showed excellent conductivity, but this circuit was tested by peeling using a tape, the peeling frequency was 100/100, and it was easy to peel off from the substrate. Comparative Example 4 9 The silver paste obtained in Comparative Example 48 was borrowed. The printed circuit was printed on a polyimide film by a screen printing method, and the solvent was volatilized at room temperature, and then heat-treated at 23 ° C, although the obtained circuit had a resistivity of 8 μΩ (; Ι η showed excellent Conductivity, but this circuit was subjected to a peeling test using a tape, the peeling frequency was 80/100, and the adhesion to the substrate was insufficient. -174- 200925171 Comparative Example 50 6 g of dodecylamine was dissolved in 75 g of onion alcohol ' 1 〇g to obtain a silver particle dispersion in this solution Adding -7 g of phthalic anhydride and 55 g of phenol resin to obtain a silver paste. The obtained silver paste is printed on a imprinted imide film by screen printing, and the solvent is volatilized at room temperature, although Heat treatment, but the film hardening takes 70 minutes. Although the obtained 0 resistivity is ΙΟμΩ ίηη, which shows excellent electrical conductivity, the peeling test using a tape, the peeling frequency is 10/100 and the originality is insufficient. Comparative Example 5 1 EVAl.Og The solution was dissolved in 1,1,2-trichloroethane, and 15 g of silver particles were added to the solution, and the silver particles were dispersed at room temperature to obtain a paste liquid, and the fruit was allowed to stand at room temperature. 1 hour of iron particle precipitation, did not show a practical use of this liquid again with the ultrasonic cleaner to disperse the silver particles, immediately by printing a printed circuit on the polyimide film, at room temperature to dissolve at 230 ° C, However, the precipitation of silver particles showed a good electrical conductivity although the resistivity was 6 μΩ οιη, but the electric power was subsequently peeled off by using a tape, and the peeling frequency was such that no adhesion was observed at all. Comparative Example 5 2 Addition of methyl groups of silver particles Hexahydro brush The circuit of the circuit which is carried out at a concentration of 230 ° C is ultrasonically washed by the polymerization of 2 〇 g with the substrate to wash the dispersion of the dispersion. After the evaporation of the screen printing agent, the circuit is The circuit was not dissolved with the substrate 100/100 and -175- 200925171, and 1.0 g of L-LDPE was dissolved in 1,1,2-trichloroethane to obtain 20 g.

In the polymer solution, 15 g of copper particles were added to the solution, and copper particles were dispersed in an ultrasonic cleaner at room temperature to obtain a paste liquid. The dispersion was allowed to stand at room temperature, and copper particles were precipitated after 1 time, and were not shown. Practical dispersion. The liquid was again dispersed in the ultrasonic cleaner using an ultrasonic cleaner, and the printed circuit was immediately printed on the polyimide film by screen printing. After the solvent was volatilized at room temperature, the copper particles were precipitated after heat treatment at 220 ° C. Although the resistivity of the circuit is 7 μΩ cm, it shows excellent conductivity, but this circuit is not bonded to the substrate, and the peeling frequency is 10 0/1 00 through the peeling test using the tape, and the adhesion is not observed. . While the present invention has been described in detail with reference to the specific embodiments thereof, various modifications and modifications can be applied without departing from the spirit and scope of the invention. This will be understood by those skilled in the art. The present invention is based on the Japanese franchise application (Japanese Patent Application No. 2007-2104 64) filed on August 10, 2007, and the Japanese Special S (Autumn Wish 2007-210465) filed on August 10, 2007, August 17, 2007 Japan's application for the privilege of the Japanese franchise (Special Wish 2007-213100), the Japanese franchise application filed on September 3, 2007 (Special Wish 2007-228055), and the Japanese franchise application for September 6, 2007 (Special Wish 2007- 231,554, Japan's franchise application (2007-294826), which was applied for on November 13th, 2007, Japan's privilege, which was filed on November 28, 2007 (Special Wishes 2007-3 07897), and the Japanese franchise applied for on November 30, 2007 I wished for a wish (2007-3 1 0203), a Japanese franchise application filed on July 11, 2008 (Special Wish 2008-181970), Japan-176-200925171, which was applied for on July 11, 2008. 181971) The invention of the Japanese franchise (Japanese Patent Application No. 2008-181 1 972) filed on July 11, 2008, the contents of which are hereby incorporated by reference. [Industrial Applicability] According to the present invention, it is possible to provide an unsaturated carboxylic acid grafted polyolefin which is excellent in adhesion not only to a plastic material but also to a dissimilar material and has wide usefulness.

hydrocarbon. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] is a view showing a configuration of a sample which is subsequently tested using a conductive film. Fig. 2 is a graph showing the relationship between current and voltage at the time of sputtering discharge in the first embodiment. Fig. 3 is a graph showing the relationship between current and voltage at the time of sputtering discharge in Example 106. -177-

Claims (1)

200925171 X. Patent Application No. 1 - An unsaturated carboxylic acid grafted polyolefin characterized in that the content of the gel insoluble in xylene heated to 140 ° C is less than 〇.〇2% by weight, and The graft amount of the saturated carboxylic acid is 0.1 to 10% by weight. 2. The unsaturated carboxylic acid grafted polyolefin according to claim 1, which is in the form of an insoluble gel in xylene heated to 140 °C. 3. A method for producing an unsaturated carboxylic acid grafted polyolefin according to claim 1 or 2, which is characterized in that, when a unsaturated carboxylic acid is graft-reacted to a polyolefin in a solvent, the removal is performed using 1,1. 1,1,2-trichloroethane as an impurity of an alcohol compound and/or an epoxy compound contained in 2-trichloroethane, and a reaction temperature of 40 to 130 ° C, and a reaction pressure of 1 MPa or less. A method for producing an unsaturated carboxylic acid grafted polyolefin according to claim 1 or 2, which is characterized in that the unsaturated carboxylic acid is bonded to a halogen-based solvent having a boiling point of 120 ° C or less under normal pressure. The graft reacts with the polyolefin in the grafting reaction step; the solvent is volatilized and removed by supplying the reaction solution after the grafting reaction to a drum dryer; and the isolation step of the unsaturated carboxylic acid grafted polyolefin isolating the reaction product to make. • A thermal-melting film characterized by being formed from an unsaturated carboxylic acid grafted polyolefin of claim 1 or 2. 6. A multilayer laminate comprising at least one of a metal layer and a resin layer and an elastic electrically insulating layer, and the metal layer and/or the resin layer and the elastic electrically insulating layer are followed by a multilayer laminate 'It is characterized by an elastic electrically insulating layer made of an unsaturated carboxylic acid grafted polyolefin of the first or second aspect of the patent application. - 178 - 200925171 7. The multilayer laminate of claim 6, wherein the metal layer and/or the resin layer and the elastic electrically insulating layer are followed by heat pressing. 8. The multilayer laminate according to claim 6 or 7, which further comprises 20 to 40 parts by weight of a flame retardant relative to 1 part by weight of the unsaturated carboxylic acid graft polyolefin. A flexible wiring film characterized by having a conductive circuit formed of a metal on at least one side of a film formed of the unsaturated carboxylic acid grafted polyolefin of claim 1 or 2. 10. A conductive film characterized by being unsaturated carboxylic acid grafted polyolefin of claim 1 or 2 containing conductive fine particles. 1. Conductive according to the first aspect of the patent application. Film, wherein the conductive microparticles are made of gold, silver, copper, molybdenum, nickel, carbon, tin, indium, palladium, rhodium, samarium, bismuth, antimony, aluminum, iron, indium, magnesium, platinum, bismuth, tin, zinc. One or more kinds of fine particles selected from cobalt, chromium, titanium, molybdenum, tungsten, and carbon black. 12. The conductive film according to claim 10 or 11, which contains 30 to 99 parts by weight of conductive fine particles with respect to 100 parts by weight of the unsaturated carboxylic acid graft polyolefin. A sputter target which is characterized in that a pair of target bodies and a back sheet are formed by using a conductive film according to any one of claims 10 to 12. An inorganic fine particle dispersion comprising the unsaturated carboxylic acid grafted polyolefin, inorganic fine particles and a solvent of the first or second aspect of the patent application. -179-