JP2004269872A - Polypropylene copolymer, composition containing the same and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a propylene polymer excellent in adhesiveness to a crystalline propylene-based polymer, solubility and compatibility with polar resins, and provide a method for producing the same and a composition containing the propylene copolymer. <P>SOLUTION: The polypropylene copolymer comprises a polymer main chain (A) derived from a propylene-based polymer having a predetermined requirement defined by 13C-NMR spectrum measurement and ≤100°C melting point [Tm] by differential scanning calorimeter or <5J/g heat of crystal melting, and a side chain containing a polymer chain (B) different from the main chain, and the weight ratio of (A)/(B) is 20/1-1/20. The composition containing the copolymer and the method for producing the copolymer are also claimed. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention has good compatibility with a polar resin, a surface treatment agent for an olefin polymer having crystallinity, a polypropylene copolymer useful as an adhesive or a paint, and a composition containing the same, Furthermore, it relates to the production method.

  Propylene polymers and propylene / α-olefin copolymers are inexpensive and have excellent mechanical properties, heat resistance, chemical resistance, water resistance and the like, and are therefore used in a wide range of fields. However, such a propylene-based polymer generally has low polarity since it does not have a polar group in a molecule, and has a drawback that painting and adhesion are difficult. In order to remedy this drawback, the surface of the molded article of the propylene polymer is chemically treated with a chemical or the like, or the surface of the molded article is oxidized by a method such as corona discharge treatment, plasma treatment, or flame treatment. Various approaches have been tried. However, these methods not only require special equipment, but also cannot be said to have a sufficient effect of improving paintability and adhesiveness.

  Therefore, so-called chlorinated polypropylene and acid-modified propylene / α-olefin copolymer have been developed as a device for imparting good coatability and adhesion to a propylene-based polymer by a relatively simple method. Normally, isotactic polypropylene is insoluble in a solvent. Therefore, various measures have been devised for chlorinating isotactic polypropylene or copolymerizing propylene with an α-olefin to reduce crystallinity and increase solubility. In addition, since the crystallinity is reduced by the acid modification, a resin having relatively good solubility has been obtained by the acid modification. However, as the amount of modification increases, the adhesiveness to the polypropylene resin is inferior, and the solubility and the adhesiveness are contradictory subjects. Further, in addition to this problem, there is a problem that these resins have low compatibility with polar resins used in paints and the like and cannot be mixed with acrylic resins and the like.

As a resin having improved compatibility, JP-A-3-229772 discloses that a reactive unsaturated compound having at least one hydroxyl group, glycidyl group or amino group is grafted to an acid-modified propylene / α-olefin copolymer. A resin obtained by polymerization is shown, and a coating composition for polyolefin resin containing the resin is also disclosed. However, in this composition, the solubility and compatibility are improved, but the adhesion is inferior, by modifying the resin contained therein by modification with α-olefin, such as acid modification, and grafting of a polar resin. As a problem.
JP-A-3-229772

  The present invention can provide good adhesion to a crystalline propylene-based polymer, coatability, and solubility, a polypropylene copolymer excellent in compatibility with a polar resin, a method for producing the same, and It is intended to provide a composition containing the polypropylene copolymer, particularly an aqueous dispersion.

The present inventors have intensively studied to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the gist of the present invention is to provide a polymer main chain (A) derived from a propylene-based polymer having the following properties (1) and (2) and a polymer chain (B) different from the main chain. A polypropylene copolymer having a chain and a weight ratio of (A) / (B) in a range of 20/1 to 1/20, and a method for producing the copolymer.
(1) In ¹³ C-NMR, a peak derived from a carbon atom of a methyl group in a propylene unit chain composed of a head-to-tail bond was observed, and a peak top chemical attributed to a pentad expressed in mmmm was observed. When the shift is 21.8 ppm, the ratio (S ₁ / S) of the peak area S ₁ having a peak top at 21.8 ppm to the total area S of the peaks appearing from 19.8 ppm to 22.2 ppm is 20%. or more and 60% or less, and about 21.5~21.7ppm that the area of the peak (mmmr) having a peak top is _{4 + S 1 / S 2>} 5 when the _{S 2} (2) propylene heavy The melting point [Tm] measured by a differential scanning calorimeter of the combined product is 100 ° C. or less, or the heat of crystal fusion does not show 5 J / g or more.

Another aspect of the present invention resides in the above polypropylene copolymer having the following properties (a) to (c), and a composition and an aqueous dispersion containing the copolymer.
(A) When dissolved in toluene at 25 ° C. with polymethyl methacrylate at a weight ratio of 50/50 and a solid concentration of 12% by weight, the transmittance (650 nm) is 80% or more. (B) Toluene at 25 ° C. When dissolved at a concentration of 10% by weight in water, the insoluble content is 1% by weight or less based on the whole polymer. (C) Adhesion to a polypropylene substrate by a test for adhesion (cross-cut tape method) is 50%. / 100 or more

  The polypropylene copolymer of the present invention has good compatibility with a polar resin and excellent adhesion to an olefin polymer having crystallinity. It is very useful because it can be used as a compatibilizer with resins.

Hereinafter, the present invention will be described in detail.
The polymer main chain (A) in the polypropylene copolymer of the present invention is derived from a polypropylene-based polymer having the specific properties shown in the above properties (1) and (2). Properties (1) such as a modified propylene polymer modified with an acid or the like of a propylene polymer having 1) and (2) but having no functional group, or a copolymer of propylene and a functional group-containing monomer It is derived from a propylene polymer having a functional group having (2) and (2), but is preferably derived from a propylene polymer modified with an acid or the like.

  The propylene polymer having no functional group to be modified may be a propylene homopolymer or a copolymer with another monomer. Other monomers include olefinic hydrocarbons such as ethylene, butene, 1-pentene, 1-hexene, and 1-octene.

Examples of the propylene-based polymer having a functional group such as a copolymer include a carboxylic acid group, a hydroxyl group, an amino group, an epoxy group, and a copolymer of propylene with a monomer having a group such as an isocyanate group, These monomers include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, (dimethylamino) ethyl (meth) acrylate, (meth) Ethyl (2-isocyanato) acrylate, maleic anhydride, and the like.
In addition to the copolymerization of propylene and a functional group-containing monomer, a propylene polymer having a functional group can be obtained by using a terminal stopper and a chain transfer agent in propylene polymerization. Examples of the terminal stopper include the above-mentioned copolymerizable monomers.

  The preferred propylene content of the propylene-based polymer in the present invention is at least 80 mol%, more preferably at least 90 mol%, further preferably at least 95 mol%, most preferably at least 98 mol%. If the propylene content in the propylene-based polymer is less than 80%, the adhesion to the propylene-based resin having crystallinity as a substrate may decrease.

The propylene-based polymer in the present invention preferably has a weight average molecular weight Mw of 5,000 to 200,000 measured by GPC (Gel Permeation Chromatography). When Mw is smaller than 5,000, not only the deterioration of the film forming property after application of the target polypropylene copolymer obtained from the polymer becomes remarkable, but also the stickiness is remarkable, which is not preferable. Further, when Mw exceeds 200,000, although there is no major problem with respect to film forming properties and stickiness, the viscosity when the polymer is dissolved in a solvent becomes too high, so that the production or the handling of the polymer solution is difficult. It is not preferable because it causes inconvenience. In the present invention, the range of the weight average molecular weight Mw is from 5,000 to 200,000, preferably from 10,000 to 180,000, and more preferably from 20,000 to 150,000.
The GPC can be measured by a conventionally known method using a commercially available device using orthodichlorobenzene or the like as a solvent and polystyrene as a standard sample.

  The molecular weight distribution of the propylene-based polymer in the present invention is not particularly limited. However, an excessively wide molecular weight distribution should be avoided because it means that the content of low molecular weight components is necessarily large. When the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn is used as an index of the molecular weight distribution, it is preferably Mw / Mn <20, more preferably Mw / Mn <10, and most preferably Mw / Mn <5. Are preferably used.

As a feature of the propylene-based polymer in the present invention, a highly crystalline block and a highly amorphous block coexist in the main chain thereof, and the highly crystalline block is rich in isotacticity (isotacticity). Can be mentioned. However, if there are too many blocks having high crystallinity, the solubility in a solvent is deteriorated. Therefore, the balance between blocks having high crystallinity and blocks having high amorphousness is important. In the present invention, a requirement defined by a ¹³ C-NMR spectrum is applied as a part of the index indicating this balance, and the requirement satisfies the above-mentioned predetermined range to provide excellent structural characteristics.

The method for measuring the ¹³ C-NMR spectrum in the present invention is as follows.
A sample of 350 to 500 mg is completely dissolved in a 10 mmφ sample tube for NMR using about 2.2 ml of orthodichlorobenzene. Next, about 0.2 ml of deuterated benzene is added as a lock solvent to homogenize, and the measurement is performed at 130 ° C. by a complete proton decoupling method. Measurement conditions, a flip angle 90 °, pulse interval 5T ₁ or more (T _1, the spin of the methyl groups - maximum value of the lattice relaxation time) and. In the propylene-based polymer, the spin-lattice relaxation time of the methylene group and the methine group is shorter than that of the methyl group, so that the recovery of the magnetization of all carbons is 99% or more under this measurement condition. In order to improve the quantification accuracy, it is preferable to use an NMR apparatus having a resonance frequency of ¹³ C nucleus of 125 MHz or more and perform integration for 20 hours or more.

  The chemical shift is defined as a methyl branch among ten kinds of pentads (mmmm, mmmmr, rmmr, mmrr, mmrm, rmrr, rmrm, rrrr, rrrm, mrrm) of a propylene unit chain composed of a head-to-tail bond. Are set to be the same, that is, the chemical shift of the peak based on the methyl group of the third unit of 5 chains of propylene units represented by mmmm is set as 21.8 ppm, and the other carbon peaks are set on the basis of this. Determine the chemical shift. According to this criterion, in the case of the other five chains of propylene units, the chemical shift is approximately as follows. That is, mmmr: 21.5 to 21.7 ppm, rmmr: 21.3 to 21.5 ppm, mmrr: 21.0 to 21.1 ppm, mmrm and rmrr: 20.8 to 21.0 ppm, rmrm: 20.6 to 20.8 ppm, rrrr: 20.3 to 20.5 ppm, rrrm: 20.1 to 20.3 ppm, and mrrm: 19.9 to 20.1 ppm. It should be noted that the chemical shifts of the peaks derived from these pentads vary somewhat depending on the NMR measurement conditions, and that the peaks are not necessarily single peaks, but rather complex splitting patterns ( It is necessary to pay attention to the fact that it often indicates a split pattern.

The propylene polymer according to the present invention, wherein the chemical shift of the peak attributable to the pentad represented by mmmm is 21.8 ppm, and the pentad, which appears in the range of 19.8 ppm to 22.2 ppm, That is, the ratio of the area S ₁ having a peak top of 21.8 ppm to the total area S of the peaks belonging to mmmm, mmmr, rmmr, mmrr, mmrm and all pentads of rmrr, rmrm, rrrm, and mrrm (S ₁ / S ) 20% or more and 60% or less, the area of the peak (mmmr) of and the 21.5~21.7ppm the peak top is _{4 + 2S 1 / S 2>} 5 when the _{S 2.}

These requirements are such that a highly crystalline block and a highly amorphous block coexist in the main chain of the propylene polymer, and the highly crystalline block has a structure rich in isotacticity. Has to do with it. If the ratio of S ₁ to S is less than 20%, the crystallinity is too low, sufficient adhesiveness cannot be obtained, and problems such as stickiness tend to occur. On the other hand, if the ratio of S ₁ to S exceeds 60%, the crystallinity is too high and the solubility in a solvent is reduced, which is not preferable. Range of the ratio of _{S 1} with respect to S defined in the present invention is 60% or less than 20%, preferably 55% or more and 25% or less, more preferably 50% or less than 25%.

Further, the propylene polymer in the present invention needs to satisfy the relationship of 4 + 2S ₁ / S ₂ > 5. This relational expression is closely related to an index named Isotactic Block Index (BI) by Waymouth et al. (See Japanese Patent Application Laid-Open No. 9-510745). BI is an index indicating the stereoblock property of the polymer, and is defined as BI = 4 + 2 [mmmm] / [mmmr]. More specifically, BI represents the average chain length of isotactic blocks having 4 or more propylene units (JW Collete et al., Macromol., 22, 3858 (1989); JC Randall, J. Polym Sci. Polym. Phys. Ed., 14, 2083 (1976)). For a statistically perfect atactic polypropylene, BI = 5. Therefore, 4 + 2 [mmmm] / [mmmr]> 5 means that the average chain length of the isotactic block contained in the polymer is longer than that of the atactic polypropylene.

Although 4 + 2S ₁ / S ₂ , which is a requirement of the propylene-based polymer of the present invention, is not completely the same as the above-mentioned BI, but roughly corresponds, the requirement that 4 + 2S ₁ / S ₂ > 5 is satisfied by the present invention. Is different from atactic polypropylene in that it contains a crystallizable chain-length isotactic block. The presence of an isotactic block means that, in other words, a block consisting of a sequence having a stereospecificity disorder is also present in the main chain at the same time.

As described above, the propylene-based polymer of the present invention has a structure in which a crystalline block and an amorphous block coexist in its main chain, and the crystalline block has an isoform having a relatively long average chain length. It is a unique structure that is formed from a tactic block and has a structure rich in isotactic block properties. In the propylene polymer of the present invention, 4 + 2S ₁ / S ₂ > 5 may be sufficient, preferably 25> 4 + 2S ₁ / S ₂ > 6, more preferably 10> 4 + 2S ₁ / S ₂ > 7. is there.
When 4 + 2S ₁ / S ₂ > 5, it means that the average chain length of the isotactic block contained in the polymer is not excessively large. If the average chain length of the isotactic block is too large, the solubility of the polymer in a solvent is reduced, which is not preferable.

  The propylene-based polymer of the present invention is required to have a melting point [Tm] of 100 ° C. or less or a crystal heat of fusion of 5 J / g or more measured by a differential scanning calorimeter. The melting point is related to the uniform and random existence of the crystalline block structure and the amorphous block structure. Accordingly, a propylene polymer having a melting point [Tm] of 100 ° C. or less or a heat of crystal fusion of 5 J / g or more does not show a good solubility in a solvent of a propylene copolymer formed from the propylene polymer. It is easy to form a solution, and also to form an aqueous dispersion, it is easy to carry out mechanical emulsification and phase inversion emulsification from a solution or a melt. When [Tm] exceeds 100 ° C., the crystallinity is too high, which is not preferable in terms of solubility in a solvent.

The method for producing the propylene-based polymer of the present invention may be any method as long as a polymer satisfying the requirements of the present invention can be produced. For example, a method of polymerizing with a Ziegler-Natta catalyst; a method of polymerizing with a single-site catalyst or a Kaminsky catalyst; a method of epimerizing highly stereoregular isotactic polypropylene in the presence of hydrogen using a Pd / C catalyst, and the like. . As a preferred production method, a production method using a single-site catalyst can be exemplified. Reasons for this include the fact that single-site catalysts can generally control microtacticity through ligand design, can easily produce polymers with relatively low molecular weight, and in particular, have sharp molecular weight distribution and stereoregularity distribution. Is mentioned. If the molecular weight distribution or the stereoregularity distribution is irregular, there may be a difference in solubility, and there is a possibility that partially unnecessary ones may be produced.
Among the single-site catalysts, metallocene catalysts are preferably used because microtacticity can be precisely controlled.

As the single-site catalyst for producing a propylene-based polymer of the present invention, a metallocene catalyst containing a metallocene compound ([A] component) and a cocatalyst ([B] component) as essential components is preferably used.
As the metallocene compound (component (A)), a C ₁ -symmetric ansa-metallocene having a transition metal-containing crosslinking group is preferable. Non-crosslinked metallocenes can also be applied to the production of the propylene-based polymer of the present invention, but in general, since an answer-metallocene having a crosslinking group is more excellent in thermal stability and the like, it is particularly preferable from an industrial point of view. .

The answer metallocene having a transition metal-containing bridging group used in the present invention is a metallocene having a C ₁ -symmetry of a bridged Group 4 transition metal compound having a conjugated 5-membered ring ligand. Such transition metal compounds are known, and their use as catalyst components for α-olefin polymerization is also known.

一般式（１）において、Ｑは２つの共役５員環配位子を架橋する結合性基を、Ｍは周期表４族遷移金属を、ＸおよびＹは、それぞれ独立して、水素、ハロゲン、炭素原子数１〜２０の炭化水素基、炭素原子数１〜２０の酸素含有炭化水素基、炭素原子数１〜２０の窒素含有炭化水素基、炭素原子数１〜２０のリン含有炭化水素基または炭素原子数１〜２０のケイ素含有炭化水素基を、Ｒ^２およびＲ^３はそれぞれ独立して、炭素原子数１〜２０の炭化水素基、ハロゲン、炭素原子数１〜２０のハロゲン含有炭化水素基、アルコキシ基、アリールオキシ基、ケイ素含有炭化水素基、リン含有炭化水素基、窒素含有炭化水素基またはホウ素含有炭化水素基を示す。また、隣接する２個のＲ^２および／またはＲ^３がそれぞれ結合して４〜１０員環を形成していてもよい。ａ及びｂは、それぞれ独立して、０≦ａ≦４、０≦ｂ≦４を満足する整数である。 The metallocene compound of the component [A] is a compound represented by the following general formula (1) and having C ₁ -symmetry. Further, a plurality of metallocene compounds represented by the general formula may be used as a mixture.

In the general formula (1), Q is a bonding group bridging two conjugated 5-membered ring ligands, M is a transition metal of Group 4 of the periodic table, and X and Y are each independently hydrogen, halogen, A hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, ^{R 2} and ^{R 3} are each independently a hydrocarbon group having 1 to 20 carbon atoms, halogen, halogen-containing hydrocarbon group having 1 to 20 carbon atoms , An alkoxy group, an aryloxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group. Further, two adjacent R ² and / or R ³ may be bonded to each other to form a 4- to 10-membered ring. a and b are each independently an integer satisfying 0 ≦ a ≦ 4 and 0 ≦ b ≦ 4.

  Among the metallocene compounds represented by the general formula (1), dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium is most preferred, and dichloro [dimethyl] is more preferred. Germylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium and dichloro [dimethylsilylene (2-methyl-1-indenyl) (2,4-dimethyl-4H-1-azulenyl) Hafnium is also a suitable catalyst.

  As the metallocene compound, a mixture of a plurality of compounds having different structures may be used, or two or more kinds may be used in combination. Further, a known solid catalyst containing titanium trichloride as a main component or a carrier-supported catalyst containing magnesium, titanium, and halogen as essential components can be used as an auxiliary. Further, at the end of the first stage of polymerization or before the start of the second stage of polymerization, the component [A] may be newly added and used.

  In the present invention, the cocatalyst used as the component [B] includes, as essential components, (1) an organoaluminum oxy compound and (2) a reaction with the transition metal of the component [A] to convert the component [A] to a cation. Or at least one substance selected from the group consisting of (3) a Lewis acid, and (4) an ion-exchange layered compound or an inorganic silicate excluding silicate.

  In the production of the propylene-based polymer of the present invention, an organoaluminum compound may be used as the optional component [C] in addition to the cocatalyst [B] component. Specifically, it is a trialkyl aluminum, a halogen or alkoxy-containing alkyl aluminum, or a hydrogen-containing organic aluminum compound. Of these, particularly preferred are trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum. These optional components may be used in combination of two or more. Further, the optional component [C] may be newly added after the start of the polymerization.

The metallocene-based catalyst can be obtained by contacting the component [A], the component [B], and the optional component [C], but the contact method is not particularly limited. This contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization or polymerization of propylene.
At the time of contact of each component of the catalyst or after the contact, a solid of an inorganic oxide such as a propylene polymer, silica, or alumina may coexist or may be brought into contact.
The contact may be performed in an inert gas such as nitrogen, or may be performed in an inert hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, toluene, and xylene. It is preferable to use those solvents which have been subjected to an operation for removing poisonous substances such as water and sulfur compounds. The contact temperature is between −20 ° C. and the boiling point of the solvent used, and particularly preferably between room temperature and the boiling point of the solvent used.

  The amount of each catalyst component is not particularly limited, but when an ion-exchange layered compound other than silicate or an inorganic silicate is used as the component [B], the component [A] per 1 g of the component [B] Is 0.0001 to 10 mmol, preferably 0.001 to 5 mmol, and the component [C] is 0 to 10,000 mmol, preferably 0.01 to 100 mmol. Further, the atomic ratio between the transition metal in the component [A] and the aluminum in the component [C] is controlled to be 1: 0 to 1,000,000, preferably 1: 0.1 to 100,000. Is preferable in terms of polymerization activity and the like.

The catalyst thus obtained may be used after being washed with an inert hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, toluene, xylene, or may be used without washing. Good.
At the time of washing, a new component [C] may be used in combination as needed. It is preferable that the amount of the component [C] used at this time is 1: 0 to 10,000 in terms of the atomic ratio of the aluminum in the component [C] to the transition metal in the component [A].

A catalyst obtained by preliminarily polymerizing propylene and washing as necessary can be used as the catalyst. This prepolymerization may be carried out in an inert gas such as nitrogen, or in an inert hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, toluene and xylene.
The polymerization reaction of propylene is performed in the presence or absence of an inert hydrocarbon such as propane, n-butane, n-hexane, n-heptane, toluene, xylene, cyclohexane, and methylcyclohexane, or a liquid of liquefied propylene. Of these, the polymerization is preferably performed in the presence of the above-mentioned inert hydrocarbon.

  Specifically, a propylene polymer is produced in the presence of the components [A] and [B], or the components [A], [B] and [C]. The polymerization temperature, polymerization pressure, and polymerization time are not particularly limited, but usually, optimal settings can be made from the following ranges in consideration of productivity and process capability. That is, the polymerization temperature is usually 0 to 150 ° C, preferably 20 to 100 ° C, and the polymerization pressure is 0.1 to 100 MPa, preferably 0.3 to 10 MPa, more preferably 0.5 to 4 MPa, and the polymerization time. Is selected from the range of 0.1 to 10 hours, preferably 0.3 to 7 hours, more preferably 0.5 to 6 hours.

  In the present invention, as described above, the weight average molecular weight Mw of the propylene-based polymer is preferably in the range of 5,000 to 200,000. For this purpose, a conventionally known method can be used for adjusting the molecular weight of the polymer. That is, there are a method of controlling the molecular weight by controlling the polymerization temperature, a method of controlling the molecular weight by controlling the monomer concentration, and a method of controlling the molecular weight by using a chain transfer agent. When a chain transfer agent is used, hydrogen is preferred.

Further, in the present invention, the propylene-based polymer produced by controlling the stereoselectivity of the propylene unit chain composed of a head-to-tail (head to tail) bond is obtained by ¹³ C-NMR as described above. -Observing a peak derived from a carbon atom of a methyl group in a propylene unit chain portion comprising a tail bond, and setting a chemical shift of a peak attributable to a pentad represented by mmmm to 21.8 ppm, a value of 191.8 ppm; When the ratio (S ₁ / S) of the peak area S ₁ having the peak top at 21.8 ppm to the peak area S belonging to all the pentads appearing in the range of 2.8 ppm to 22.2 ppm (S ₁ / S) is 20% or more and 60% or less. There, and 21.5~21.7ppm is necessary to be _{4 + S 1 / S 2>} 5 when the area of the peak (mmmr) having a peak top was _{S 2} That.

  The method for controlling the stereoselectivity related to such properties of the propylene-based polymer is not particularly limited, but generally includes a method of controlling by controlling the structure of the catalyst and a method of controlling by controlling the polymerization conditions. . When controlling the stereoselectivity by controlling the polymerization conditions, the desired stereoregularity is obtained by controlling the polymerization temperature and the monomer concentration, and, in some cases, in combination with the above-described catalyst structure control. A propylene-based polymer can be obtained.

  The polymer main chain (A) of the propylene copolymer of the present invention is derived from a propylene-based polymer having the above-mentioned properties. However, the propylene-based polymer is different from a propylene homopolymer or an olefinic hydrocarbon. In the case of a polymer having no functional group (hereinafter also referred to as a non-functional propylene polymer) such as a copolymer of the above, the propylene polymer is derived from the modified propylene polymer with an acid or the like. Is a polymer having a functional group such as a copolymer of propylene and a monomer having a functional group (hereinafter, sometimes referred to as a functional propylene-based polymer), it can be directly induced without modification. .

  The modified propylene polymer used in the present invention has the above-mentioned specific properties (1) and (2), and is obtained by grafting, for example, a radical polymerizable unsaturated compound having a reactive group to a non-functional propylene polymer. It is a modified polymer which can be obtained by copolymerization and has a reactive group introduced into a propylene-based polymer. Examples of the reactive group to be introduced include a carboxylic acid group, an acid group of a dicarboxylic anhydride group, a hydroxyl group, an amino group, an epoxy group, and an isocyanate group, and a carboxylic acid group or a dicarboxylic anhydride group is preferable. .

  As the radical polymerizable unsaturated compound having a reactive group, specifically, as a compound having a carboxylic acid group or a dicarboxylic anhydride group, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itacone Acids, itaconic anhydride, crotonic acid, crotonic anhydride, citraconic acid, citraconic anhydride and the like having a hydroxyl group include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Examples of those having an amino group include (meth) acrylamide and (dimethylamino) ethyl (meth) acrylate, those having an epoxy group include glycidyl (meth) acrylate, and those having an isocyanate group include ( (Meth) acrylic acid (2-isocyanato) ethyl and the like. Among them, maleic anhydride is preferred.

  As a method for graft-copolymerizing a non-functional propylene-based polymer with a radically polymerizable unsaturated compound containing a carboxylic acid group, various known methods can be used. For example, a non-functional propylene polymer is dissolved in an organic solvent, a polymerizable unsaturated compound to be graft-copolymerized (hereinafter, also referred to as a graft copolymer component) and a radical polymerization initiator are added, and the mixture is heated and stirred. A non-functional propylene-based polymer by heating and dissolving, adding a polymerizable unsaturated compound to be graft-copolymerized to the melt and a radical polymerization initiator, and stirring the mixture to stir the graft. A method of copolymerizing; or a method of supplying each component of a non-functional propylene polymer, a polymerizable unsaturated compound and a radical initiator to an extruder and graft-copolymerizing while heating and kneading; a non-functional propylene polymer Powder is impregnated with a solution of the polymerizable unsaturated compound to be graft-copolymerized and the radical polymerization initiator dissolved in an organic solvent. After heated to a temperature that does not dissolve the powder may be mentioned a method of graft copolymerization.

  The graft ratio of the graft copolymerization component with the carboxyl group-containing radically polymerizable unsaturated compound in the modified propylene-based polymer, that is, the content in the modified propylene-based polymer is preferably 0.01 to 5% by weight. Preferably it is 0.1 to 3% by weight. When the content is less than 0.01% by weight, the adhesion of the polypropylene copolymer derived from the modified propylene-based polymer to a primer such as a top-coat paint deteriorates. Gets worse.

The usage ratio of the radical polymerization initiator / graft copolymerization component at the time of modification is usually in the range of 1/100 to 2/1, preferably 1/20 to 1/1 in molar ratio.
The reaction temperature is preferably 50 ° C. or higher, particularly 80 to 200 ° C., and the reaction time is about 2 to 10 hours.

  The radical polymerization initiator used for the graft copolymerization can be appropriately selected from ordinary radical initiators and used, and examples thereof include organic peroxides and azonitrile. Examples of the organic peroxide include diisopropyl peroxide, di (t-butyl) peroxide, t-butyl hydroperoxide, benzoyl peroxide, dicumyl peroxide, cumyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide. , Methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, t-butyl peroxyisopropyl monocarbonate, diisopropyl peroxycarbonate, dicyclohexyl peroxycarbonate and the like. Examples of azonitrile include azobisbutyronitrile and azobisisopropylnitrile. Among them, t-butyl peroxyisopropyl monocarbonate, benzoyl peroxide and dicumyl peroxide are preferred.

  When the modification by the graft copolymerization is performed using an organic solvent, specific examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; n-hexane, n-heptane, and n-octane. , N-decane and other aliphatic hydrocarbons; trichloroethylene, perchlorethylene, chlorobenzene, halogenated hydrocarbons such as o-dichlorobenzene, and the like. Among these, aromatic hydrocarbons and halogenated hydrocarbons are preferred. Preferred are toluene, xylene and chlorobenzene.

  The acid-modified propylene-based polymer of the present invention has a weight average molecular weight Mw of 5,000 to 200,000 as measured by GPC. Preferably, it is between 10,000 and 180,000, more preferably between 20,000 and 150,000.

  The polypropylene copolymer of the present invention contains a polymer main chain (A) derived from a propylene-based polymer having the above properties (1) and (2), and a polymer chain (B) different from the main chain. It is a polypropylene copolymer having side chains at a specific ratio.

  The polymer main chain (A) is derived from a modified polymer of a non-functional propylene polymer or a functional propylene polymer, but is preferably modified with an acid having a carboxylic acid group or a dicarboxylic anhydride group. The polymer chain (B) derived from an acid-modified propylene polymer and having a side chain is preferably a polymer chain in which a repeating unit is formed by an addition reaction, an ester bond, or an ether bond. Here, the polymer chain in which the repeating unit is formed by an addition reaction, an ester bond, or an ether bond means a (meth) acrylic polymer chain, a polyester polymer chain, or a polyether polymer chain, The (meth) acrylic polymer chain is specifically a polymer chain formed by radical polymerization of (meth) acrylic acid and / or a derivative thereof.

  A preferred polypropylene copolymer of the present invention comprises a polymer main chain (A) composed of an acid-modified propylene polymer modified with an acid having a carboxylic acid group or a dicarboxylic anhydride group, and the carboxylic acid group or the dicarboxylic anhydride. Having a side chain containing a polymer chain (B) formed by a covalent bond or an ionic bond between a substance group and a reactive group, and a repeating unit formed by an addition reaction, an ester bond, or an ether bond. It is a copolymer.

A polymer (A) comprising a propylene polymer having a functional group, particularly an acid-modified propylene polymer modified with an acid having a carboxylic acid group or a dicarboxylic anhydride group, a poly (meth) acrylic polymer Examples of a method for connecting the side chain containing the chain (B) via a bond with a group capable of reacting with the carboxylic acid group or dicarboxylic anhydride group include the following methods (1) and (2). The bond may be formed by any method.
(1) A compound (C1) having a radical polymerizable unsaturated bond and a group capable of reacting with a carboxylic acid group or a dicarboxylic anhydride group of the acid-modified propylene polymer in the molecule, to the acid-modified propylene polymer. After binding, a method of graft copolymerizing a radically polymerizable unsaturated compound (C2) containing at least (meth) acrylic acid and / or a derivative thereof (eg, an ester).
(2) a compound (C1) having a group capable of reacting with a carboxylic acid group or a dicarboxylic anhydride group of an acid-modified polypropylene polymer and a radically polymerizable unsaturated bond in a molecule, and at least (meth) acrylic acid and / or Or a method of copolymerizing a radically polymerizable unsaturated compound (C2) containing a derivative thereof (for example, an ester) and reacting the resulting copolymer with an acid-modified propylene-based polymer.

Examples of the group capable of reacting with the carboxylic acid group or dicarboxylic anhydride group of the acid-modified propylene polymer of the compound (C1) having a radical polymerizable unsaturated bond include an amino group, a hydroxyl group, an epoxy group or an isocyanate group. Can be
The reaction between these groups and a carboxylic acid group or a dicarboxylic anhydride group includes an esterification reaction between a carboxylic acid and a hydroxy group, a ring opening reaction between a carboxylic acid and an epoxy group, and a primary or secondary amino group with a carboxylic acid. Amidation reaction of a carboxylic acid with a tertiary amino group, a urethane reaction of a carboxylic acid with an isocyanate group, and the like.
When the acid-modified propylene-based polymer is a polymer modified with a dicarboxylic anhydride, the acid-modified polymer may be used after being opened with water or esterified with an alcohol.

Examples of the compound (C1) having a group capable of reacting with a carboxylic acid group or a dicarboxylic anhydride group of an acid-modified propylene polymer and a radically polymerizable unsaturated bond in a molecule include the following.
Examples of the radical polymerizable unsaturated compound having a hydroxyl group include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. (Meth) acrylamide N-methylol; (meth) acrylic acid 2-hydroxyethyl-6-hexanolide addition polymer; alkenyl alcohol such as 2-propen-1-ol; alkynyl alcohol such as 2-propyn-1-ol; Hydroxy vinyl ether and the like.

  Examples of the radical polymerizable unsaturated compound having an epoxy group include unsaturated carboxylic acids such as glycidyl (meth) acrylate, mono and diglycidyl esters of maleic acid, mono and diglycidyl esters of itaconic acid, and mono and diglycidyl esters of allyl succinic acid. Acid glycidyl ester; glycidyl ester of p-styrene carboxylic acid; glycidyl ether such as allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether; p-glycidyl styrene; 3,4-epoxy-1-butene; Epoxy olefins such as 3,4-epoxy-3-methyl 1-butene; and vinylcyclohexene monoxide.

Examples of the radical polymerizable unsaturated compound having an isocyanate group include 2-isocyanatoethyl (meth) acrylate, methacryloyl isocyanate, and the like.
Examples of the radical polymerizable unsaturated compound having a primary or secondary amino group include (meth) acrylamide and the like.
Examples of the radical polymerizable unsaturated compound having a tertiary amino group include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.

  Further, the functional propylene polymer and the modified propylene polymer, which are the propylene polymers derived from the polymer main chain (A) of the present invention, contain the (meth) acrylic polymer chain (B) In binding the chains, an initiator or a chain transfer agent having a reactive group capable of binding to the functional group of these propylene-based polymers can be used instead of the compound (C1). Examples of the reactive group that can be bonded include a hydroxyl group, a glycidyl group, a carboxylic acid group, and an amino group. Specific examples of the initiator include 2,2′-azobis (2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl]) propionamide and 2,2′-azobis (2- Methyl-N- [2- (hydroxyethyl)]) propionamide and the like. Specific examples of the chain transfer agent include 2-mercaptoethanol and the like. The side chain containing the (meth) acrylic polymer chain (B) is formed by introducing these initiators or chain transfer agents into the propylene polymer and then grafting the radical polymerizable compound (C2) described below. It is possible to polymerize, but by using these initiators and chain transfer agents, the (meth) acrylic monomer mentioned as the radical polymerizable compound (C2) is polymerized to form a (meth) acrylic polymer chain (B). After incorporation, it can be linked to the main chain (A) of the propylene-based polymer.

The radical polymerizable compound (C2) can be copolymerized with a compound (C1) having a group capable of reacting with a carboxylic acid group or a dicarboxylic anhydride group of an acid-modified propylene-based polymer and a radical polymerizable unsaturated bond in a molecule. It is a radical polymerizable compound, and preferably contains at least one kind of (meth) acrylic acid and / or a derivative thereof.
Specific examples of the radical polymerizable compound (C2) include (meth) acrylic acid as (meth) acrylic acid or derivatives (esters) thereof, and (meth) acrylic acid esters having an alkyl group having 1 to 12 carbon atoms. Monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) ) T-butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl hexyl (meth) acrylate, (meth) acrylic acid Nonyl and decyl (meth) acrylate dodecyl (meth) acrylate are exemplified.

  Further, a monomer of a (meth) acrylate having an aryl group or an arylalkyl group having 1 to 12 carbon atoms, for example, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, etc .; A monomer of an (meth) acrylate ester having an alkyl group having 1 to 20 carbon atoms containing atoms, for example, hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, glycidyl (meth) acrylate, ethylene oxide (meth) acrylate adduct Etc .; having an alkyl group having 1 to 20 carbon atoms containing a fluorine atom (Meth) acrylic ester monomers such as trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, and the like; (meth) acrylamide System monomers such as (meth) acrylamide, (meth) acryldimethylamide and the like can also be mentioned.

  Other radically polymerizable compounds (C2) that can be used in combination with (meth) acrylic acid and derivatives thereof include monoolefin dicarboxylic acids and acid anhydrides thereof and monoalkyl esters of monoolefin dicarboxylic acids such as maleic acid, Examples thereof include chloromaleic acid, citraconic acid, itaconic acid, glutaconic acid and acid anhydrides thereof, and these acids and lower alkyl monoesters such as methyl and ethyl. Other examples include urethane-modified polyvalent acrylates having a (meth) acryloyl group in one molecule, vinyl acetate, ethyl vinyl ether, butyl vinyl ether, hexyl vinyl ethers, and the like.

  In the above method (1), wherein the side chain containing the (meth) acrylic polymer chain (B) is linked to the main chain of the acid-modified propylene-based polymer, the radical-polymerizable unsaturated bond is added to the acid-modified propylene-based polymer. In the reaction of bonding a radical polymerizable unsaturated compound (C2) containing at least (meth) acrylic acid and / or a derivative thereof after bonding the compound (C1) having In order to prevent the formation of the (C1) or (C2) homopolymer, the reaction is preferably carried out in an atmosphere of oxygen or air, and an appropriate amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, or phenothiazine is preferably added to the reaction system.

  Reaction for bonding the compound (C1) having a radical polymerizable unsaturated bond in the method (1) to the main chain of the acid-modified propylene polymer, or the compound (C1) having a radical polymerizable unsaturated bond in the method (2) The reaction temperature at the time of reacting the resulting copolymer with the radical polymerizable unsaturated compound (C2) containing (meth) acrylic acid and / or a derivative thereof is usually 20 to 180 ° C, preferably 50 to 150 ° C. It is. At this time, as a catalyst for accelerating the reaction, an acid or basic compound such as sulfuric acid, p-toluenesulfonic acid, zinc chloride, pyridine, triethylamine, dimethylbenzylamine, tetramethylammonium bromide, 1,8 -Diazabicyclo [5.4.0] -7-undecene (DBU), 4-dimethylaminopyridine (DMAP) and the like, and dibutyl silver dilaurate and the like in the urethanization reaction.

  Reactable groups of the above compound (C1) having a radical polymerizable unsaturated bond or a formed copolymer of the compound (C1) and the radical polymerizable unsaturated compound (C2), that is, an amino group, a hydroxyl group, an epoxy group Alternatively, the molar ratio of the carboxylic acid group of the acid-modified propylene polymer to the isocyanate group is in the range of 5/1 to 1/5, preferably in the range of 2/1 to 1/2.

  In the above methods (1) and (2), the radically polymerizable unsaturated compound (C2) is replaced with a compound (C1) having a radical polymerizable unsaturated bond and a group capable of reacting with a carboxylic acid group or a dicarboxylic anhydride group. As a method of copolymerizing or a method of graft-polymerizing the (C2) to the modified propylene-based polymer to which (C1) is bonded, the above-mentioned radically polymerizable unsaturated compound containing a carboxylic acid group is converted to a propylene-based polymer. A graft copolymerization, that is, a known method similar to a method of forming an acid-modified propylene-based polymer by radical polymerization may be used.

The radical polymerization initiator used in the methods (1) and (2) and the reaction conditions such as the reaction temperature and the reaction time are also used to graft copolymerize the radically polymerizable unsaturated compound containing a carboxyl group to a propylene-based polymer. The method described in the method can be appropriately adopted. In this case, the molar ratio of the radical polymerization initiator / [radical polymerizable unsaturated compound (C1) + (C2)] is usually 1/500 to 1/10, preferably 1/200 to 1/20. Range.
Further, a chain transfer agent such as alcohol may be used to prevent gelation during copolymerization.

  In the above methods (1) and (2), when the graft copolymerization reaction or the like is performed using an organic solvent, specific examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; Aliphatic hydrocarbons such as -hexane and n-heptane; alicyclic aliphatic hydrocarbons such as cyclohexane and methylcyclohexane; halogenated hydrocarbons such as perchlorethylene, chlorobenzene and o-dichlorobenzene; methyl acetate; Carboxylic acid esters such as ethyl acetate; alcohols such as ethanol and isopropanol, and the like, and can be used alone or as a mixed solvent.

  In the present invention, the polypropylene copolymer obtained by the above method has a polymer main chain (A) composed of an acid-modified propylene polymer and a side chain containing at least a (meth) acrylic polymer chain (B). It is. Here, at least the (meth) acrylic polymer chain (B) is attached to a side chain bonded via a reactive group such as a carboxylic acid group in the polymer main chain (A) composed of an acid-modified polypropylene polymer. They are connected. The ratio (A) / (B) of the side chain containing the polymer main chain (A) composed of the acid-modified polypropylene polymer and the (meth) acrylic polymer chain (B) in the polypropylene copolymer is expressed by weight. It is in the range of 20/1 to 1/20, preferably 10/1 to 1/10, more preferably 4/1 to 1/4, and particularly preferably 3/1 to 1/3.

  Here, the weight of the (meth) acrylic polymer chain (B) indicates the weight occupied by the (meth) acrylic monomer (C2) in the (meth) acrylic polymer chain. When the weight ratio of (A) / (B) exceeds the range of 20/1 to 1/20 and the content of (A) is too large and the content of (B) is small, the compatibility with the polar resin is low and the resin is separated. If the amount of (A) is too small and the amount of (B) is too large, the adhesion to the crystalline polypropylene resin becomes poor, which is not preferable. The polar resin used here is used for general-purpose paints, primers, inks, etc., and includes poly (meth) acrylate resin, polyester resin, polyether resin, polycarbonate resin, polyurethane resin, melamine resin, alkyd resin, and the like. is there.

  When the polypropylene copolymer of the present invention is used for a non-tack property such as direct coating or interior use, a (meth) acrylic polymer chain (B), for example, a compound having a radical polymerizable unsaturated bond ( The Tg of the resulting copolymer of C1) and the radical polymerizable unsaturated compound (C2) containing (meth) acrylic acid and / or a derivative thereof is preferably in the range of 30 to 100C, more preferably 50 to 90C. If the Tg exceeds 100 ° C., the hardness may increase and cracks may occur. If the Tg is less than 30 ° C., stickiness increases. When the adhesion is more important than the non-tack property such as a primer application, the Tg is preferably in the range of -50C to 30C, more preferably -20C to 10C. If the temperature exceeds 30 ° C., the adhesiveness may decrease. If the temperature is less than −50 ° C., the cohesive force may decrease and the adhesiveness may decrease.

  The polypropylene copolymer having a polymer main chain (A) composed of a modified propylene polymer and a side chain containing a polymer chain (B) in which a repeating unit is formed by an ester bond in the present invention is a polyester-based polymer. It is a polypropylene copolymer having a side chain including a chain. The polypropylene copolymer having a polyester-based polymer chain in the side chain refers to a polymer in which a propylene-based polymer having a reactive group and a polyester or polyester polyol are bonded, and is preferably an acid having a carboxylic acid group or the like. It is a polypropylene copolymer obtained by dehydrating and condensing a modified propylene-based polymer with a polyester polyol to introduce a polyester side chain.

The polyester or polyester polyol used in the present invention can be obtained by subjecting the following polyhydric alcohol and polybasic acid to condensation polymerization by a known method, or by ring-opening polymerization of an aliphatic lactone.
Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 1,2-, 1,3-, 1,4-, and 2,3-butanediol. , 1,5-pentanediol, 3-methyl-1.5-pentanediol, 1,6-hexanediol, and one or more aliphatic polyhydric alcohols can be used in combination.

Examples of polybasic acids include maleic acid, fumaric acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and methyltetrahydrophthalic acid. And combining one or more polybasic acids such as aliphatic or aromatic dicarboxylic acids such as acid anhydrides thereof, or aromatic polycarboxylic acids such as trimellitic acid, pyromellitic acid and these acid anhydrides. Can be done.
Examples of the aliphatic lactone include one or more saturated fats such as γ-caprolactone, δ-caprolactone, ε-caprolactone, γ-valerolactone, δ-valerolactone, ε-valerolactone, and β-methyl-δ-valerolactone. Group lactones can be used in combination.

The polyester polyol preferably has a hydroxyl value of 30 to 250 KOH mg / g. 250 KOHmg / g or more is not preferred because the water resistance of the obtained polymer is reduced.
A polyester polyol having an average molecular weight of 300 to 100,000 can be used. The ratio (A) / (B) of the polymer main chain (A) composed of the acid-modified propylene polymer and the side chain containing the polyester polymer chain (B) is 20/1 to 1/20 by weight. , Preferably 10/1 to 1/10, more preferably 4/1 to 1/4, and particularly preferably 3/1 to 1/3.
When the weight ratio of (A) / (B) exceeds the range of 20/1 to 1/20 and the content of (A) is too large and the content of (B) is small, the compatibility with the polar resin is low and the resin is separated. If the amount of (A) is too small and the amount of (B) is too large, the adhesion to the crystalline polypropylene resin becomes poor, which is not preferable.

The polyester polyol can be introduced by esterification or transesterification with a carboxyl group or a dicarboxylic anhydride group of the acid-modified propylene polymer. The method of introducing the compound may be either a method of reacting by heating and melting to a temperature equal to or higher than the melting point (melting method) or a method of dissolving and reacting in an organic solvent such as toluene or xylene (solution method). The solution method is preferred in view of the fact that it can be performed.
When using a melting method, it is possible to use a device such as a Banbury mixer, a kneader, or an extruder. The reaction is usually carried out at a temperature higher than the melting point of the polymer, and the reaction time is suitably from 10 minutes to 3 hours.
The reaction temperature when the solution method is used is in the range of 20 ° C to 160 ° C, and the reaction time is appropriately 1 to 5 hours. As the solvent, the same solvent as used when binding the (meth) acrylate polymer chain can be used.

  As a catalyst for accelerating the esterification reaction, a compound (C1) or a compound having a radical polymerizable unsaturated bond and a group capable of reacting with a carboxyl group or a dicarboxylic anhydride group of an acid-modified polypropylene polymer in a molecule. The catalyst compounds listed as catalysts that can be used when the acrylate polymer chain (B) is bonded to the main chain of the acid-modified polypropylene polymer can be used in the same manner.

  Examples of the polypropylene copolymer having a polymer main chain (A) derived from the modified propylene polymer in the present invention and a side chain including a polymer chain (B) in which a repeating unit is formed by an ether bond include: It is a polypropylene copolymer having a side chain containing a polyether-based polymer chain. The polypropylene copolymer containing a polyether-based polymer chain in the side chain refers to a polymer in which a modified propylene-based polymer having a reactive group is bonded to a polyether polyol, and preferably a carboxylic acid group or the like. Is a polypropylene copolymer in which a polyether side chain is introduced by dehydration-condensation of an acid-modified propylene-based polymer having the formula (1) and polyetherpolyol.

The polyether polyol used in the present invention can be obtained, for example, by subjecting the following cyclic alkylene oxide to ring-opening polymerization by a known method.
Examples of the cyclic alkylene oxide include ethylene oxide, propylene oxide, trimethylene oxide, and tetrahydrofuran.
Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol obtained by ring-opening polymerization of the above-mentioned cyclic alkylene oxide. The polyether polyol preferably has a hydroxyl value of 30 to 250 KOHmg / g. 250 KOHmg / g or more is not preferred because the water resistance of the obtained polymer is reduced.
The polyether polyol having an average molecular weight of 300 to 100,000 can be used.

The ratio (A) / (B) of the polymer main chain (A) composed of the acid-modified polypropylene-based polymer and the side chain containing the polyether-based polymer chain (B) is 20/1 to 1 / weight ratio. 20, preferably 10/1 to 1/10, more preferably 4/1 to 1/4, and particularly preferably 3/1 to 1/3. When the weight ratio of (A) / (B) exceeds the range of 20/1 to 1/20 and the content of (A) is too large and the content of (B) is small, the compatibility with the polar resin is low and the resin is separated. If the amount of (A) is too small and the amount of (B) is too large, the adhesion to the crystalline polypropylene resin becomes poor, which is not preferable.
As a method for introducing the polyether polyol into the main chain of the acid-modified polypropylene polymer, the same reaction method, reaction conditions, and reaction catalyst as those for the above-described method for introducing the polyester polyol can be appropriately used.

  In the case of a propylene polymer having a functional group other than the acid-modified propylene polymer, a compound having a group capable of reacting with the functional group and a radical polymerizable unsaturated bond in a molecule according to the type of the functional group The polymer side chain (B) can be linked to the main chain by performing the same reaction using (C1).

The polypropylene copolymer of the present invention has excellent compatibility with polar resins and extremely good solubility in various solvents, and has the following properties (a) to (c).
(A) When dissolved in toluene at 25 ° C. with an acrylic resin at a weight ratio of 50/50 and a solid concentration of 12% by weight, the transmittance (650 nm) is 80% or more. (B) Toluene at 25 ° C. When dissolved at a concentration of 10% by weight, the insoluble content is 1% by weight or less based on the total polymer. (C) Adhesion to a polypropylene substrate by a test for adhesion (cross-cut tape method) is 50 / 100 or more

The polypropylene copolymer of the present invention has excellent compatibility with polar resins such as acrylic resins, and its characteristics are as follows: (a) toluene at 25 ° C., 50/50 weight ratio with acrylic resin, solid content concentration 12 wt. %, The transmittance (650 nm) is 80% or more. It is preferably at least 85%, more preferably at least 90%.
Here, "Hitaloid 3904" manufactured by Hitachi Chemical Co., Ltd. was used as the acrylic resin, but a resin having a viscosity equivalent to that of "Hitaloid 3904" can be used as the acrylic resin. That is, the viscosity of the resin is in the range of 3000 to 4000 mPa · s, preferably 3200 to 3600 mPa · s, and more preferably 3300 to 3500 mPa · s (concentration solids 50 wt%, xylene 40 wt%, butyl acetate 10 wt%, temperature 25 ° C.). And a solubility parameter of 10.1 to 10.5 (cal / cm ³ ) ^1/2 , preferably 10.2 to 10.4 cal / cm ³ ) ^1/2 (Fedors; Polym. Eng. Sci., 14 ( 2), 147 (1974))).
As a method for measuring the compatibility, a method is used in which a solution prepared by adjusting the concentration of the copolymer of the present invention and the polar resin to the above-mentioned concentration is placed in a quartz cell having a width of 10 mm, and the transmittance is measured using light of a predetermined wavelength.

Further, the solubility of the polypropylene copolymer of the present invention is much superior to that of a modified highly stereoregular isotactic polypropylene, and the solubility is (b) 10% by weight in toluene at 25 ° C. , The insoluble content is 1% by weight or less based on the whole polymer. Preferably, it is 0.1% by weight or less, and more preferably, there is no insoluble component.
As a method for measuring the solubility, for example, a solution dissolved at a predetermined temperature and a predetermined concentration is filtered near that temperature (or hot filtration if the temperature is high), and the filter paper or SUS wire mesh used at that time (11406 weight in advance) is used. Is measured) and the weight of the insoluble matter is measured.

Furthermore, the propylene copolymer of the present invention has excellent adhesion to a polypropylene molded article, and the adhesion is (c) an adhesion test to a polypropylene substrate (cross-cut tape method) of 50. / 100 or more. Preferably it is 80/100 or more, more preferably 100/100.
The adhesion of the propylene copolymer in the present invention is determined by the following adhesion test method.

Adhesion test method (A) The adhesion test is performed according to the cross-cut tape method described in JIS K5400 8.5.2.
(1) Summary The cuts that penetrate the coating film of the test piece and reach the bare ground are cut in a grid pattern, an adhesive tape is peeled off the grid, and the adhesion of the coated film after peeling is visually observed. Observe.
(2) Apparatus and materials (a) Cutter knife According to JIS K5400 7.2 (2) (e).
(B) Cutter guide According to JIS K5400 8.5.1 (2) (b).
(C) Cellophane adhesive tape Cellophane adhesive tape specified in JIS Z1522, having a width of 18 mm or 24 mm and an adhesive strength of 2.94 N / 10 mm or more. (D) Test plate Polypropylene molded body (150 mm x 70 mm x 3 mm) (e) ) Eraser specified in JIS S6050

(3) Preparation of test piece A sample is applied on one side of the test piece according to JIS K5400 3.3 in accordance with the method specified in the product standard of the sample, dried, and left for 24 hours in the standard condition.
(4) Operation JIS K5400 8.5.2. Obey (4)
(5) Evaluation The evaluation is as follows.
(A) Observe the state of the grid-like scratches applied to the painted surface of the test piece, and count the number of grids that were not peeled out of the 100 grids and expressed as “number of remaining grids / 100”. And make it adhesive.

  As the polypropylene substrate used in the adhesion test of the present invention, crystalline polypropylene is used. Examples of the crystalline polypropylene include a propylene homopolymer and / or a propylene / ethylene block copolymer composed of a propylene homopolymer portion and a propylene / ethylene copolymer portion. Among them, it is preferable to use a propylene homopolymer having an MFR (230 ° C., 21.18 N load) of 5 to 30 (g / 10 minutes).

  The polypropylene copolymer of the present invention has excellent compatibility with polar resins such as acrylic resins as described above, and also has good solubility in solvents, so that it can be dissolved in various solvents. Specific examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, and n-decane; cyclohexane, methyl Cyclohexane, ethylcyclohexane, dimethylcyclohexane, alicyclic aliphatic hydrocarbons such as decalin, methylene chloride, carbon tetrachloride, halogenated hydrocarbons such as trichloroethylene, perchlorethylene, chlorobenzene, o-dichlorobenzene, n-ethyl Acetates, esters such as n-butyl acetate, methyl isobutyl ketone, ketones such as cyclohexanone, polar solvents such as tetrahydrofuran, dimethyl sulfoxide and the like, among these, aromatic hydrocarbons or alicyclic hydrocarbons. Preferred, especially toluene, xylene, methyl Rohekisan, ethylcyclohexane are preferred.

  Since the polypropylene copolymer of the present invention is soluble in various solvents as described above, a coating composition obtained by dissolving the polypropylene copolymer in a solvent is a molded product of a crystalline olefin polymer (substrate). ) To form a coating film, and the coating film has excellent adhesion to a substrate and can be used as an adhesive. Examples of the olefin polymer as the base material include olefin polymers such as high-pressure polyethylene, medium-low pressure polyethylene, polypropylene, poly-4-methyl-1-pentene, poly-1-butene, and polystyrene; Examples thereof include olefin copolymers such as polymers, ethylene / butene copolymers, and propylene / butene copolymers. Of these olefin copolymers, propylene polymers are preferably used. In addition, molded products made of polypropylene and synthetic rubber, polyamide resin, unsaturated polyester resin, polybutylene terephthalate resin, molded products made of polycarbonate resin, etc., for example, molded products such as bumpers for automobiles, and further for steel plate and electrodeposition treatment It can also be used for surface treatment of steel sheets and the like. Furthermore, paints, primers, adhesives mainly composed of polyurethane resin, fatty acid modified polyester resin, oil-free polyester resin, melamine resin, epoxy resin, polycarbonate resin, polyamide resin, phenol resin, alkyd resin, polyether resin, acrylic resin, etc. It can be used to form a coating film having excellent clarity, low-temperature impact resistance, etc., while improving the adhesion of paints and the like to the surface to which the agent or the like has been applied.

  In addition, unmodified polypropylene resin, polymers of conjugated diene monomers such as butadiene and isoprene and hydrogenated products thereof, chlorinated polyethylene, chlorinated polypropylene, chlorinated polyolefins such as chlorinated polyethylene propylene, chlorosulfonated polyolefins, ethylene. A vinyl acetate copolymer or a chlorinated or chlorosulfonated product thereof can be blended with the resin of the present invention, if necessary, and used.

  Further, in preparing the coating composition containing the polypropylene copolymer of the present invention, the polymer main chain (A) or the polymer chain (B) derived from the propylene-based polymer may have a hydroxy group, an epoxy group, When there are reactive groups such as a group, a carboxylic acid group, and an isocyanate group, a hydroxy group, an epoxy group, an amino group, a carboxylic acid group, and an isocyanate group-containing compound that undergo a crosslinking reaction with these reactive groups are formed into a coating film By using it sometimes, the coating film performance can be improved.

  The polypropylene copolymer of the present invention can also be used as an aqueous dispersion. The aqueous dispersion of the present invention contains a polypropylene copolymer and a surfactant in an aqueous medium, and further contains various additives added as necessary.

  As the surfactant, any of a nonionic surfactant, an anionic surfactant, a cationic surfactant and an amphoteric surfactant can be used, but a nonionic surfactant is preferable. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and polyoxyethylene polyoxypropylene block. Examples include polymers, sorbitan fatty acid esters, polyoxyalkylene alkyl ethers, glycerin fatty acid esters, polyoxyethylene alkylamines, and alkyl alkanolamides. Examples of the anionic surfactant include fatty acid salts, alkyl sulfate salts, polyoxyethylene alkyl ether sulfate salts, sodium alkyl benzene sulfonate, sodium alkyl naphthalene sulfonate, alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, and alkyl. Phosphate, naphthalenesulfonic acid formalin condensate, and the like are included. These surfactants can be used alone or in combination of two or more. The surfactant is used usually in an amount of 1 to 100 parts by weight, preferably 3 to 50 parts by weight, based on 100 parts by weight of the polypropylene copolymer.

  The aqueous dispersion of the present invention preferably contains a basic substance in order to enhance the dispersion stability of the polypropylene copolymer. Examples of the basic substance include inorganic basic substances such as sodium hydroxide, potassium hydroxide, and sodium carbonate, ammonia and methylamine, dimethylamine, trimethylamine, ethanolamine, diethanolamine, triethanolamine, 2-ethyl-2-aminopropanol. And the like, among which amines are preferable. The basic substance is used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the polypropylene copolymer.

  When the aqueous dispersion of the polypropylene copolymer of the present invention is used for a primer or paint, a hydrophilic organic material other than water is used for the purpose of increasing the drying speed or obtaining a surface having a good finished feeling. Solvents can be blended. Examples of hydrophilic organic solvents include alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and propylene glycol and ethers thereof. No.

  The aqueous dispersion of the present invention may further contain, if necessary, other aqueous resins such as an aqueous acrylic resin, an aqueous urethane resin, an aqueous epoxy resin, an aqueous alkyd resin, an aqueous phenol resin, an aqueous amino resin, an aqueous polybutadiene resin, and an aqueous silicon resin. Can be used in combination.

Since the coating film formed when the coating composition or the aqueous dispersion of the present invention is applied shows good adhesion to the olefin polymer as the base material, the polypropylene copolymer of the present invention is It can be used as an adhesive resin for the olefin polymer. In order to obtain good adhesion to the base material of the olefin polymer, it is preferable to heat after the application. The heating temperature is not particularly limited, but is preferably 50 to 150 ° C., more preferably 60 to 130 ° C. in consideration of practicality. The method for applying the coating composition is not particularly limited, and a conventionally known method such as a method of applying with a spray, a method of applying with a roller, and a method of applying with a brush can be used.
As a method for applying the aqueous dispersion of the present invention to the surface of the molded article (substrate), spray coating is suitable, for example, spraying the surface of the molded article with a spray gun. The coating on the molded article may be performed at room temperature. After the coating, the coating can be dried by an appropriate method such as natural drying or forced drying by heating to form a coating film.

The coating composition can be applied to the surface of the molded article formed by applying the coating composition or the aqueous dispersion of the present invention and forming a coating film by electrostatic coating, spray coating, brush coating, or the like.
The coating material may be a single-layer coating film or a multi-layer coating film by applying multiple layers. After applying the paint, the coating is cured according to a usual method of heating with a nichrome wire, infrared rays, high frequency, or the like, and a molded article having a desired coating on the surface can be obtained. The method for curing the coating film is appropriately selected depending on the material and shape of the molded product, the properties of the paint used, and the like.

  The coating composition or the aqueous dispersion of the present invention is applied to the surface of a molded article comprising an α-olefin copolymer or another polymer as a main component, and the paint adherence to the surface, water resistance, and gasoline resistance It can be used as a primer or the like for improving the coating properties such as properties. In addition, it can be applied to a wide range of applications in addition to the above-mentioned use as a primer of molded articles, taking advantage of its characteristics of excellent adhesiveness, peel strength and water resistance. The present invention can also be applied to uses such as an agent and a compatibilizer between a polyolefin and a polar resin.

The coating composition or the aqueous dispersion of the present invention may further contain various stabilizers such as antioxidants, weather stabilizers, and heat inhibitors as required in addition to the above; coloring agents such as titanium oxide and organic pigments; carbon black; Various additives such as a conductivity-imparting agent such as ferrite, a preservative, a fungicide, and a rust preventive may be compounded and used. Further, in the aqueous dispersion, a thickener and an antifoaming agent may be added, and a small amount of an organic solvent may be added as needed in order to improve wettability with a substrate to be coated.
The molded article to which the composition of the present invention is applied is obtained by molding the above various polymers or resins by any of known molding methods such as injection molding, compression molding, hollow molding, extrusion molding, and rotational molding. May be used.

The coating composition and the aqueous dispersion of the present invention are particularly suitable when the molded article to which the composition is applied is blended with an inorganic filler such as talc, zinc white, glass fiber, titanium white, and magnesium sulfate, and a pigment. A coating film having good adhesion of the coating film can be formed.
Further, the molded article to which the coating composition and the aqueous dispersion of the present invention are applied may contain various stabilizers, ultraviolet absorbers and the like in addition to the above.

  Examples of the preferably used stabilizer include, for example, 2,6-di-t-butyl-4-methylphenol, tetrakis [methylene (3,5-di-4-hydroxyhydrocinnamate)] methane, metaoctadecyl-3- (4'-hydroxy-3,5-di-t-butyl-phenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butyl-phenol), 4,4'-butylidenebis (3-methyl -6-t-butylphenol), 2,2-thiobis (4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl) Phenolic stabilizers such as -4-hydroxybenzyl) benzene and 1,3,5-tris (2-methyl-4-hydroxy-5-t-butylphenol) butane; It can be mentioned tridecyl phosphite, and the like phosphorus-based stabilizers such as trinonylphenyl phosphite; Jipuroponeto, sulfur-based stabilizers such as distearyl thiodipropionate.

  Examples of the ultraviolet absorber used include, for example, 2-hydroxy-4-octoxybenzophenone, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, paraoctylphenyl salicylate and the like.

Hereinafter, the present invention will be described more specifically with reference to the following production examples and examples, but the present invention is not limited to these examples unless it exceeds the gist thereof.
In the following production examples and the like, the catalyst synthesis step and the polymerization step are all performed under a purified nitrogen atmosphere, and the solvent is dehydrated by molecular sieve (MS-4A), then degassed by bubbling with purified nitrogen. used.
In the following Production Examples and the like, physical properties of the propylene-based polymer and the like were measured as follows.

<Measurement of physical properties of propylene polymer>
(1) The weight average molecular weight Mw, number average molecular weight Mn, and molecular weight distribution Mw / Mn were measured using GPC (Waters 150CV type). As the solvent, o-dichlorobenzene was used, and the measurement temperature was 135 ° C.
(2) The pentad S ₁ / S and the block index 4 + S ₁ / S ₂ of the propylene unit chain were measured by the ¹³ C-NMR spectrum measurement method described above.
(3) The melting point [Tm] and the heat of crystal fusion were determined by the following method using a thermal analysis system TA2000 manufactured by DuPont.
A sample (about 5 to 10 mg) was melted at 200 ° C. for 3 minutes, then cooled to 30 ° C. at a rate of 10 ° C./min, and then heated to 200 ° C. at a rate of 10 ° C./min to obtain a melting curve. The peak top temperature of the main endothermic peak in the temperature rising stage was determined as the melting point.

(4) -1 As a method for quantifying the ethylene component [E], the above-described measurement of the ¹³ C-NMR spectrum is used, and (1) a method of calculating only from α-methylene and (2) a method of calculating only from β-methylene. The method was calculated by two methods, and the average value was used as the ethylene content (mole fraction).

(1) α-methylene method

(2) β-methylene method

(4) -2 As a method for measuring the content of α-olefin, the monomer content can be calculated by the following method, and the pentad S ₁ / S of the propylene chain portion and the block index 4 + S ₁ / S ₂ can be calculated in combination. . In the following, 1-hexene is used as an example, but olefin monomers having 4 or more carbon atoms, such as 1-butene, 1-pentene, and 1-octene, can be similarly measured.

(Equation 4)
Propylene content = ([PP] + 1/2 [PH]) / ([HH] + [PH] + [PP])
1-hexene content = ([HH] +1/2 [PH]) / ([HH] + [PH] + [PP])
[PP] indicates a propylene-propylene chain diad, the value of which is based on a skeleton CH ₂ (Sαα) having a chemical shift of δ48.0-45.5 ppm, and [PH] indicates a propylene-hexene chain diad. from the chemical shift δ45.0-43.5ppm backbone _CH 2 (S [alpha] [alpha]) is, [HH] hexene - indicates a chain portion diad of hexene, the value of the chemical shift δ43.0-41.0ppm backbone _CH 2 (S [alpha] [alpha]) Required from. The following literature can be referred to for the measurement method.
Soga K., Uozumi T .; Park, JR; Makromol. Chem. 1990, 191, 2853-2864.
Soga K., Lee DH, Shiono T., Kashiwa, N .; Makrmol. Chem. 1989, 190, 2683.

(4) -3 As a method for quantifying a monomer component having a functional group such as (meth) acrylic acid and maleic anhydride, the monomer content was calculated by IR or another titration method, and the pentad S ₁ / It can be calculated by combining with S, and block index _{4 + S} 1 / S _2.

<Production of propylene polymer>
[Production Example 1]
(1) Synthesis of dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl] hafnium (1) -1 Synthesis of ligand 2-Methylazulene (4.01 g) was converted to tetrahydrofuran ( After cooling to 0 ° C. in an ice bath, methyllithium (diethyl ether solution (1.14 mol / l), 24.8 ml) was added dropwise at the same temperature. This solution was slowly added dropwise to a solution of dimethylsilyl dichloride (34.0 ml, 0.280 mol) in tetrahydrofuran (140 mL) cooled to 0 ° C. in an ice bath. After stirring for 3 hours, the solvent and unreacted dimethylsilyl dichloride were distilled off under reduced pressure. ) And cooled to 0 ° C., and cyclopentadienyl sodium (2.1 mol / l, 26.9 ml, 56.5 mmol) was gradually added dropwise, and after the addition was completed, the mixture was stirred at room temperature for 12 hours. Thereafter, water was added, and the desired compound was extracted with diethyl ether, and the extracted solution was dehydrated with magnesium sulfate and then dried to obtain a crude product of the desired ligand. The crude product was purified by silica gel column chromatography to obtain the desired ligand (6.29 g) in a yield of 79%.

(1) -2 Complex synthesis The ligand (6.29 g) obtained in (1) -1 was dissolved in tetrahydrofuran (100 ml) and cooled to 0 ° C in an ice bath. At the same temperature, an n-hexane solution of n-butyllithium (1.56 mol / l, 28.4 ml) was slowly added dropwise. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred for 3 hours, and the solvent was distilled off under reduced pressure. After toluene (60 ml) was added to the residue obtained after the distillation, the mixture was cooled to -78 ° C. To this, a suspension of hafnium tetrachloride (7.17 g) in toluene (140 ml) cooled to -78 ° C was slowly added. Thereafter, the cooling bath was removed and the mixture was stirred overnight. After completion of the stirring, the reaction solution was filtered using a G3 frit. The solid on the frit was further washed with toluene, and the filtrate was concentrated to give a brown powder. From the brown powder, the target complex was extracted with hot n-hexane (180 ml × 3 times). After the extract solution is dried, the obtained solid is suspended and washed with n-hexane (20 ml × 5 times), and then dried under reduced pressure to obtain the desired dichloro [dimethylsilylene (cyclopentadienyl). ) (2,4-Dimethyl-4H-1-azulenyl] hafnium (2.90 g) was obtained (yield 25%).

The results of ¹ H-NMR measurement of the above compound are shown below.
¹ H-NMR (CDCl ₃ ): δ 0.85 (s, 3H), 0.86 (s, 3H), 1.47 (d, J = 7.1 Hz, 3H), 2.25 (s, 3H), 3.42-3.52 (m, 1H), 5.42 (dd, J = 4.7, 10.1 Hz, 1H), 5.80-5.85 (m, 2H), 5.90-5.95 (m, 1H), 6.16-6.20 (m, 2H), 6.65 (d, J = 11.4H), 6.80-6.85 (m, 1H), 6.98-7.02 (m, 1H).

(2) Chemical treatment of clay mineral In a 1,000 ml round bottom flask, demineralized water (110 ml), magnesium sulfate heptahydrate (22.2 g) and sulfuric acid (18.2 g) were collected and dissolved with stirring. Was. In this solution, commercially available granulated montmorillonite (manufactured by Mizusawa Chemical Co., Ltd .; Benclay SL, 16.7 g) was dispersed, heated to 100 ° C. over 2 hours, and stirred at 100 ° C. for 2 hours. Thereafter, the mixture was cooled to room temperature over 1 hour, and the obtained slurry was filtered to collect a wet cake. The collected cake was again slurried in deionized water (500 ml) in a 1,000-ml round bottom flask, and filtered. This operation was repeated twice. The cake finally obtained was dried overnight at 110 ° C. under a nitrogen atmosphere to obtain chemically treated montmorillonite (13.3 g).

(3) Polymerization To the chemically treated montmorillonite (0.88 g) obtained in Production Example 1 (2), a toluene solution of triethylaluminum (0.4 mmol / ml, 4.0 ml) was added, and the mixture was stirred at room temperature for 1 hour. Toluene (16 ml) was added to this suspension, and after stirring, the supernatant was removed. After repeating this operation twice, toluene was added to obtain a clay slurry (slurry concentration = 99 mg clay / ml).
In a separate flask, triisobutylaluminum (0.342 mmol) manufactured by Tosoh Akzo was collected, and the clay slurry (11.4 ml) obtained here and the complex (18) obtained in Production Example 1 (1) -2 were collected. (0.06 mg, 34.2 mmol) in toluene was added and stirred at room temperature for 10 minutes to obtain a catalyst slurry.

  Next, toluene (2250 ml), triisobutylaluminum (5.7 mmol) and liquid propylene (540 ml) were introduced into an induction stirring type autoclave having an internal volume of 5 liters. At room temperature, the whole amount of the catalyst slurry was introduced, the temperature was raised to 60 ° C., and stirring was continued at the same temperature for 1 hour while maintaining the total pressure during polymerization at 0.7 MPa. After completion of the stirring, unreacted propylene was purged to terminate the polymerization. The autoclave was opened, the entire amount of the toluene solution of the polymer was recovered, and the solvent and the clay residue were removed. As a result, 69 g of a propylene polymer was obtained. Table 1 summarizes the results of the analysis of the obtained polymer.

[Production Example 2]
As a clay slurry material, 17.8 mg (34.2 mmol) of a complex, triisobutylaluminum (0.342 mmol), and a clay slurry (11.4 ml) were used, and toluene (1100 ml) and triisobutylaluminum (0.5 mmol) were used. , Liquid propylene (264 ml), the temperature during the polymerization was 80 ° C., the total pressure was 0.8 MPa, and the polymerization time was 1.83 hours. As a result, 245 g of a propylene polymer was obtained. Table 1 summarizes the results of the analysis of the obtained polymer.

[Production Example 3]
(1) Synthesis of racemic dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azulenyl]} hafnium 2-fluoro-4-bromobiphenyl ( 6.35 g, 25.3 mmol) was dissolved in a mixed solvent of diethyl ether (50 ml) and n-hexane (50 ml), and a solution of t-butyllithium in n-pentane (33 ml, 50.6 mmol, 1.54 N) was added. It was added dropwise at -78 ° C. After stirring at −10 ° C. for 2 hours, 2-ethylazulene (3.55 g, 22.8 mmol) was added to the solution, and the mixture was stirred at room temperature for 2 hours. n-Hexane (30 ml) was added, and the supernatant was removed by decantation. This operation was repeated once. To the obtained yellow precipitate, n-hexane (30 ml) and tetrahydrofuran (40 ml) were added at 0 ° C. Next, N-methylimidazole (50 ml) and dimethyldichlorosilane (1.4 ml, 11.4 mmol) were added, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 1 hour. Thereafter, dilute hydrochloric acid was added, and the mixture was separated. The organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-biphenyl) -1. , 4-dihydroazulene) (8.3 g).

Next, the crude product obtained above was dissolved in diethyl ether (30 ml), and an n-hexane solution of n-butyllithium (14.9 ml, 22.8 mmol, 1.53 N) was added dropwise at −70 ° C. The temperature was gradually raised, and the mixture was stirred at room temperature overnight. Further, toluene (200 ml) was added, the mixture was cooled to -70 ° C, hafnium tetrachloride (3.6 g, 11.4 mmol) was added, the temperature was gradually raised, and the mixture was stirred at room temperature for 4 hours. Most of the solvent was distilled off from the obtained slurry under reduced pressure, diethyl ether (50 ml) was added, and the obtained slurry was filtered. After washing with diethyl ether (5 ml × 2), ethanol (15 ml × 2), and n-hexane (10 ml × 2), dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4) [Biphenylyl) -4H-azulenyl] {hafnium racemic / meso mixture (4.53 g, 42% yield) was obtained. The obtained racemic / meso mixture was analyzed by ¹ H-NMR, and as a result, it was found that the mixture was a racemic 76.6% and a meso 23.4% mixture.

  The obtained racemic-meso mixture (4.5 g) was suspended in dichloromethane (35 ml) and irradiated with light using a high-pressure mercury lamp (100 W) for 1 hour. The solvent was distilled off under reduced pressure, and toluene (25 ml) and dichloromethane (11 ml) were added to the obtained solid, followed by heating to 60 ° C. to obtain a homogeneous solution. Dichloromethane was distilled off under reduced pressure to precipitate crystals. The obtained crystals were filtered, washed twice with hexane (5 ml), and dried under reduced pressure to obtain a racemic form (1.79 g).

(2) Chemical treatment of clay mineral 55.85 g of demineralized water, 32.70 g of sulfuric acid and 8.01 g of lithium hydroxide were added to a 500-ml round-bottomed flask, stirred, and then montmorillonite (Mizusawa Chemical; Mizusawa Smectite) 51.65 g Was added, and the mixture was heated and refluxed for 140 minutes. After adding 300 ml of demineralized water and performing suction filtration, the solid components were dispersed in 600 ml of demineralized water and suction filtered. This operation was repeated once more. The residue obtained by filtration was dried at 100 ° C. to obtain montmorillonite treated with acid and metal salt.
1.05 g of the obtained montmorillonite treated with an acid and a metal salt was collected in a 100-ml round bottom flask, and dried by heating at 200 ° C. under reduced pressure for 2 hours. To this was added 4.0 ml of a toluene solution of triethylaluminum (0.5 mmol / ml) under purified nitrogen, reacted at room temperature for 30 minutes, washed twice with 30 ml of toluene, and contained chemically treated montmorillonite. A toluene slurry was obtained.

(3) Preliminary polymerization Toluene was extracted from the slurry (containing 914.2 mg as a solid content) obtained in Production Example 3 (2), and the amount of residual toluene was adjusted to 1.0 ml. To this slurry was added a toluene solution of triisobutylaluminum (0.5 mmol / ml, 0.5 ml), and the dichloro {1,1′-dimethylsilylenebis [2-ethyl-) synthesized in Production Example 3 (1) was further added. 4- (2-Fluoro-4-biphenylyl) -4H-azulenyl] {hafnium racemic toluene solution (3.0 mmol / ml, 9.2 ml) was added and stirred at room temperature for 1 hour to obtain a catalyst slurry. .
Into a 2-liter induction-stirring autoclave, 40 ml of toluene and the entire amount of the catalyst slurry were introduced under purified nitrogen. 11.0 g of propylene was introduced with stirring, and prepolymerization was performed at 30 ° C. for 2 hours and then at 50 ° C. for 0.5 hour. After the prepolymerization, unreacted propylene was purged, and the pressure was replaced by 0.5 MPa with purified nitrogen twice, and then the prepolymerized catalyst was taken out. It contained 9.7 g of polymer per gram of chemically treated montmorillonite component.

(4) Polymerization A 2-liter induction-stirring autoclave having a built-in anchor type stirring blade was replaced with purified nitrogen, and then 750 g of liquefied propylene was charged at 25 ° C. After a toluene solution of triisobutylaluminum (0.1 mmol / ml, 5.0 ml) was injected at the same temperature, the temperature was raised to 70 ° C. After hydrogen was added so that the concentration of hydrogen in the gas phase became 0.2 mol%, 30.0 mg of the prepolymerized catalyst obtained in the above (3) was added at 70 ° C. to initiate polymerization. One hour later, unreacted propylene was purged to terminate the polymerization. The amount of the obtained propylene-based polymer was 384 g. The results of analyzing the obtained polymer are shown in Table 1.

[Production Example 4]
Highly stereospecific isotactic polypropylene (31.1 g), heptane (180 ml), Pd / C (Aldrich: 10% by weight Pd / C) (7.87 g) in an induction stirring type micro autoclave having an inner volume of 50 mL. Was added, the system was closed, and the atmosphere was replaced with nitrogen. Thereafter, 8.0 MPa of hydrogen was introduced, the temperature was raised to 275 ° C., and stirring was continued for 6 hours. After cooling, the reaction was stopped by purging with hydrogen. The autoclave was opened to collect the entire heptane solution of the polymer, and the solvent and the Pd / C residue were removed. As a result, 30.6 g of a propylene polymer was obtained. The results of analyzing the obtained polymer are shown in Table 1.

The physical properties of the high stereospecific isotactic polypropylene used are as follows.
MFR: 15,000
Tm: 154.9
Mw: 37,000
Mn: 18,000
Mw / Mn: 2.1
[Mmmm]: 98.4%, [mmmr]: 0.0%, [rmrm]: 0.1%, [rrrr]: 0.2%

[Production Example 13]
(1) Chemical treatment of clay mineral In a 1000 mL round bottom flask, demineralized water (72 mL), lithium sulfate monohydrate (11 g) and sulfuric acid (17 g) were collected and dissolved under stirring. A commercially available granulated montmorillonite (Benclay SL, manufactured by Mizusawa Chemical Co., Ltd., 22 g) was dispersed in this solution, the temperature was raised to 100 ° C., and stirring was performed for 5 hours. Thereafter, the mixture was cooled to room temperature over 1 hour, and the obtained slurry was filtered to collect a wet cake. The collected cake was re-slurried in demineralized water (500 mL) in a 1000 mL round bottom flask, and filtered. This operation was repeated three times. The cake finally obtained was dried under reduced pressure at 200 ° C. for 1 hour under a nitrogen atmosphere to obtain chemically treated montmorillonite (15.6 g).

(2) Polymerization To the chemically treated montmorillonite (0.25 g) obtained in Production Example 1- (2), a toluene solution of triisobutylaluminum (0.5 mmol / ml, 1.0 ml) was added, and the mixture was stirred at room temperature for 30 minutes. did. Toluene (8 ml) was added to this suspension, and after stirring, the supernatant was removed. After repeating this operation twice, toluene was added to obtain a clay slurry (slurry concentration = 99 mg clay / ml).
In a separate flask, triisobutylaluminum (0.15 mmol) manufactured by Nippon Alkali Aluminum Co., Ltd. was collected, and the clay slurry (total amount) obtained here and the complex (4.0 mg) obtained in Example 1 (1) -2 were collected. , 7.5 mmol) in toluene and stirred at room temperature for 10 minutes to obtain a catalyst slurry.

  Next, toluene (1100 ml), triisobutylaluminum (0.13 mmol), liquid propylene (264 ml), and 1-hexene (0.60 mol, 50 g) were introduced into an induction stirring autoclave having an internal volume of 2 liters. At room temperature, the whole amount of the catalyst slurry was introduced, the temperature was raised to 80 ° C., and stirring was continued at the same temperature for 1 hour while maintaining the total pressure during polymerization at 0.85 MPa. After completion of the stirring, unreacted propylene was purged to terminate the polymerization. The autoclave was opened to collect the entire amount of the toluene solution of the polymer, and the solvent and the clay residue were removed. As a result, 35 g of a propylene-1-hexene copolymer was obtained. The results of analyzing the obtained polymer are summarized in Table 1.

[Reference Example 1]
The physical properties of Ube Tack UT-2115 manufactured by Ube Industries, Ltd. were measured in the same manner. Table 1 shows the measurement results.
[Reference Example 2]
Physical properties of Tuffmer S4030 manufactured by Mitsui Chemicals, Inc. were measured in the same manner. Table 1 shows the measurement results.

<Production of acid-modified propylene polymer>
[Production Example 5]
In a glass flask equipped with a reflux condenser, a dropping funnel, a thermometer, and a stirrer, toluene (160 g), the propylene polymer obtained in Production Example 1 (40 g), and maleic anhydride (6 g) were added. The atmosphere was replaced with nitrogen gas, and the temperature was raised to 110 ° C. After the temperature was raised, a toluene solution of perbutyl I (t-butyl peroxyisopropyl monocarbonate, manufactured by NOF Corporation) (2.8 g) was supplied using a metering pump in 2 hours, and then stirred at the same temperature for 3 hours. The reaction was continued. After completion of the reaction, the system was cooled to around room temperature, acetone was added, and the precipitated polymer was separated by filtration. Further, precipitation and filtration were repeated with acetone, and the finally obtained polymer was washed with acetone. The polymer obtained after the washing was dried under reduced pressure to obtain a modified polymer in the form of a white powder. As a result of infrared ray absorption spectrum measurement, neutralization titration and the like of this modified polymer, the content (graft ratio) of maleic anhydride groups was 1.5% by weight. Table 2 shows the results of measurement of the graft ratio and physical properties of the resulting modified polymer.

[Production Example 6]
Same as Production Example 5 except that toluene (40 g), the propylene polymer obtained in Production Example 1 (10 g), maleic anhydride (2.4 g), and perbutyl I (manufactured by NOF Corporation) (1 g) were used. Operation. Table 2 shows the results of measurement of the graft ratio and physical properties of the resulting modified polymer.

[Production Example 7]
The same operation as in Production Example 5 except that toluene (40 g), the propylene polymer (10 g) obtained in Production Example 1, maleic anhydride (5 g), and perbutyl I (manufactured by NOF Corporation) (3 g) were used. I went in. Table 2 shows the results of measurement of the graft ratio and physical properties of the resulting modified polymer.

[Production Example 8]
Except that the propylene polymer synthesized in Production Example 2 was used, the same operation as in Production Example 5 was performed. Table 2 shows the results of measurement of the graft ratio and physical properties of the resulting modified polymer.

[Production Example 9]
In a glass flask equipped with a reflux condenser, a dropping funnel, a thermometer, and a stirrer, chlorobenzene (160 g), the propylene polymer obtained in Production Example 3 (40 g), and maleic anhydride (6 g) were added. The atmosphere was replaced with nitrogen gas, and the temperature was raised to 110 ° C. After the temperature was increased, a chlorobenzene solution of Park Mill D (dicumyl peroxide, manufactured by NOF CORPORATION) (2.8 g) was supplied using a metering pump in 2 hours, and the reaction was continued by stirring at the same temperature for 3 hours. went. After completion of the reaction, the system was cooled to around room temperature, acetone was added, and the precipitated polymer was separated by filtration. Further, precipitation and filtration were repeated with acetone, and the finally obtained polymer was washed with acetone. The polymer obtained after the washing was dried under reduced pressure to obtain a modified polymer in the form of a white powder. Table 2 shows the results of measurement of the graft ratio and physical properties of the resulting modified polymer.

[Production Example 10]
The same operation as in Production Example 5 was performed except that the propylene polymer synthesized in Production Example 4 was used. Table 2 shows the results of the graft ratio and physical properties of the resulting modified polymer.
[Production Example 11]
The same operation as in Production Example 5 was performed except that the polypropylene of Reference Example 1 (Ubetac UT-2115) was used. Table 2 shows the results of the graft ratio and physical properties of the resulting modified polymer.

[Production Example 12]
The procedure was performed in the same manner as in Production Example 5, except that the propylene copolymer of Reference Example 2 (Tuffmer S4030) was used. Table 2 shows the results of the graft ratio and physical properties of the resulting modified polymer.
[Production Example 14]
Except that the propylene copolymer synthesized in Production Example 13 was used, the same operation as in Production Example 5 was performed. Table 2 shows the results of the graft ratio and physical properties of the resulting modified polymer.

<Production of polypropylene copolymer and its composition>
[Example 1]
In a glass flask equipped with a reflux condenser, a dropping funnel, a thermometer, and a stirrer, 10 g of the maleated anhydride polypropylene (maleic anhydride content: 1.5% by weight) obtained in Production Example 5 and 50 g of toluene were charged. The temperature was raised to 100 ° C. in an air stream to dissolve. 0.2 g of 2-hydroxyethyl acrylate [compound (C1)], 0.05 g of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) and 0.02 g of hydroquinone monomethyl ether were added thereto, The reaction was performed at the same temperature for 5 hours. As a result of an infrared absorption spectrum analysis of the obtained product, 2.0% by weight of 2-hydroxyethyl acrylate was added.

  Next, 12 g of n-butyl acrylate, 8 g of methyl methacrylate, 0.2 g of methacrylic acid, and azobisisobutyl nitrile (as an initiator) were added to 60 g (solid content: 10 g) of a toluene solution of the obtained acid-modified polypropylene to which 2-hydroxyethyl acrylate was added. Hereinafter, 0.2 g of AIBN) and 70 g of toluene were charged, and the internal temperature was raised to 90 ° C in about 1 hour under a nitrogen stream, and the reaction was carried out at the same temperature for 2 hours. 0.3 g of AIBN was added and reacted for 2 hours. After 0.3 g of AIBN was added and further reacted for 2 hours, the mixture was cooled to obtain a transparent and uniform coating composition comprising a 20% by weight polymer solution in toluene. .

[Example 2]
In a glass flask equipped with a reflux condenser, a dropping funnel, a thermometer, and a stirrer, 10 g of the anhydrous maleated polypropylene obtained in Production Example 5 and 50 g of toluene were charged, and the mixture was heated to 110 ° C. in an air stream and dissolved. To this were added 0.2 g of glycidyl methacrylate, 0.05 g of DBU and 0.02 g of hydroquinone monomethyl ether, and reacted at the same temperature for 5 hours. As a result of an infrared absorption spectrum analysis of the obtained product, 2.1% by weight of glycidyl methacrylate was added.

  Next, 6 g of n-butyl acrylate, 8 g of methyl methacrylate, 6 g of styrene, 0.2 g of methacrylic acid, 0.2 g of AIBN as an initiator, and 60 g of a toluene solution of the acid-modified polypropylene to which the glycidyl methacrylate was added (10 g of solid content), 70 g of toluene was charged, the internal temperature was raised to 90 ° C. in about 1 hour under a nitrogen stream, and the reaction was carried out at the same temperature for 2 hours. 0.3 g of AIBN was added and reacted for 2 hours. After adding 0.3 g of AIBN and further reacting for 2 hours, the mixture was cooled to obtain a transparent and uniform coating composition comprising a 20% by weight polymer solution in toluene.

[Example 3]
In a glass flask equipped with a reflux condenser, a dropping funnel, a thermometer, and a stirrer, 3.1 g of dimethylaminoethyl methacrylate, 36.9 g of methyl methacrylate, and 160 g of isopropanol were added, and the temperature was raised to 82 ° C. under a nitrogen stream. 0.6 g of AIBN was added thereto and reacted for 6 hours. The temperature was lowered to 40 ° C., and 300 g of methanol was added to completely crystallize the product, followed by filtration. It was dried at 60 ° C. for 4 hours in a vacuum dryer to obtain 22 g of a polymer.
A solution prepared by dissolving 3 g of this polymer in 12 g of toluene and 6 g of anhydrous maleated polypropylene obtained in Production Example 6 were dissolved in 24 g of toluene, and placed in an atmosphere of 95% humidity and 80 ° C. for one day to remove acid anhydride groups. ring-opened so solution (result of measuring the ring opening of the ring closed form and 1740 cm ^-1 in 1780 cm ^-1 in infrared absorption spectrum, the ring-opening rate ^{(= (abs1740cm- 1) / (} abs1780cm- 1 + abs1740cm- 1) × 100 (%) was 90%), and the mixture was stirred at 50 ° C. for 2 hours to obtain a transparent, pale yellow, uniform coating composition comprising a 20% by weight polymer solution in toluene.

[Example 4]
In a glass flask equipped with a reflux condenser, a dropping funnel, a thermometer, and a stirrer, 1.9 g of dimethylaminoethyl methacrylate, 38.1 g of cyclohexyl methacrylate, and 160 g of isopropanol were added, and the temperature was raised to 82 ° C. under a nitrogen stream. 0.6 g of AIBN was added thereto and reacted for 6 hours. The temperature was lowered to 40 ° C., and 300 g of methanol was added to completely crystallize the resulting polymer, followed by filtration. It was dried at 60 ° C. for 4 hours in a vacuum dryer to obtain 24 g of a polymer.
A solution prepared by dissolving 3 g of this polymer in 17 g of toluene and 6 g of a maleic anhydride-modified propylene polymer obtained in Production Example 5 in 34 g of toluene were placed in an atmosphere of 95% humidity and 80 ° C. for one day, and then acid anhydride was obtained. a result of measuring the ring opening of the ring closed form and 1740 cm ^-1 in 1780 cm ^-1 at the proximal solution obtained by ring-opening (infrared absorption spectrum, the ring-opening rate ^{(= (abs1740cm- 1) / (} abs1780cm- 1 + abs1740cm- ¹ ) × 100 (%) was 90%), and the mixture was stirred at 50 ° C. for 2 hours to obtain a clear, pale yellow, uniform coating composition comprising a 20% by weight polymer solution in toluene. .

[Example 5]
A coating composition was obtained in the same manner as in Example 1, except that the maleic anhydride-modified propylene polymer synthesized in Production Example 6 was used.
[Example 6]
A coating composition was obtained in the same manner as in Example 1, except that the maleic anhydride-modified polypropylene synthesized in Production Example 7 was used.

[Example 7]
A coating composition was obtained in the same manner as in Example 1, except that the maleic anhydride-modified polypropylene synthesized in Production Example 8 was used.

[Comparative Example 1]
The same operation as in Example 1 was performed except that the maleic anhydride-modified polypropylene synthesized in Production Example 9 was used. However, the produced polymer did not dissolve in toluene and became a swollen product, and could not be applied.
[Comparative Example 2]
A coating composition was obtained in the same manner as in Example 1, except that the maleic anhydride-modified polypropylene synthesized in Production Example 10 was used.

[Comparative Example 3]
The same operation as in Example 1 was performed except that the maleic anhydride-modified polypropylene synthesized in Production Example 11 was used, but the produced polymer did not dissolve in toluene and became a swollen product, and could not be applied.
[Comparative Example 4]
A coating composition was obtained in the same manner as in Example 1, except that the maleic anhydride-modified propylene-based copolymer synthesized in Production Example 12 was used.

[Comparative Example 5]
In a glass flask equipped with a reflux condenser, a dropping funnel, a thermometer, and a stirrer, 10 g of the polypropylene obtained in Production Example 1 and 50 g of toluene were charged, and heated to 50 ° C. under an air stream to dissolve. Next, 12 g of n-butyl acrylate, 8 g of methyl methacrylate, 0.2 g of methacrylic acid, 0.2 g of AIBN as an initiator, and 70 g of toluene were charged, and the internal temperature was raised to 90 ° C. in about 30 minutes under a nitrogen stream. The reaction was performed at a temperature for 2 hours. After adding 0.3 g of AIBN and reacting for 2 hours, after adding 0.3 g of AIBN and further reacting for 2 hours, a toluene solution of 20% by weight of the polymer was obtained by cooling. Occurred and no coating composition was obtained.

[Comparative Example 6]
10 g of the modified polypropylene obtained in Production Example 5 was dissolved in 40 g of toluene to obtain a transparent and uniform coating composition composed of a 20% by weight solution of a polymer in toluene.

Example 8
A coating composition was obtained in the same manner as in Example 1, except that the maleic anhydride-modified propylene / 1-hexene copolymer synthesized in Production Example 14 was used.

[Example 9]
0.8 g of dimethylaminoethyl methacrylate, 39.2 g of methyl methacrylate, and 160 g of isopropanol were added to a glass flask equipped with a reflux condenser, a dropping funnel, a thermometer, and a stirrer, and the temperature was raised to 82 ° C. under a nitrogen stream. 0.6 g of AIBN was added thereto and reacted for 6 hours. The temperature was lowered to 40 ° C., and 300 g of methanol was added to completely crystallize the product, followed by filtration. The obtained product was dried in a vacuum dryer at 60 ° C. for 4 hours to obtain 22 g of a polymer.
A solution prepared by dissolving 7 g of this polymer in 28 g of toluene and 3 g of anhydrous maleated polypropylene obtained in Production Example 6 were dissolved in 12 g of toluene and placed in an atmosphere of 95% humidity and 80 ° C. for one day to open the acid anhydride group. ring is not the solution (a result of measuring the ring opening of the ring closed form and 1740 cm ^-1 in 1780 cm ^-1 in infrared absorption spectrum, the ring-opening rate ^{(= (abs1740cm -1) / (} abs1780cm -1 + abs1740cm -1) × (100%) was 90%), and the mixture was stirred at 50 ° C. for 2 hours to obtain a clear, pale yellow, uniform coating composition comprising a toluene solution of 20% by weight of a polymer.

[Example 10]
In a glass flask equipped with a reflux condenser, a dropping funnel, a thermometer, and a stirrer, 10 g of the anhydrous maleated polypropylene obtained in Production Example 5 and 20 g of toluene were charged, and heated to 100 ° C. under an air stream to dissolve. 1 g of 2-hydroxyethyl acrylate, 0.4 g of dimethylbenzylamine and 0.02 g of hydroquinone monomethyl ether were added thereto and reacted at the same temperature for 5 hours. A 0.5 g solution was withdrawn, reprecipitated with acetone, washed, and subjected to infrared absorption spectrum analysis. As a result, 0.4% by weight of 2-hydroxyethyl acrylate was added.
Next, 9 g of n-butyl methacrylate, 9 g of methyl methacrylate, 0.2 g of V-59 (manufactured by Wako Pure Chemical Industries) as an initiator, and toluene in 30 g (solid content: 10 g) of the obtained toluene solution of 2-hydroxyethyl acrylate-added polypropylene. 70 g was charged, the internal temperature was raised to 85 ° C. in about 1 hour under a nitrogen stream, and the reaction was carried out at the same temperature for 3 hours. 0.2 g of V-59 was added and reacted for 3 hours, followed by cooling to obtain a transparent and uniform coating resin composition comprising a 20% by weight resin solution of toluene having an OH value of 20 mgKOH / g.

[Example 11]
In a glass flask equipped with a reflux condenser, a dropping funnel, a thermometer, and a stirrer, 10 g of the anhydrous maleated polypropylene obtained in Production Example 6, 5 g of polyester polyol P-2010 (manufactured by Kuraray Co., Ltd.), and 20 g of toluene were placed. It was charged and heated to 110 ° C. in an air stream to dissolve. To this was added 0.2 g of dimethylbenzylamine, and reacted at the same temperature for 5 hours. Toluene (40 g) was added to obtain a transparent and uniform coating resin composition comprising a 20% by weight resin solution in toluene.

[Example 12]
Using the coating composition manufactured in Example 10, evaluation as a coating material was performed. Table 4 shows the results.

[Comparative Example 7]
10 g of the maleic anhydride-modified propylene polymer synthesized in Production Example 6 was dissolved in 40 g of toluene to produce a coating composition, which was evaluated as a coating agent. Table 4 shows the results.

<Evaluation of physical properties of coating composition>
The coating compositions obtained in the above Examples and Comparative Examples were evaluated for physical properties by the following methods. Table 3 summarizes the evaluation results.
<Preparation of test piece>
[Example of substrate]
A test substrate having a wall thickness of 3 mm and a size of 150 mm x 70 mm was molded from a polypropylene MA3U manufactured by Nippon Polychem Co., Ltd. (propylene homopolymer: MFR 15 g / 10 min (230 ° C, 21.18N load)) at a molding temperature of 240 ° C using a screw inline injection molding machine.

<Evaluation of physical properties>
(1) Solubility The solubility test was determined by the following method. The solution (coating composition) prepared in each example is heated in a constant temperature bath at 50 ° C. for 1 hour, then naturally cooled to room temperature, allowed to stand for 1 hour, and filtered through a SUS wire mesh No. 400. What was left in the wire net was made into an insoluble matter, and what passed as a solution was made into a soluble matter, and dried in a vacuum dryer at 80 ° C., 1 mmHg or less for 4 hours. Weigh and calculate the fraction of insolubles.

(2) Low-temperature fluidity The coating composition was placed in a sample bottle, left in a low-temperature incubator set at −10 ° C., and observed one week later.
Evaluation criteria ○: There is fluidity, ×: There is no fluidity

(3) Adhesion <Preparation of test piece>
(3-1) Evaluation as a primer (adhesion -1)
The coating composition obtained in each of the examples and comparative examples was spray-coated on the injection-molded substrate (the surface of which was wiped with isopropyl alcohol) prepared in the substrate example. The application amount was 3 to 5 g / m ² . Next, the molded substrate after the application was allowed to stand at 25 ° C. for 10 minutes, and then dried at 80 ° C. for 30 minutes in a Safeven dryer. Next, the dried product was allowed to stand at 25 ° C. for 1 hour, and then an acrylic polyol urethane paint, ethane PG80III (manufactured by Kansai Paint Co., Ltd .: trade name) was blended as a base coat from the coated film with a predetermined amount of a curing agent. Then, adjust the viscosity with a special thinner at Ford Cup No. 4 and adjust the viscosity to 12 to 13 seconds, then spray-coat so that the dry coating amount is 50 to 60 g, and At 100 ° C. for 30 minutes. Furthermore, after standing at 25 ° C. for 24 hours, an interlayer adhesion test was performed.

(3-2) Evaluation as coating material (adhesion-2)
The coating composition obtained in each of the examples and comparative examples was spray-coated on the injection-molded substrate (the surface of which was wiped with isopropyl alcohol) prepared in the substrate example. In addition, the application amount was 10 to 20 g / m ² . Next, the molded substrate after the application was allowed to stand at 25 ° C. for 10 minutes, and then dried at 80 ° C. for 30 minutes in a Safeven dryer.

<Adhesion test>
The interlayer adhesion test is performed according to the cross-cut test method described in JIS K5400, a cross-cut test piece is prepared, and Nichiban Cellotape (trade name) is placed on the cross-section of the test piece. After sticking, this was quickly pulled in the vertical direction and peeled off, and the number of grids that were not peeled out of the 100 grids was counted and used as an index of adhesion.

(4) Water resistance test In the same manner as in the preparation of the test piece in (3) above, each coating composition was used as a primer, a base coat was applied and baked on the coating film, and cured at room temperature to obtain a coated product. Obtained. The coated product was immersed in warm water maintained at 40 ° C. for 10 days, and then subjected to a peeling test in the same manner as in the adhesion test.

(5) Non-tack test Non-tack was evaluated by a finger tack test.
Evaluation criteria ○: excellent non-tackiness, △: slightly tacky, ×: tacky

(6)-(Compatibility 1)
Hitaloid 3904 manufactured by Hitachi Chemical Co., Ltd. [viscosity = 3400 mPa · s, (resin concentration 50 wt%, xylene 40 wt%, butyl acetate 10 wt%: 25 ° C.), SP value = 10.3 (cal / cm ³ ) ^{1 / 2} ] was diluted with toluene to a solid content of 20 wt%, and the diluted solution and the coating composition were mixed at a solution weight ratio of 1: 1 to prepare a solution. Stir the solution with a spatula and apply lightly on a scoop glass plate. After drying at room temperature, the state of the film was visually observed.
Evaluation criteria ○: uniform, Δ: cloudy, ×: separated

(6)-(Compatibility 2)
Hitaloid 3904 (resin solid content concentration: 50%) manufactured by Hitachi Chemical Co., Ltd. was diluted with toluene to a solid content of 12 wt% as an acrylic resin, and the diluted solution and the coating composition were mixed at a solution weight ratio of 1: 1. To prepare a solution. The transmittance (650 nm) of the solution was measured.
Evaluation criteria ○: 80% or more, $ 80% to 50%, × 50% or less

Claims (17)

(A) having a polymer main chain (A) derived from a propylene polymer having the following properties (1) and (2), a side chain containing a polymer chain (B) different from the main chain, and (A A) / (B) weight ratio in the range of 20/1 to 1/20.
(1) In ¹³ C-NMR, a peak derived from a carbon atom of a methyl group in a propylene unit chain composed of a head-to-tail bond was observed, and a peak top chemical attributed to a pentad represented by mmmm was observed. When the shift is 21.8 ppm, the ratio (S ₁ / S) of the peak area S ₁ having a peak top at 21.8 ppm to the total area S of the peaks appearing from 19.8 ppm to 22.2 ppm is 20%. or more and 60% or less, and about 21.5~21.7ppm that the area of the peak (mmmr) having a peak top is _{4 + S 1 / S 2>} 5 when the _{S 2} (2) propylene heavy The melting point [Tm] measured by a differential scanning calorimeter of the combined product is 100 ° C. or less, or the heat of crystal fusion does not show 5 J / g or more.   2. The polypropylene copolymer according to claim 1, wherein the polymer main chain (A) has the above properties (1) and (2) and comprises a propylene polymer having a functional group.   The propylene-based polymer having a functional group has the above properties (1) and (2), and comprises a modified propylene-based polymer of a propylene-based polymer having no functional group. 3. The polypropylene copolymer according to 2.   The polypropylene copolymer according to any one of claims 1 to 3, wherein the modified propylene polymer is an acid-modified propylene polymer modified with an acid having a carboxylic acid group or a dicarboxylic anhydride group. Coalescing.   The polypropylene chain according to any one of claims 1 to 4, wherein the side chain polymer chain (B) is a polymer chain in which a repeating unit is formed by an addition reaction, an ester bond, or an ether bond. Polymer.   The polypropylene copolymer according to claim 1, wherein the side chain polymer chain (B) includes a (meth) acrylic polymer chain.   The polymer main chain (A) is composed of an acid-modified propylene polymer modified with an acid having a carboxylic acid group or a dicarboxylic anhydride group, and the side chain containing the (meth) acrylic polymer chain (B) has 7. The polypropylene copolymer according to claim 4, wherein the polypropylene copolymer is linked via a covalent bond or an ionic bond to a group capable of reacting with the carboxylic acid group or dicarboxylic anhydride group.   The polypropylene copolymer according to any one of claims 1 to 4, wherein the propylene-based polymer is produced using a single-site catalyst.   A compound (C1) having a group capable of reacting with the functional group of the propylene polymer having a functional group according to claim 2 and a radical polymerizable unsaturated bond in the molecule is reacted with the propylene polymer. The method for producing a polypropylene copolymer according to any one of claims 2 to 8, wherein (meth) acrylic acid and / or its derivative (C2) is graft-copolymerized.   After reacting a compound (C1) having a group capable of reacting with a carboxylic acid group or a dicarboxylic anhydride group of an acid-modified propylene polymer and a radical polymerizable unsaturated bond in the molecule with the acid-modified propylene polymer The method for producing a polypropylene copolymer according to any one of claims 3 to 8, wherein (meth) acrylic acid and / or its derivative (C2) is graft-copolymerized.   A compound (C1) having a group capable of reacting with the functional group of the propylene polymer having a functional group according to claim 2 and a radical polymerizable unsaturated bond in a molecule, and (meth) acrylic acid and / or a derivative thereof ( The method for producing a polypropylene copolymer according to any one of claims 2 to 8, wherein the copolymer with C2) is reacted with the propylene-based polymer.   A compound (C1) having a group capable of reacting with a carboxylic acid group or a dicarboxylic anhydride group of an acid-modified propylene polymer and a radically polymerizable unsaturated bond in a molecule, and (meth) acrylic acid and / or a derivative thereof The method for producing a polypropylene copolymer according to any one of claims 3 to 8, wherein the copolymer with (C2) is reacted with an acid-modified propylene-based polymer.   The group capable of reacting with a carboxylic acid group or a dicarboxylic anhydride group of the acid-modified propylene polymer is a group selected from an amino group, a hydroxyl group, an epoxy group and an isocyanate group. 13. The polypropylene copolymer according to any one of 12 above and a method for producing the same.   The polypropylene copolymer according to any one of claims 4, 7, 10 and 12, wherein the acid content (graft ratio) of the acid-modified propylene polymer is 0.01% by weight to 5% by weight. The manufacturing method. The polypropylene copolymer according to any one of claims 1 to 8, having the following properties (a) to (c).
(A) When dissolved in toluene at 25 ° C. with an acrylic resin at a weight ratio of 50/50 and a solid concentration of 12% by weight, the transmittance (650 nm) is 80% or more. (B) Toluene at 25 ° C. When dissolved at a concentration of 10% by weight, the insoluble content is 1% by weight or less based on the whole polymer. (C) Adhesion to a polypropylene substrate by a test for adhesion (cross-cut tape method) is 50 / 100 or more   A coating composition comprising the polypropylene copolymer according to claim 15. An aqueous dispersion comprising the polypropylene copolymer according to claim 15, a surfactant, and water.