JP2004269866A - Coating composition containing propylene-based polymer and method for using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a coating composition containing a propylene-based polymer and/or its modified polymer containing no chlorine, imparting good adhesiveness and paintability to a crystalline polypropylene molded product and having good preservation stability at low temperatures, and provide a method for using the same. <P>SOLUTION: The coating composition comprises at least one species of polymers selected from propylene-based polymers and their modified propylene-based polymers, and at least one species of 7-12C alicyclic hydrocarbons as a solvent. The polymer has following characteristics; (a) when the polymer is dissolved in toluene at 25°C in 10 wt.% concentration, the insoluble part to the whole polymer is ≤1% and (b) the adhesiveness by adhesion test (cross cut tape test) to a crystalline polypropylene base material is ≥50/100. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a coating composition comprising a propylene polymer and / or a modified propylene polymer thereof and an organic solvent. Specifically, the present invention relates to a propylene polymer having good solubility in an organic solvent such as toluene and / or a modified propylene polymer thereof, and a coating composition containing a specific alicyclic hydrocarbon as a solvent. The composition has excellent adhesion to a crystalline olefin polymer as a base material, and is useful as a surface treatment agent, an adhesive, a paint, or the like for the polymer.

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

  Thus, so-called chlorinated polypropylene has been developed as a device for imparting good paintability and adhesion to a propylene-based polymer by a relatively simple method. Chlorinated polypropylene is generally soluble in a hydrocarbon solvent such as toluene and xylene, and has relatively good adhesion to a propylene polymer as a base material. Therefore, the coating property and adhesion of the propylene polymer are improved by a relatively simple method of applying the hydrocarbon solution of the chlorinated polypropylene to the surface of the propylene polymer as a base material and removing the solvent. be able to. It is known that modified chlorinated polypropylene obtained by further modifying chlorinated polypropylene by graft copolymerization with a polar monomer is further excellent in improving paintability and adhesiveness.

  Thus, chlorinated polypropylene and modified chlorinated polypropylene can improve the paintability and adhesiveness of propylene-based polymers relatively easily, but the problem is that they contain a large amount of chlorine. Is mentioned. In recent years, there are concerns about the generation of harmful substances due to the recycling and incineration of resins, and in addition, problems such as the poor weather resistance of resins containing chlorine remain. Therefore, for chlorinated polypropylene, like vinyl chloride resin, development of an alternative resin containing no halogen such as chlorine is strongly desired.

  Against this background, on the other hand, the development of resins that do not contain chlorine has been carried out. For example, Japanese Examined Patent Publication No. 44-958 discloses a treating agent in which an amorphous polypropylene polymer modified with a specific proportion of maleic acid or its anhydride is dissolved in a solvent. Here, the amorphous polypropylene polymer is an amorphous polypropylene containing at least about 20 mol% of propylene units in an atactic polypropylene and a copolymer, and comprising a copolymer of at least one copolymer monomer and propylene. The polymer. Further, as a similar treating agent, there is JP-A-8-217835, in which an amorphous polypropylene or an amorphous propylene-1-butene copolymer is graft copolymerized with an unsaturated carboxylic acid having 3 to 10 carbon atoms. A crystalline polymer is disclosed. When such a graft-modified product is used, the solubility is improved and the paintability is excellent compared to a general modified propylene resin, but it is sticky and inferior in adhesiveness, particularly in a solvent at room temperature. Solubility is still low.

As a measure for improving the solubility, JP-A No. 2000-219846 discloses a coating composition comprising a modified propylene-butene-ethylene terpolymer, an aromatic hydrocarbon and an alicyclic hydrocarbon. However, basically, the higher the copolymerizability of the modified product, the lower the adhesion to the propylene-based resin as the base material. The most important performance has not been clarified. In addition, storage stability in winter requires a low-temperature stability test below freezing point, but only a low-temperature fluidity test at 5 ° C or higher is not described, and the low-temperature storage performance is not clear. .
Japanese Patent Publication No. 44-958 JP-A-8-217835 Japanese Unexamined Patent Publication No. 2000-219846

  The present invention does not contain a halogen such as chlorine, can impart good adhesion and paintability to a crystalline propylene polymer or the like as a base material, and has storage stability at low temperatures. The present invention provides a coating composition containing a good propylene polymer and / or a modified propylene polymer and a method of using the same.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the gist of the present invention includes at least one polymer selected from a propylene polymer and a modified propylene polymer thereof, and at least one alicyclic hydrocarbon having 7 to 12 carbon atoms as a solvent. It is a coating composition, and the polymer exists in the coating composition characterized by having the following properties (a) and (b).
(A) When dissolved in toluene at 25 ° C. at a concentration of 10% by weight, the insoluble content is 1% by weight or less based on the total polymer,
(B) Adhesiveness to a crystalline polypropylene base material (cross cut tape method) is 50/100 or more.

  By using the present invention, it does not contain a halogen such as chlorine, and can impart good adhesion and paintability to a crystalline propylene polymer molded product, and storage stability at low temperatures. It is possible to provide a coating composition of a good propylene polymer and / or a modified propylene polymer.

Hereinafter, the present invention will be described in detail.
The propylene-based polymer in the present invention is a propylene-only polymer or a propylene-olefin copolymer containing propylene as a monomer and containing less than 20 mol% of other olefins, and is substantially a propylene component [ P] is a polymer in the range of 80 ≦ [P] ≦ 100 (mol%), and the olefin component [O] is present in the range of 0 ≦ [O] <20 (mol%). In the present invention, the preferable propylene content is 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, and further preferably 99 mol% or more.
The modified propylene polymer has a main chain of the propylene polymer and a side chain containing a carboxylic acid group, a carboxylic acid anhydride group, or a carboxylic acid ester group. It is obtained by graft copolymerizing a polymerizable monomer having a carboxylic acid group or the like with the resulting propylene polymer.

  As other olefin components, for example, a suitable one is selected from ethylene, butene, pentene, hexene, octene, decene, butadiene, hexadiene, octadiene, cyclobutene, cyclopentene, cyclohexene, norbornene, norbornadiene, styrene, and derivatives thereof. can do. Of these, ethylene, butene, pentene, hexene and octene are preferred.

As a method for quantifying the other olefin component [O] in the propylene-based polymer, (A) a method for measuring the ethylene content by using measurement of ¹³ C-NMR spectrum described later, and (B) an α-olefin. It can be calculated by a method of measuring the content.

  (A) As a quantification method of ethylene component [E], it calculates by two types of methods, (1) The method of calculating only from (alpha) -methylene, (2) The method of calculating only from (beta) -methylene, The average value Is an ethylene content (molar fraction).

(1) α-methylene method

(2) β-methylene method

(B) As a method of measuring the content of α-olefin, the monomer content can be calculated by the following method, and can be calculated by combining pentad S ₁ / S and block index 4 + S ₁ / S ₂ of the propylene chain portion. In the following, 1-hexene was 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 part diad, the value thereof is from a skeleton CH ₂ (Sαα) having a chemical shift δ48.0-45.5 ppm, and [PH] indicates a propylene-hexene chain part 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]) It is requested from. The following literature can be referred 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.

  The most practical method for controlling the olefin component [O] in the propylene polymer to be 0 ≦ [O] <20 (mol%) is to control the ratio of propylene and olefin used during polymerization. is there. Although the specific ratio of propylene and olefin differs depending on the catalyst used, it cannot be said unconditionally. However, the ratio of propylene and olefin used for polymerization under conditions such as desired temperature and pressure, and [O] By previously obtaining a relationship of 0 ≦ [O] <20 (mol%) of [O], using this relationship, 0 ≦ [O] <20 (mol%) of [O] is set to a desired value. Can be controlled. When the olefin component is [O] ≧ 20 (mol%), although the solubility of the copolymer in a solvent is improved, it tends to be inferior in non-tackiness and adhesion, which is not preferable.

  The propylene-based polymer in the present invention preferably has a weight average molecular weight Mw measured by GPC (Gel Permeation Chromatography) of 5,000 to 200,000. When Mw is smaller than 5,000, not only the deterioration of the film forming property after coating becomes remarkable, but also the stickiness is remarkable, which is not preferable. On the other hand, when Mw exceeds 200,000, there is no significant problem with respect to film-forming property and stickiness, but the viscosity when the polymer is dissolved in the solvent becomes too high, and the production or handling of the polymer solution is difficult. This is not preferable because it causes inconvenience. In the present invention, the range of the weight average molecular weight Mw is usually 5,000 to 200,000, preferably 10,000 to 180,000, more preferably 30,000 to 150,000. In addition, the measurement of GPC is performed by a conventionally well-known method using ortho dichlorobenzene etc. as a solvent using a commercially available apparatus.

  The molecular weight distribution of the propylene-based polymer in the present invention is not particularly limited, but an excessively wide molecular weight distribution means that the content of low molecular weight components is inevitably high and should be avoided. 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, preferably Mw / Mn <20, more preferably Mw / Mn <10, most preferably Mw / Mn <5. Are preferably used.

The propylene-based polymer in the present invention has a feature of having a stereo block structure including an isotactic block, and a highly crystalline block and a highly amorphous block coexist in the main chain, and It is mentioned that the block with high crystallinity has a structure rich in isotacticity. However, since the solubility in a solvent deteriorates when there are too many highly crystalline blocks, the balance between the highly crystalline block and the highly amorphous block is important. In the present invention, the requirement defined by the ¹³ C-NMR spectrum is applied as a part of the index representing the balance, and the requirement satisfies the predetermined range, thereby having excellent structural characteristics.

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

  The chemical shift is a methyl branch of 10 types of pentads (mmmm, mmmr, rmrr, mmrr, mmrm, rmrr, rmrm, rrrr, rrrr, mrrm) of propylene unit linkages composed of head-to-tail bonds. The chemical shift of the peak based on the methyl group of the third unit of the 5-unit propylene unit expressed in mmmm is set to 21.8 ppm, and the other carbon peaks are based on this. Determine chemical shift. According to this standard, in the case of other five 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 They are 20.8 ppm, rrrr: 20.3-20.5 ppm, rrrm: 20.1-20.3 ppm, mrrm: 19.9-20.1 ppm. The chemical shift of the peak derived from these pentads varies slightly depending on the NMR measurement conditions, and the peak is not necessarily a single peak, but a complex splitting pattern based on a fine structure ( It should be noted that the split pattern) is often shown.

The propylene-based polymer in the present invention is the above pentad that appears in the range of 19.8 ppm to 22.2 ppm when the chemical shift of the peak top of the peak represented by mmmm is 21.8 ppm. That is, the ratio of the area S ₁ having a peak top of 21.8 ppm to the total area S of peaks belonging to all pentads of mmmm, mmr, rmr, mmrr, mmrm and rmrr, rmrm, rrrm, mrrm (S ₁ / S) is 10% or more and 60% or less, and 4 + 2S ₁ / S ₂ > 5, where S ₂ is an area of a peak (mmmmr) having a peak top of 21.5 to 21.7 ppm. desirable.

These requirements are as described above: “A highly crystalline block and a highly amorphous block coexist in the main chain, and the highly crystalline block has a structure rich in isotacticity. related to being. Incidentally, when the ratio of S ₁ with respect to S is less than 10%, the crystallinity is too low, can not be obtained sufficient adhesion, furthermore, it is prone for problems such as stickiness undesirable. on the other hand, when the ratio of S ₁ with respect to S exceeds 60%, the crystallinity is too high, S for S defined in order to decrease solubility in a solvent, which is not preferable. the present invention The range of the ratio of ₁ is 10% or more and 60% or less, preferably 20% or more and 50% or less, more preferably 25% or more and 45% or less.

Further, it is desirable that the propylene-based polymer in the present invention satisfies the relationship of 4 + 2S ₁ / S ₂ > 5. This relational expression is closely related to an index named as an isotactic block index (BI) by Waymouth et al. BI is an index representing the stereoblock property of the polymer, and is defined by BI = 4 + 2 [mmmm] / [mmmr]. More specifically, BI represents the average chain length of isotactic blocks having 4 or more propylene units (JW Colllete et al., Macromol., 22, 3858 (1989); JC Randall, J. Polym. Sci. Polym. Phys. Ed., 14, 2083 (1976)). For statistically perfect atactic polypropylene, BI = 5. Therefore, 4 + 2 [mmmm] / [mmmr]> 5 means that the average chain length of isotactic blocks contained in the polymer is longer than that of atactic polypropylene.

The 4 + 2S ₁ / S ₂ required by the propylene-based polymer in the present invention is not completely identical to the above-mentioned BI, but generally corresponds to the requirement 4 + 2S ₁ / S ₂ > 5. This means that, unlike atactic polypropylene, this polymer contains an isotactic block having a crystallizable chain length. The presence of an isotactic block means that, in other words, a block composed of a sequence having a disordered stereospecificity is also present in the main chain.

As described above, the propylene-based polymer of the present invention has a crystalline block and an amorphous block coexisting in the main chain, and the crystalline block has an isochron having a relatively long average chain length. It is a unique structure that is formed from a tactic block and is rich in isotacticity. In the propylene polymer of the present invention, 4 + 2S ₁ / S ₂ > 5 may be satisfied, but 4 + 2S ₁ / S ₂ > 6 is preferable, and 4 + 2S ₁ / S ₂ > 7 is more preferable.
In 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 the solvent decreases, which is not preferable.

  The propylene-based polymer of the present invention preferably has a melting point [Tm] measured by a differential scanning calorimeter of 100 ° C. or lower, or does not exhibit a heat of crystal fusion of 5 J / g or higher. The melting point is related to the uniform and random presence of the crystalline block structure and the amorphous block structure. Therefore, in the case of a propylene polymer having a melting point [Tm] of 100 ° C. or lower or no crystal melting heat of 5 J / g or more, the solubility of the modified propylene polymer formed from the propylene polymer in a solvent is good. It is easy to make a coating solution. When [Tm] exceeds 100 ° C., the crystallinity is too high, which is not preferable in terms of solubility in a solvent.

  The production method of the propylene polymer of the present invention may be any production 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 using a Pd / C catalyst in the presence of hydrogen, etc. . A preferable production method includes a production method using a single site catalyst. The reason for this is that, in general, single-site catalysts can control microtacticity by ligand design, can easily produce polymers with relatively low molecular weight, and are particularly sharp in molecular weight distribution and stereoregularity distribution. Is mentioned. If the molecular weight distribution or the stereoregular distribution is irregular, the solubility may be different, and a partially insoluble one may be formed.

Of the single-site catalysts, metallocene catalysts are preferably used in that the microtacticity can be precisely controlled.
As the single site catalyst for producing the propylene polymer of the present invention, a metallocene catalyst having a metallocene compound ([A] component) and a cocatalyst ([B] component) as essential components is preferably used.

The metallocene compound ([A] component), C ₁ having a transition metal-containing bridging group - Symmetry ansa - metallocene (ansa-metallocene) is preferred. Non-crosslinked metallocene is also applicable to the production of the propylene-based polymer of the present invention. In general, an ansa-metallocene having a crosslinking group is preferable from an industrial standpoint because it is superior in thermal stability and the like. .

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

The [A] component metallocene compound preferably used for the production of the propylene polymer is a compound represented by the following general formula (1) and having C ₁ -symmetry. A plurality of metallocene compounds represented by the general formula may be mixed and used.

In the general formula (1), Q is a bonding group that bridges two conjugated 5-membered ring ligands, M is a group 4 transition metal of the periodic table, 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, and a 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. 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.

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

  In addition, as a metallocene compound, the mixture of the compound which has several different structures may be used, and may be used in combination of 2 or more types. Further, a known solid catalyst mainly composed of titanium trichloride and a carrier-supported catalyst containing magnesium, titanium, and halogen as essential components can be used supplementarily. Further, the [A] component may be newly added at the end of the first stage of polymerization or before the start of polymerization in the second stage.

  In the present invention, the cocatalyst used as the component [B] includes (1) an organoaluminum oxy compound as an essential component and (2) a reaction with a transition metal of the component [A] to convert the component [A] into a cation. One or more substances selected from the group consisting of an ionic compound capable of forming (3) a Lewis acid, and (4) an ion-exchange layered compound or an inorganic silicate excluding silicate are used.

  In the production of the main chain of the propylene polymer of the present invention, an organoaluminum compound may be used as an optional component [C] in addition to the cocatalyst [B] component. Specifically, it is a trialkylaluminum, a halogen- or alkoxy-containing alkylaluminum, or a hydrogen-containing organoaluminum compound. Of these, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, and triisobutylaluminum is particularly preferable. Two or more of these optional components may be used in combination. Further, an optional component [C] may be newly added after the start of polymerization.

The metallocene-based catalyst can be obtained by contacting the [A] component, the [B] component, and the optional [C] component, but the contacting method is not particularly limited. This contact may be performed not only during catalyst preparation but also during prepolymerization or polymerization of propylene.
A solid of an inorganic oxide such as a propylene polymer, silica, alumina, or the like may be allowed to coexist or contact when the catalyst components are contacted or after 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 poisoning 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.

  Although there is no restriction | limiting in particular in the usage-amount of each component of a catalyst, When using the ion-exchange layered compound except a silicate, or an inorganic silicate as a [B] component, [A] component per 1g of [B] component Is 0.0001 to 10 mmol, preferably 0.001 to 5 mmol, and the [C] component is 0 to 10,000 mmol, preferably 0.01 to 100 mmol. The atomic ratio of the transition metal in the [A] component and the aluminum in the [C] component is controlled to be 1: 0 to 1,000,000, preferably 1: 0.1 to 100,000. Is preferable in terms of polymerization activity.

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

  As the catalyst, it is also possible to use a polymer obtained by preliminarily polymerizing propylene and washing it as necessary. 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, or 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, methylcyclohexane, or a liquid of liquefied propylene. Of these, the polymerization is preferably performed in the presence of the above-described inert hydrocarbon.

  Specifically, the propylene polymer is produced in the presence of the [A] component and the [B] component, or the [A] component, the [B] component, and the [C] component. The polymerization temperature, polymerization pressure, and polymerization time are not particularly limited, but usually optimum settings can be made in consideration of productivity and process capability from the following ranges. That is, the polymerization temperature is usually 0 to 150 ° C., preferably 20 to 100 ° C., 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 reason, conventionally known methods can be used to adjust the molecular weight of the polymer. That is, 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. Hydrogen is preferred when a chain transfer agent is used.

Further, the head in the present invention - tail (head to tail) propylene-based polymer produced by controlling the stereoselectivity of propylene unit chain consisting of binding, as described above at ^{13 C-NMR,} head - When a peak derived from the carbon atom of the methyl group in the propylene unit chain portion composed of a tail bond was observed, and the chemical shift of the peak top of the peak attributed to the pentad represented by mmmm was 21.8 ppm, 19. The ratio (S ₁ / S) of the peak area S ₁ having a peak top of 21.8 ppm to the peak area S belonging to all pentads appearing in the range of 8 ppm to 22.2 ppm is 10% or more and 60% or less. and it is preferable the area of the peak (mmmr) having a peak top is _{4 + S 1 / S 2>} 5 when the _{S 2} to 21.5~21.7ppm

  There is no particular limitation on the method for controlling the stereoselectivity related to such properties of the propylene-based polymer, but in general, a method of controlling by the structure of the catalyst and a method of controlling by controlling the polymerization conditions can be mentioned. . When controlling the stereoselectivity by controlling the polymerization conditions, the desired stereoregularity can be achieved by controlling the polymerization temperature and the monomer concentration, and, in some cases, in conjunction with the above-described catalyst structure control. A propylene polymer can be obtained.

  The modified propylene polymer in the present invention has a main chain composed of the propylene polymer and a side chain containing a carboxylic acid group, an acid anhydride group, or a carboxylic acid ester group, and is generally a main chain. It is obtained by graft copolymerizing a polymerizable monomer having a carboxylic acid group or the like with the propylene polymer. Examples of the polymerizable monomer to be graft copolymerized include (meth) acrylic acid and esters thereof, and monoolefin dicarboxylic acid, acid anhydrides and monoalkyl esters thereof, and at least one selected from them is Used.

  Specifically, (meth) acrylic acid and esters thereof include (meth) acrylic acid; (meth) acrylic acid ester monomers having an alkyl group having 1 to 12 carbon atoms, such as (meth) Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t- (meth) acrylic acid Butyl, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, (meth) acryl Decyl acid, dodecyl (meth) acrylate, etc .; aryl group or arylalkyl having 6 to 12 carbon atoms Having a group (meth) acrylic acid ester monomers such as (meth) acrylate, phenyl (meth) toluyl acrylate include benzyl (meth) acrylate and the like.

  Furthermore, as other (meth) acrylic acid esters, a (meth) acrylic acid ester-based monomer having a C 1-20 alkyl group containing a hetero atom, for example, hydroxyethyl (meth) acrylic acid, (meta ) Dimethylaminoethyl acrylate, diethylaminoethyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, (meth ) Glycidyl acrylate, adducts of (meth) acrylic acid ethylene oxide, etc .; (meth) acrylic acid ester monomers having 1 to 20 carbon atoms containing fluorine atoms, such as trifluoro (meth) acrylic acid Methylmethyl, 2-trifluoromethylethyl (meth) acrylate, (meth) Acrylic acid 2-perfluoroethyl ethyl, and the like; (meth) acrylamide monomers such as (meth) acrylamide, (meth) acrylic dimethyl amides.

  Monoolefin dicarboxylic acid and acid anhydrides thereof, and monoalkyl esters of monoolefin dicarboxylic acid may be mentioned. Examples of monoolefin dicarboxylic acid include maleic acid, chloromaleic acid, citraconic acid, itaconic acid, glutaconic acid, 3 -Methyl-2-pentene / diacid, 2-methyl-2-pentene / dioic acid, 2-hexene / dioic acid and the like. Examples of monoalkyl esters of monoolefin dicarboxylic acids include esters of these acids with alkyl alcohols having 1 to 12 carbon atoms. Specific examples of alkyl alcohols include methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol. , Pentyl alcohol, octyl alcohol, cyclohexyl alcohol and the like.

  When a coating film is formed using the coating composition of the present invention, from the viewpoint of adhesion between the coating film and the paint, as a polymerizable monomer containing these grafted carboxylic acid groups, the solubility parameter is The higher one is preferable, that is, an unsaturated carboxylic acid derivative component composed of an unsaturated carboxylic acid having 3 to 10 carbon atoms, an acid anhydride and an ester thereof is preferable. Particularly preferred is maleic anhydride. Here, the solubility parameter is represented by a minute heat of dissolution representing the interaction between the solute and the solvent (R. F. Fedors, Polym. Eng. Sci., 14, 147 (1974)).

  Among the graft-modified propylene polymers used in the present invention, the modified propylene polymer having a monoolefin dicarboxylic acid monoalkyl ester as a graft copolymer unit is, for example, a monoolefin dicarboxylic acid monoalkyl ester converted to a propylene polymer. A method of graft copolymerization with a monoolefin dicarboxylic acid or an acid anhydride thereof onto a propylene polymer, followed by esterification of one of the carboxylic acid groups with an alkyl alcohol.

  The graft amount of at least one graft copolymer unit selected from polymerizable monomers containing a carboxyl group or the like in the modified propylene polymer, that is, the content (graft ratio) in the modified propylene polymer is 0. The graft copolymerization may be carried out so as to be 0.01 to 25% by weight, preferably 0.1 to 15% by weight. When a modified propylene polymer having a graft ratio within this range is applied to a molded product using a composition containing this as a primer, a coating film with high adhesion of the paint is obtained. Is preferable in terms of good adhesion and good appearance.

  Various known methods can be used as a method of graft copolymerizing a polymerizable monomer such as monoolefin dicarboxylic acid, its acid anhydride and monoolefin dicarboxylic acid monoalkyl ester with the propylene-based polymer. For example, a method of conducting a graft copolymerization reaction by dissolving a propylene polymer in an organic solvent, adding the above-mentioned grafting polymerizable monomer and radical polymerization initiator and stirring under heating; heating the propylene polymer; Graft copolymerization by adding a polymerizable monomer and a radical polymerization initiator which are dissolved and grafted to the melt and stirring; or graft copolymerization while heating and kneading each component to an extruder A method of impregnating a propylene-based polymer powder with a solution obtained by dissolving the graft copolymerization unit and the radical polymerization initiator in an organic solvent, and then heating to a temperature at which the powder does not dissolve to graft copolymerize. It is done.

At this time, the ratio of radical polymerization initiator / polymerizable monomer to be grafted is usually in the range of 1/100 to 3/5, preferably 1/20 to 1/2 in terms of 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 examples thereof include organic peroxides and azonitriles. Organic peroxides 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-butylperoxyisopropyl monocarbonate, diisopropyl peroxycarbonate, dicyclohexyl peroxycarbonate, and the like. Examples of the azonitrile include azobisbutyronitrile and azobisisopropylnitrile. Of these, benzoyl peroxide, dicumyl peroxide, and t-butylperoxyisopropyl monocarbonate are preferred.

  When the graft copolymerization reaction is performed using an organic solvent, specific examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, xylene; n-hexane, n-heptane, n-octane, Aliphatic hydrocarbons such as n-decane; halogenated hydrocarbons such as trichloroethylene, perchlorethylene, chlorobenzene, o-dichlorobenzene and the like. Among these, aromatic hydrocarbons or halogenated hydrocarbons are preferable. In particular, toluene, xylene and chlorobenzene are preferred.

The propylene polymer and the modified propylene polymer in the present invention can be dissolved in toluene, which is a general-purpose solvent for paints, adhesion, primers, inks, and the like.
The solubility of the propylene-based polymer and the modified propylene-based polymer of the present invention is very superior to that of a normal highly stereoregular isotactic polypropylene-modified product, and is 10% by weight in room temperature toluene (25 ° C.). When dissolved, the insoluble component is 1% by weight or less of the whole polymer. Preferably it is 0.1 weight% or less, More preferably, it is a state without an insoluble component.
As a measuring method, for example, a solution dissolved at a predetermined temperature and a predetermined concentration is filtered in the vicinity of the temperature (filtered when hot when the temperature is high), and the filter paper used at that time or a SUS wire mesh (weight in advance) The method of measuring the weight of insoluble matter is used.

Usually, even if the solution of the crystalline polymer is a solution having excellent solubility, the solubility decreases as the temperature is lowered, particularly below freezing point, and as a result, the solution tends to be gelled or crystallized.
The coating composition of the present invention contains at least one of the propylene polymer and modified propylene polymer and a specific organic solvent, that is, an alicyclic hydrocarbon having 7 to 12 carbon atoms. The propylene polymer and the modified propylene polymer are extremely soluble in the alicyclic hydrocarbon solvent having 7 to 12 carbon atoms, and the propylene polymer and the modified propylene polymer are converted into the alicyclic carbonization. A composition in which 50 parts by weight or less is dissolved in a hydrogen solvent has excellent properties at low temperature fluidity.

  The alicyclic hydrocarbon solvent having 7 to 12 carbon atoms is an alicyclic hydrocarbon that may have a lower alkyl group having 1 to 4 carbon atoms. Specific examples thereof include methylcyclohexane, ethylcyclohexane, dimethyl Examples include cyclohexane and decalin. Among these, methylcyclohexane is preferable.

The ratio (weight) of the propylene polymer and / or modified propylene polymer and the solvent in the coating composition of the present invention is 5/95 to 50/50, preferably 10/90 to 40/60. More preferably, it is 15/85 to 30/70.
In the solvent, it is essential to contain an alicyclic hydrocarbon having 7 to 12 carbon atoms, but other solvents may coexist as long as the properties of the composition of the present invention are not impaired. The content ratio (weight ratio) of the alicyclic hydrocarbon and the other solvent is 100/0 to 50/50, preferably 100/0 to 70/30. If the amount of the other solvent is too much beyond this range, the low temperature fluidity is lowered, which is not preferable.

  Specific examples of other solvents include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane and n-decane; Halogenated hydrocarbons such as methylene, carbon tetrachloride, trichloroethylene, perchlorethylene, chlorobenzene, o-dichlorobenzene, esters such as n-ethyl acetate and n-butyl acetate, ketones such as methyl isobutyl ketone and cyclohexanone, Examples include polar solvents such as tetrahydrofuran and dimethyl sulfoxide. Among these, aromatic hydrocarbons are preferable, and toluene and xylene are particularly preferable.

  The coating composition of the present invention has excellent adhesion to a molded body (base material) of an olefin polymer having crystallinity, and can be applied to a base material and used for coating film formation. Examples of the olefin polymer as the base material include high-pressure polyethylene, medium-low pressure polyethylene, polypropylene, poly-4-methyl-1-pentene, poly-1-butene, polystyrene and other olefin polymers, ethylene / propylene copolymer. Examples thereof include olefin copolymers such as polymers, ethylene / butene copolymers, and propylene / butene copolymers. Of these olefin copolymers, propylene-based polymers are preferably used. Also, molded products made of polypropylene and synthetic rubber, molded products made of polyamide resin, unsaturated polyester resin, polybutylene terephthalate resin, polycarbonate resin, etc., such as molded products such as bumpers for automobiles, and also for steel plates and electrodeposition treatment It can also be used for surface treatment of steel plates and the like. In addition, the surface is coated with paint, primer, adhesive, etc. mainly composed of polyurethane resin, fatty acid-modified polyester resin, oil-free polyester resin, melamine resin, epoxy resin, etc., and adherence of paint, etc. to the surface Can be used to form a coating film that is excellent in sharpness and low-temperature impact properties.

  The propylene-based polymer and modified propylene-based polymer of the present invention have excellent adhesion to a crystalline polypropylene molded body as a base material, and the adhesion by an adhesion test (cross-cut tape method) described below. 50/100 or more. Preferably it is 80/100 or more, More preferably, it is 100/100.

In the present invention, the adhesion between the propylene polymer and the modified propylene polymer is determined by the following adhesion test method.
Adhesion test method (A) The adhesion test was conducted according to JIS K5400 8.5.2. Is performed according to the cross-cut tape method described in 1.
(1) Summary
Cut through the coating film on the test piece and reach the ground surface in a grid pattern, apply adhesive tape on the grid pattern, and visually observe the state of adhesion of the coating film after peeling.
(2) Apparatus and material (a) Cutter knife According to JIS K5400 7.2 (2) (e).
(B) Cutter guide JIS K5400 8.5.1. (2) According to (b).
(C) Cellophane adhesive tape A 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 A polypropylene molded body (150 mm × 70 mm × 3 mm) is used.
(E) Eraser Those specified in JIS S6050.

(3) Preparation of a test piece A sample prepared on one side of a test plate is coated and dried by the method specified in the product standard of the sample according to JIS K5400 3.3, and then left in a standard state for 24 hours.
(4) Operation
JIS K5400 8.5.2. Follow (4).
(5) Evaluation Evaluation is as follows.
(A) Observe the state of the grid-like scratches on the coated surface of the test piece, count the number of grids that were not peeled out of the 100 grids, and indicate the number of residual grids / 100. And adherence.

The polypropylene substrate used in the adhesion test of the present invention is a crystalline polypropylene molded body. The crystalline polypropylene here is a propylene homopolymer and / or a propylene / ethylene block copolymer comprising a propylene homopolymer portion and a propylene / ethylene copolymer portion.
The propylene / ethylene block copolymer is a propylene / ethylene block copolymer containing a crystalline polypropylene part (a unit part) and an ethylene / propylene random copolymer part (b unit part). The a unit is usually obtained by homopolymerization of propylene, and in some cases, by copolymerizing propylene with a small amount of other α-olefin. On the other hand, the b unit is a rubbery component obtained by random copolymerization of propylene and ethylene.

  The propylene content of the propylene / ethylene copolymer part (b unit part) is preferably 30 to 85% by weight, more preferably 40 to 80% by weight, and still more preferably 50 to 75% by weight. Although there is no restriction | limiting in particular about the quantity of a unit part and b unit part, Generally a unit part becomes like this. Preferably it is 50 to 100 weight% of total polymerization amount, More preferably, it is 60 to 100 weight%.

  Since the coating film formed when the coating composition of the present invention is applied exhibits good adhesion to the base olefin polymer, it can be used as an adhesive for the olefin polymer. it can. In addition, in order to obtain favorable adhesiveness, it is preferable to heat after application. Although there is no restriction | limiting in particular in heating temperature, Considering practicality, it is preferable to set it as 50-150 degreeC, Furthermore, it is 60-130 degreeC. There is no restriction | limiting in particular also in the method of application | coating, A conventionally well-known method, such as the method of apply | coating with a spray, the method of apply | coating with a roller, the method of applying with a brush, can be used.

A coating material can be applied to the surface of a molded article on which the coating composition of the present invention has been applied to form a coating film by a method such as electrostatic coating, spray coating, or brush coating.
The coating may be applied by a method of overcoating after undercoating. After applying the paint, the coating film is cured in accordance with a normal method of heating with nichrome wire, infrared rays, high frequency, etc., and a molded product having a desired coating film 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 of the present invention is applied to the surface of a molded product comprising an α-olefin copolymer or other polymer as a main component, and the coating film has adhesiveness, water resistance and gasoline resistance to the surface. It can be used as a primer or the like for improving performance. In addition to the use as a primer for the above-mentioned molded product, taking advantage of its excellent adhesion, peel strength, and water resistance, it can be applied to a wide range of applications. For example, it can be added for adhesives and paints. Needless to say, the present invention can also be applied to the use of agents.
Furthermore, in addition to the above, the coating composition of the present invention may contain various stabilizers such as antioxidants, weathering stabilizers, heat resistance inhibitors, etc .; colorants such as titanium oxide and organic pigments; carbon black, ferrite, etc. It may contain a conductivity imparting agent or the like.

In addition, a molded article to which the coating composition of the present invention is applied is obtained by molding the above-mentioned various polymers or resins by any of known molding methods such as injection molding, compression molding, hollow molding, extrusion molding, and rotational molding. It may be what was done.
The coating composition of the present invention is particularly suitable for coatings even when the molded product to which it is applied contains an inorganic filler such as talc, zinc white, glass fiber, titanium white, magnesium sulfate, or a pigment. A coating film with good properties can be formed.

In addition to the above, the molded article to which the coating composition of the present invention is applied may contain various stabilizers, ultraviolet absorbers and the like.
Stabilizers preferably used for molded products include, for example, 2,6-di-tert-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-tert-butylphenol), 2,2-thiobis (4-methyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-) phenolic stabilizers such as t-butyl-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; thiodiglycol propoxycarbonyl sulfonates, sulfur-based stabilizers such as distearyl thiodipropionate.
Examples of the ultraviolet absorber used include 2-hydroxy-4-octoxybenzophenone, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, paraoctylphenyl salicylate, and the like.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited by these Examples, unless the summary is exceeded.
In the following examples and comparative examples, the physical properties and performance of the polymers were measured as follows. In each example, the catalyst synthesis step and the polymerization step were all carried out under a purified nitrogen atmosphere, and the solvent was dehydrated with molecular sieve (MS-4A) and then degassed by bubbling with purified nitrogen.

Measurement of physical properties of propylene polymer 1) Molecular weight measurement of propylene polymer Weight average molecular weight Mw, number average molecular weight Mn, and molecular weight distribution Mw / Mn were measured using GPC (150CV type manufactured by Waters). As a solvent, o-dichlorobenzene was used, and the measurement temperature was 135 ° C.
2) The pentad S ₁ / S and the block index 4 + S1 / S ₂ of the propylene unit chain part were measured and calculated by the ¹³ C-NMR spectrum measurement method described above.

3) Solubility test method A polymer is charged in toluene at a concentration of 10% by weight in a separable flask equipped with a stirring blade, and the temperature is raised to about 110 ° C. to dissolve. Stirring is continued for 2 hours after the internal temperature becomes constant. Then, after naturally cooling to 30 ° C., it is allowed to stand for 1 hour and filtered through a SUS wire mesh No. 400. What remains in the wire mesh is insoluble, and what is passed as a solution is soluble, and is dried in a vacuum dryer at 80 ° C., 1 mmHg or less for 4 hours. Weigh and calculate the fraction of insoluble matter.
Evaluation criteria ○: Insoluble matter 1% or less, x: Insoluble matter 1% or more.

4) Non-tackiness was evaluated by a finger tackiness test.
Evaluation criteria ○: Excellent non-tackiness, Δ: Slightly tacky, ×: Tacky.

5) Adhesion test of propylene-based polymer and the like (a) The adhesion test was performed according to the above-described adhesion test method.
The preparation conditions of the test pieces are described in the examples.
The following molded product was used as the substrate of the test piece <Substrate Example 1>
Polypropylene MA3U (Propylene Homopolymer; MFR 15g / 10 min (230 ° C, 21.18N load) made by Nippon Polychem Co., Ltd.) Molded a test piece substrate with a thickness of 3mm and 150mm x 70mm at a molding temperature of 240 ° C with a screw in-line injection molding machine did.
(B) In the water resistance test, a test piece (painted product) is prepared in the same manner as the adhesion test, and the coated product cured at room temperature is immersed in warm water kept at 40 ° C. for 10 days. Thereafter, after moisture on the surface was dried, the test was performed in the same manner as the adhesion test method.

[Production Example 1]
(1) Synthesis of dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl] hafnium

(1) -1 Ligand Synthesis 2-Methylazulene (4.01 g) was dissolved in tetrahydrofuran (56 ml), cooled to 0 ° C. with an ice bath, and then at the same temperature with a diethyl ether solution of methyllithium (1. 14 mol / l) 24.8 ml was added dropwise. After completion of dropping, the ice bath was removed and the mixture was stirred for 2 hours. This solution was slowly added dropwise to a tetrahydrofuran solution (140 ml) of dimethylsilyl dichloride (34.0 ml, 0.280 mol) cooled to 0 ° C. in an ice bath. After completion of the dropping, the ice bath was removed and the mixture was stirred for 3 hours, and then the solvent and unreacted dimethylsilyl dichloride were distilled off under reduced pressure. Tetrahydrofuran (80 ml) was added and the mixture was cooled to 0 ° C., and cyclopentadienyl sodium (2.1 mol / l, 26.9 ml, 56.5 mmol) was gradually added dropwise. After completion of the addition, the mixture was stirred at room temperature for 12 hours. After completion of the stirring, water was added and the target compound was extracted with diethyl ether. The extracted solution was dehydrated with magnesium sulfate and then dried to obtain an unpurified product of the target ligand. The crude product was purified by silica gel column chromatography using n-hexane as an elution solvent to obtain the target 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. with 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 dropping, the ice bath was removed and the mixture was stirred for 3 hours, and the solvent was distilled off under reduced pressure. Toluene (60 ml) was added to the residue obtained after distilling off, followed by cooling to -78 ° C. A suspension of toluene (140 ml) in hafnium tetrachloride (7.17 g) cooled to -78 ° C was slowly added thereto. 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. The target complex was extracted from this brown powder with hot n-hexane (180 ml × 3 times). After the extract solution was dried to dryness, the obtained solid was 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 listed below.
¹ H-NMR (CDCl ₃ ): δ0.85 (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 minerals Demineralized water (110 ml), magnesium sulfate heptahydrate (22.2 g) and sulfuric acid (18.2 g) were collected in a 1,000 ml round bottom flask and dissolved with stirring. It 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. Then, it cooled to room temperature over 1 hour, and obtained slurry was filtered and the wet cake was collect | recovered. The collected cake was slurried again with demineralized water (500 ml) in a 1,000 ml round bottom flask and filtered. This operation was repeated twice. The finally obtained cake 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 (0.44 g) obtained in Production Example 1 (2) was added a toluene solution of triethylaluminum (0.4 mmol / ml, 2.0 ml), and the mixture was stirred at room temperature for 1 hour. 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 another flask, triisobutylaluminum (0.114 mmol) manufactured by Tosoh Akzo Corporation was collected, and the clay slurry (3.8 ml) obtained here and the complex (6) obtained in Production Example 1 (1) -2 were used. (0.02 mg, 11.4 mmol) of toluene diluted solution was added and stirred at room temperature for 10 minutes to obtain a catalyst slurry.

  Subsequently, toluene (750 ml), triisobutylaluminum (1.9 mmol) and liquid propylene (180 ml) were introduced into an induction stirring autoclave having an internal volume of 2 liters. The whole amount of the catalyst slurry was introduced at room temperature, the temperature was raised to 60 ° C., and the total pressure during polymerization was kept constant at 0.7 MPa, and stirring was continued for 1 hour at the same temperature. After completion of the stirring, unreacted propylene was purged to terminate the polymerization. The autoclave was opened and the whole toluene solution of the polymer was recovered, and the solvent and the clay residue were removed. As a result, 23.2 g of a propylene polymer was obtained. The results of analyzing the obtained polymer are summarized in Table 1.

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

[Production Example 3]
(2) Chemical treatment of clay mineral Demineralized water (72 ml), lithium sulfate monohydrate (11 g) and sulfuric acid (17 g) were collected in a 1,000 ml round bottom flask and dissolved under stirring. In this solution, commercially available granulated montmorillonite (manufactured by Mizusawa Chemical Co., Ltd .; Benclay SL, 22 g) was dispersed, heated to 100 ° C. over 0.5 hours, and stirred at 100 ° C. for 5 hours. Then, it cooled to room temperature over 1 hour, and obtained slurry was filtered and the wet cake was collect | recovered. The collected cake was slurried again with demineralized water (500 ml) in a 1,000 ml round bottom flask and filtered. This operation was repeated twice. The finally obtained cake was dried overnight at 200 ° C. under a nitrogen atmosphere to obtain chemically treated montmorillonite (15.6 g).

(3) Polymerization To a chemically treated montmorillonite (0.25 g) obtained in Production Example 3 (2), a toluene solution of triethylaluminum (0.5 mmol / ml, 1.0 ml) was added and stirred at room temperature for 0.5 hour. did. Toluene (10 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).
To another flask, triisobutylaluminum (0.015 mmol) manufactured by Tosoh Akzo Corporation was collected, and a toluene diluted solution of the complex (3.89 mg, 7.5 μmol) obtained in Production Example 1 (1) -2 was added. The mixture was stirred at room temperature for 10 minutes to obtain a catalyst slurry.

  Next, triisobutylaluminum (0.13 mmol), toluene (1100 ml) and the above catalyst slurry were all introduced into an induction stirring autoclave having an internal volume of 2 liters. At 25 ° C., liquid propylene (264 ml) was introduced, and ethylene was further introduced at an ethylene partial pressure of 0.025 MPa. After raising the temperature to 80 ° C., ethylene gas was sequentially added at a rate of 0.1 MPa · L per hour, and propylene was successively added so that the total pressure in the container was maintained at 0.85 MPa. And stirring was continued for 1.5 hours. After completion of the stirring, the unreacted monomer was purged to terminate the polymerization. The autoclave was opened and the entire toluene solution of the polymer was recovered, and the solvent and clay residue were removed. As a result, 146 g of a propylene-ethylene copolymer was obtained. The results of analyzing the obtained coaggregates are summarized in Table 1.

[Production Example 4]
(1) Synthesis of racemic dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azurenyl]} 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 an n-pentane solution of t-butyllithium (33 ml, 50.6 mmol, 1.54N) was added. Added dropwise at -78 ° C. The mixture was stirred at −10 ° C. for 2 hours, 2-ethylazulene (3.55 g, 22.8 mmol) was added to this 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 more. N-Hexane (30 ml) and tetrahydrofuran (40 ml) were added to the obtained yellow precipitate at 0 ° C. Next, N-methylimidazole (50 μl) 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 phases were separated. The organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-biphenyl)- A crude product (8.3 g) of 1,4-dihydroazulene was obtained.

Next, the crude product obtained above was dissolved in diethyl ether (30 ml), and an n-butyllithium n-hexane solution (14.9 ml, 22.8 mmol, 1.53N) was added dropwise at -70 ° C. The temperature was gradually raised and the mixture was stirred overnight at room temperature. Furthermore, toluene (200 ml) was added, and 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. From the resulting slurry, most of the solvent was distilled off under reduced pressure, diethyl ether (50 ml) was added, and the resulting slurry was filtered. After washing with diethyl ether (5 ml × 2), ethanol (15 ml × 2), n-hexane (10 ml × 2), dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4 A racemic meso mixture (4.53 g, 42% yield) of -biphenylyl) -4H-azurenyl]} hafnium was obtained. The obtained racemic / meso mixture was analyzed by ¹ H-NMR. As a result, it was found to be a mixture of racemic 76.6% and meso 23.4%.

  The racemic / meso mixture (4.5 g) obtained here 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. Toluene (25 ml) and dichloromethane (11 ml) were added to the obtained solid, and the mixture was heated to 60 ° C. to obtain a homogeneous solution. When dichloromethane was distilled off under reduced pressure, crystals were precipitated. The obtained crystals were filtered, washed twice with hexane (5 ml), and dried under reduced pressure to obtain a racemate (1.79 g).

(2) Chemical treatment of clay mineral After adding 55.85 g of demineralized water, 32.70 g of sulfuric acid and 8.01 g of lithium hydroxide to a 500 ml round bottom flask and stirring, montmorillonite (Mizusawa Chemical; Mizusawa smectite) 51. 65 g was added, heated to 140 minutes under reflux. After adding 300 ml of demineralized water and suction filtration, the solid component was dispersed in 600 ml of demineralized water and subjected to suction filtration. This operation was repeated once more. The residue obtained by filtration was dried at 100 ° C. to obtain acid and metal salt-treated montmorillonite.
1.05 g of the acid and metal salt-treated montmorillonite obtained here was collected in a 100 ml round bottom flask and dried by heating at 200 ° C. for 2 hours under reduced pressure. To this, 4.0 ml of a toluene solution of triethylaluminum (0.5 mmol / ml) was added under purified nitrogen, reacted at room temperature for 30 minutes, washed twice with 30 ml of toluene, and containing 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 4 (2) to make the amount of residual toluene 1.0 ml. To this slurry was added a toluene solution of triisobutylaluminum (0.5 mmol / ml, 0.5 ml), and dichloro {1,1′-dimethylsilylenebis [2-ethyl-] synthesized in Production Example 4 (1) was further added. 4- (2-Fluoro-4-biphenylyl) -4H-azurenyl]} hafnium racemic toluene solution (3.0 μmol / 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 total amount of the catalyst slurry were introduced under purified nitrogen. Under stirring, 11.0 g of propylene was introduced, and prepolymerization was performed at 30 ° C. for 2 hours and then at 50 ° C. for 0.5 hour. After pre-polymerization, unreacted propylene was purged, and after pressure substitution with purified nitrogen 0.5 MPa twice, the pre-polymerization catalyst was taken out. This contained 9.7 g of polymer per gram of chemically treated montmorillonite component.

(4) Polymerization A 2-liter induction-stirring autoclave containing a built-in stirring blade was replaced with purified nitrogen, and then 750 g of liquefied propylene was charged at 25 ° C. A toluene solution of triisobutylaluminum (0.1 mmol / ml, 5.0 ml) was injected at the same temperature, and the temperature was raised to 70 ° C. Hydrogen was added so that the hydrogen concentration in the gas phase was 0.2 mol%, and then at 3O0C, 30.0 mg of the prepolymerized catalyst obtained in (3) above was added to initiate polymerization. After 1 hour, unreacted propylene was purged to complete the polymerization. The amount of the obtained propylene polymer was 384 g. The results of analyzing the obtained polymer are summarized in Table 1.
In addition, the peak derived from the carbon atom of the methyl group of the propylene unit chain part consisting of a head-to-tail bond by ¹³ C-NMR: [mmmm]> 99.9 (%), and most peaks derived from other pentads are I couldn't see it.

[Production Example 5]
Highly stereospecific isotactic polypropylene (31.1 g), heptane (180 ml), Pd / C (Aldrich: 10 wt% Pd / C) (7.87 g) in an induction-stirring microautoclave with an internal volume of 50 mL Was added, and the system was closed and 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, hydrogen was purged to stop the reaction. The autoclave was opened and the entire amount of the polymer heptane solution was recovered, 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 summarized in Table 1.
The physical properties of the highly 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%, [mmmmr]: 0.0%, [rmrm]: 0.1%, [rrrr]: 0.2%

[Production Example 17]
(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. In this solution, commercially available granulated montmorillonite (Mizusawa Chemical Benclay SL, 22 g) was dispersed, heated to 100 ° C., and stirred for 5 hours. Then, it cooled to room temperature over 1 hour, and obtained slurry was filtered and the wet cake was collect | recovered. The collected cake was slurried again with demineralized water (500 mL) in a 1000 mL round bottom flask and filtered. This operation was repeated three times. The finally obtained cake 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 a chemically treated montmorillonite (0.25 g) obtained in Production Example 1- (2) was added a toluene solution of triisobutylaluminum (0.5 mmol / ml, 1.0 ml), and the mixture was stirred at room temperature for 30 minutes. Stir. 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).
Triisobutylaluminum (0.15 mmol) manufactured by Nippon Alkyl Aluminum Co. was collected in another flask, 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) of toluene diluted, and stirred at room temperature for 10 minutes to obtain a catalyst slurry.

  Subsequently, 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. The whole amount of the catalyst slurry was introduced at room temperature, the temperature was raised to 80 ° C., and stirring was continued for 1 hour at the same temperature while keeping the total pressure during polymerization at 0.85 MPa. After completion of the stirring, unreacted propylene was purged to terminate the polymerization. When the autoclave was opened and the entire toluene solution of the polymer was recovered and the solvent and the clay residue were removed, 35 g of a propylene-1-hexene copolymer was obtained. The results of analyzing the resulting polymer are summarized in Table 1.

[Reference Example 1]
The physical properties of Ubekku UT-2115 manufactured by Ube Industries, Ltd. were measured in the same manner. The results are shown in Table 1.
[Reference Example 2]
The physical properties of Mitsui Chemicals Toughmer S4030 were measured in the same manner. The results are shown in Table 1.

[Production Example 6]
(1) Maleic anhydride modification of propylene polymer In a stainless pressure-resistant reaction vessel equipped with a thermometer and a stirrer, toluene (80 g), the propylene polymer obtained in Production Example 1 (3) (20 g) and maleic anhydride (2 g) was added, the inside of the container was replaced with nitrogen gas, and the temperature was raised to 110 ° C. After raising the temperature, a toluene solution of perbutyl I (t-butylperoxyisopropyl monocarbonate; manufactured by NOF Corporation) (1.4 g) was supplied in 2 hours using a metering pump, 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 filtered off. Further, precipitation and filtration were repeated with acetone, and the finally obtained polymer was washed with acetone. The polymer obtained after washing was dried under reduced pressure to obtain a white powdery modified polymer. As a result of infrared absorption spectrum measurement and neutralization titration of this modified polymer, the content of maleic anhydride groups was 1.1% by weight.

[Production Example 7]
The same operation as in Production Example 6 was carried out except that the amount of maleic anhydride was changed from 2 g to 3 g and the amount of perbutyl I was changed from 1.4 g to 2 g. Table 2 shows the measurement results of the graft ratio and physical properties of the resulting modified polymer.

[Production Example 8]
The same operation as in Production Example 6 was performed except that the polypropylene synthesized in Production Example 2 was used. Table 2 shows the measurement results of the graft ratio and physical properties of the resulting modified polymer.
[Production Example 9]
The same operation as in Production Example 8 was carried out except that 2 g of maleic anhydride was changed to 5 g of methacrylic acid and the amount of perbutyl I was changed from 1.4 g to 0.5 g. Table 2 shows the measurement results of the graft ratio and physical properties of the resulting modified polymer.

[Production Example 10]
The same operation as in Production Example 10 was performed except that 5 g of methacrylic acid was changed to 5 g of 2-ethylhexyl methacrylate. Table 2 shows the measurement results of the graft ratio and physical properties of the resulting modified polymer.
[Production Example 11]
The same operation as in Production Example 10 was performed except that 5 g of methacrylic acid was changed to 5 g of 2-ethylhexyl methacrylate and 5 g of styrene. Table 2 shows the measurement results of the graft ratio and physical properties of the resulting modified polymer.

[Production Example 12]
The same operation as in Production Example 6 was performed except that the polypropylene synthesized in Production Example 3 was used. Table 2 shows the measurement results of the graft ratio and physical properties of the resulting modified polymer.
[Production Example 13]
Same as Production Example 6 except that 20 g of the polypropylene synthesized in Production Example 2 was changed to 20 g of the polypropylene synthesized in Production Example 4, 80 g of toluene was changed to 80 g of chlorobenzene, and 1.4 g of perbutyl I was changed to 1.4 g of dicumyl peroxide. The operation was performed. Table 2 shows the measurement results of the graft ratio and physical properties of the resulting modified polymer.

[Production Example 14]
The same operation as in Production Example 6 was performed except that the polypropylene synthesized in Production Example 5 was used. Table 2 shows the measurement results of the graft ratio and physical properties of the resulting modified polymer.
[Production Example 15]
The same operation as in Production Example 6 was performed except that “Ubetak UT-2115” in Reference Example 1 was used. Table 2 shows the measurement results of the graft ratio and physical properties of the resulting modified polymer.

[Production Example 16]
The same operation as in Production Example 6 was performed except that “Toughmer S4030” in Reference Example 2 was used. Table 2 shows the measurement results of the graft ratio and physical properties of the resulting modified polymer.
[Production Example 18]
The same operation as in Production Example 6 was performed except that the propylene-1-hexene copolymer synthesized in Production Example 17 was used. Table 2 shows the measurement results of the graft ratio and physical properties of the resulting modified polymer.

[Example 1]
To 15 g of the modified propylene polymer obtained in Production Example 6, 85 g of methylcyclohexane was added as a solvent, heated to 110 ° C. and dissolved for 1 hour. After cooling the obtained solution to near room temperature, a 15% by weight solution of a modified propylene polymer was prepared as a coating composition through a # 400 SUS wire mesh. The following physical properties of the obtained coating composition were measured. The results are summarized in Table 3.

(1) Low temperature fluidity The coating composition was placed in a sample bottle and allowed to stand in a low temperature incubator set at -10 ° C, and the state was observed after 1 week.
Evaluation criteria ○: With fluidity, ×: Without fluidity

(2) Adhesion <Creation of test piece>
The coating composition obtained in Example 1 was spray applied to the injection-molded piece prepared in Substrate Example 1 (the surface was wiped with isopropyl alcohol). The application amount was 3 to 5 g / m ² . Next, this molded piece after application was allowed to stand at 25 ° C. for 10 minutes, and then dried in a safe ben dryer at 80 ° C. for 30 minutes. Next, the dried product was allowed to stand at 25 ° C. for 1 hour, and then, acrylic polyol urethane paint Retan PG80III (manufactured by Kansai Paint Co., Ltd .: trade name) was blended as a base coat on the coating film with a predetermined amount of curing agent. Then, adjust the viscosity with Ford Cup No. 4 with a special thinner, adjust the viscosity to 12 to 13 seconds, and then spray coat so that the dry coating amount is 50 to 60 g, in the Safe Ben dryer Was baked at 100 ° C. for 30 minutes. Furthermore, it left still at 24 degreeC for 24 hours, and was cured. Then, the adhesion test was done about the obtained coating material.

<Adhesion test>
In the adhesion test, a test piece with a grid pattern is created in accordance with the grid pattern test method described in JIS K5400, and cello tape (trade name) manufactured by Nichiban Co., Ltd. is pasted on the grid pattern of the test specimen. After that, this was quickly pulled in the vertical direction to be peeled off, and the number of grids that were not peeled out of 100 grids was counted as an index of adhesion.

(3) Water resistance test In the same manner as the preparation of the test piece of (2) above, the 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. . The coated product was immersed in warm water maintained at 40 ° C. for 10 days, and the state of the coating film was visually determined.
(4) Non-tack property test It evaluated by the above-mentioned finger tack property test.

[Examples 2 to 17, 19, 20]
In each example, in the same manner as in Example 1, coating compositions were prepared according to the blending ratios described in Table 3, and low-temperature fluidity, adhesion, water resistance, and non-tackiness were evaluated. The results are summarized in Table 3.

[Comparative Examples 1 to 17]
In each comparative example, in the same manner as in Example 1, coating compositions were prepared according to the blending ratios described in Table 3, and the low temperature fluidity, adhesion, water resistance, and non-tackiness were evaluated. The results are summarized in Table 3.

[Example 18]
To 15 g of the propylene polymer obtained in Production Example 2, 59.5 g of methylcyclohexane and 25.5 g of toluene were added as solvents, heated to 110 ° C. and dissolved over 1 hour. After cooling the resulting solution to near room temperature, a 15 wt% solution of the coating composition was prepared through a # 400 SUS wire mesh. Using the resulting coating composition, the coating composition was spray applied and dried on the substrate example 1 in the same manner as in Example 1 to prepare a test piece, and an adhesion test was performed. The low temperature storage test and the non-tack property test were also performed in the same manner as in Example 1. The results are summarized in Table 3.

Claims (10)

A coating composition containing at least one polymer selected from a propylene-based polymer and a modified propylene-based polymer, and at least one alicyclic hydrocarbon having 7 to 12 carbon atoms as a solvent; and A coating composition, wherein the polymer has the following properties (a) and (b):
(A) When dissolved in toluene at 25 ° C. at a concentration of 10% by weight, the insoluble content is 1% by weight or less based on the total polymer,
(B) Adhesiveness to a crystalline polypropylene base material (cross cut tape method) is 50/100 or more.   The coating composition according to claim 1, wherein the propylene-based polymer has a stereoblock structure including an isotactic block.   The coating composition according to claim 1 or 2, wherein the propylene-based polymer is produced by a single site catalyst. For a propylene-based polymer, a peak derived from a carbon atom of a methyl group in a propylene unit chain part composed of a head-to-tail bond was observed by ¹³ C-NMR, and a peak attributed to a pentad represented by mmmm Ratio of peak area S ₁ with 21.8 ppm peak top to total peak area S appearing from 19.8 ppm to 22.2 ppm when the top chemical shift is 21.8 ppm (S ₁ / S) Is not less than 10% and not more than 60%, and 4 + 2S ₁ / S ₂ > 5, where S ₂ is an area of a peak (mmmmr) having a peak top of about 21.5 to 21.7 ppm. The coating composition according to any one of claims 1 to 3.   The modified propylene polymer is obtained by graft-copolymerizing a polymerizable compound having a carboxylic acid group, a carboxylic anhydride group or a carboxylic ester group to the propylene polymer. 5. The coating composition according to any one of 4 above.   The coating composition according to any one of claims 1 to 5, wherein a ratio (weight) of the polymer and the solvent is 5/95 to 50/50.   The coating composition according to any one of claims 1 to 6, wherein the solvent is a mixture of an alicyclic hydrocarbon having 7 to 12 carbon atoms and an aromatic hydrocarbon having 6 to 12 carbon atoms. Stuff.   The content ratio (weight ratio) of the alicyclic hydrocarbon having 7 to 12 carbon atoms and the aromatic hydrocarbon having 6 to 12 carbon atoms in the solvent is 100/0 to 50/50. Item 8. The coating composition according to Item 7.   The coating composition according to claim 1, wherein the alicyclic hydrocarbon having 7 to 12 carbon atoms is selected from cyclohexane containing an alkyl group having 1 to 4 carbon atoms.   A method of using the coating composition according to claim 1 as a primer for a crystalline olefin polymer.