JP2015174884A - coating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating agent which meets requirements of baking sealing properties at low temperatures and high adhesion strength.SOLUTION: A coating agent contains a modified 1-butene-based copolymer obtained by graft-modifying 100 pts. mass of a 1-butene-α-olefin copolymer (Y) having (i) a ratio (Mw/Mn) of the wt. average molecular wt. Mw to the number average molecular wt. Mn of 1.0-3.5, measured by GPC, and (ii) a crystal fusion heat of 20-70 J/g with 0.1-15 pts. mass of a polar monomer.

Description

  The present invention relates to a primer comprising a modified product of 1-butene / α-olefin copolymer having specific physical property parameters, and a coating agent useful as an adhesive. Specifically, the present invention relates to a non-chlorine coating agent that has good low-temperature sealing properties and adhesive strength, and enables baking at low temperatures.

  Polyolefins such as polypropylene have excellent properties such as various moldability, light weight and impact properties, and are widely used as materials for automobile interiors and exteriors, home appliances, building materials and the like. On the other hand, since these polyolefins are non-polar, it is generally difficult to apply them using general-purpose paints, adhesives, etc., and adhere them to different materials such as metals. Therefore, there are known methods for directly processing the polyolefin surface, such as etching with a solvent, corona discharge treatment, and methods using a primer obtained by acid-modifying or chlorinating polyolefin. (For example, Patent Document 1-2). The primer is used at the time of applying a polyolefin, or in PTP packaging for bonding a polyolefin and a different material such as metal.

  On the other hand, in recent years, with the growing awareness of environmentally conscious processes and energy savings, it has been required that the coating agent have high performance such as low temperature adhesiveness and low baking process. On the other hand, a method of lowering the melting point of the propylene-based resin as the primer raw material or lowering the melting point of the resin by chlorination can be considered.

  For example, Patent Document 3 discloses a method of using a propylene polymer and a butene polymer in combination. However, according to the knowledge of the present inventors, although it is possible to improve the seizure property at a low temperature by chlorination, it is described that the adhesion to a nonpolar polyolefin is lowered. In addition, the chlorine-based coating agent has a large environmental burden. Therefore, the development of a non-chlorine coating agent composition that satisfies seizure / sealability at low temperatures and high adhesive strength is still desired.

  In recent years, the development of catalyst technology for polyolefin production has led to the development of homogeneous catalysts typified by metallocene catalysts, enabling precise resin design. This makes it possible to achieve higher mechanical strength, better flexibility, drastically lower melting point, and lower molecular weight components after the denaturation process, based on narrow molecular weight distribution and narrow comonomer distribution, which was difficult with conventional heterogeneous catalysts. The design preferable as a composition for coating agents, such as reduction, is possible.

Japanese Patent Publication No. 6-23361 International Publication No. 2003/002659 Pamphlet JP 2007-91933 A

  The subject of this invention is obtaining the coating agent which satisfy | fills the baking and sealing property in low temperature, and high adhesive strength.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that a specific 1-butene / α-olefin copolymer has been modified, in particular, the modified 1-butene / α-olefin copolymer. By using a coating agent containing a modified propylene copolymer and a non-chlorine coating agent, a non-chlorine coating agent can provide a coating composition having an excellent balance of sealing properties at low temperatures, seizure properties at low temperatures, and adhesive strength. The headline, the present invention has been reached.

  That is, the present invention is (i) the ratio (Mw / Mn) of weight average molecular weight Mw and number average molecular weight Mn determined by GPC is in the range of 1.0 to 3.5, and (ii) the heat of crystal melting is 20 to 70 J. A modified 1-butene copolymer obtained by graft-modifying 100 parts by mass of a 1-butene / α-olefin copolymer (Y) in the range of 0.1 g / g with a polar monomer of 0.1 to 15 parts by mass The coating agent which consists of is provided.

  The coating agent comprising the modified 1-butene copolymer of the present invention has an excellent balance of adhesiveness and adhesive strength at low temperatures as compared with conventional coating agents.

<1-Butene / α-Olefin Random Copolymer (Y)>
The 1-butene / α-olefin copolymer (Y), which is the basis of the modified 1-butene copolymer contained in the coating agent of the present invention, is (i) a weight average molecular weight Mw and a number average molecular weight determined by GPC. The ratio of Mn (Mw / Mn) is in the range of 1.0 to 3.5, preferably 1.0 to 3, and (ii) the heat of crystal fusion is 20 to 70 J / g, preferably in the range of 30 to 60 J / g. 1-butene and a random copolymer of an α-olefin having 2 to 20 carbon atoms other than 1-butene.

  Specific examples of the α-olefin having 2 to 20 carbon atoms copolymerized with 1-butene include ethylene, propylene, 1-pentene, 1-hexene, 1-octene and 1-decene. The α-olefin (including ethylene) copolymerized with 1-butene may be one type or two or more types.

  The 1-butene / α-olefin random copolymer (Y) according to the present invention preferably has a melting point (Tm-I) measured by a differential scanning calorimeter (DSC) of 55 ° C. or higher, more preferably 120 ° C. or lower. It is preferable that it is 55 degreeC or more and 90 degrees C or less especially. A coating agent containing a modified 1-butene copolymer obtained by modifying a 1-butene / α-olefin random copolymer (Y) having a melting point in this range has low-temperature adhesiveness and low-temperature seizure properties. Good in terms.

The melting point (Tm-I) and the heat of crystal fusion (J / g) are values measured by the following methods.
The 1-butene / α-olefin random copolymer (Y) according to the present invention is heated from room temperature (usually 23 ° C.) to 200 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC). After raising the temperature and holding at 200 ° C. for 5 minutes, the temperature is lowered to room temperature at a cooling rate of 10 ° C./min and left at room temperature for about 10 days. Then, after cooling from room temperature to −50 ° C. at a cooling rate of 10 ° C./min and holding at −50 ° C. for 5 minutes, the sample was heated from −50 ° C. to 200 ° C. at a heating rate of 10 ° C./min. The melting curve was measured, and the largest peak among the expressed melting peaks was defined as the melting point (Tm-I), and the heat of crystal melting (J / g) was measured from the melting curve at the time of measuring the melting point.

  When a polymer having a heat of crystal fusion of less than 20 g / J, that is, a polymer obtained by modifying so-called amorphous polybutene or liquid polybutene is used as a coating agent, the cohesive force is lowered and sufficient adhesive strength is obtained. There is a risk of not being able to

  The 1-butene / α-olefin random copolymer (Y) according to the present invention is a ratio (Mw) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC). / Mn) has a lower limit of 1.0 and an upper limit of 3.5. Furthermore, the upper limit is preferably 3.0. When a polymer having a value of Mw / Mn exceeding 3.5 is used, a gel is generated when graft-modifying with a polar monomer or a coating agent solution containing a modified 1-butene copolymer. There is a risk that the stability of the material will be lowered.

In the 1-butene / α-olefin random copolymer (Y) according to the present invention, the lower limit of the weight average molecular weight (Mw) is preferably 2 × 10 ⁵ , and the upper limit is preferably 7 × 10 ^5. . Furthermore, the lower limit is more preferably 3 × 10 ⁵ , and the upper limit is more preferably 6 × 10 ⁵ .

  The 1-butene / α-olefin random copolymer (Y) according to the present invention has (iii) preferably a pentad isotacticity of preferably 80% or more, more preferably 85 to 95%, More preferably, it is 88-94%, Most preferably, it is 88.0-93.0%. When the pentad isotacticity is within the above range, the coating agent containing a modified 1-butene copolymer obtained by graft modification with a polar monomer has an excellent balance between rigidity and elongation that affects the adhesive strength. preferable.

The pentad isotacticity (mmmm) of the 1-butene / α-olefin random copolymer (Y) according to the present invention is obtained by extending the 1-butene / α-olefin random copolymer (Y) to a chain having a zigzag structure. And the ethyl groups in the side chain of 5 consecutive 1-butene units are all defined in the same direction. When the chemical shift of the peak top attributed to this structure is 27.50 ppm, the peak area S having 27.50 ppm as the peak top and the total area S ′ of peaks appearing in the range of 27.35 ppm to 26.30 ppm are Obtained and calculated by the following formula.
(Mmmm) = S / (S + S ′) X100 (%)
Here, main peaks appearing in the range of 27.35 ppm to 26.30 ppm are peaks attributed to mmr (27.35 ppm), mmrr and rmmr (27.15 ppm), and mrrm (26.32 ppm).
The measurement of ¹³ C-NMR spectrum is defined by the values measured with the following apparatus and conditions.

An ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd. was used as an apparatus, a mixed solvent of o-dichlorobenzene / deuterated benzene (volume ratio: 80/20) as a solvent, a sample concentration of 50 mg / 0.6 mL, and a measurement temperature were 120 ° C, the observation nucleus is ¹³ C (125 MHz), the sequence is single-pulse proton decoupling, the pulse width is 4.7 μsec (45 ° pulse), the repetition time is 5.5 seconds, the number of integration is 10,000 times or more, chemical The shift reference value was such that the carbon signal of tetramethylsilane (TMS) was 0 ppm. In this case, a signal derived from a butene side chain methylene group is usually observed around 27.50 ppm.

  In the 1-butene / α-olefin random copolymer (Y) according to the present invention, preferably, the proportion of position irregular units based on 4,1-insertion of all 1-butene monomers is less than 0.1%. It is desirable. If the 1-butene monomer enters the molecular chain in the form of 4,1-insertion, the mechanical strength may be insufficient.

The identification of the 4,1-insert of the 1-butene / α-olefin random copolymer (Y) according to the present invention is, for example, As reported by Busico et al., Macromol. Rapid. Comun. 16, 269 (1995). It can calculate | require by calculating from the following formula | equation using the peak intensity of main chain (gamma) (31.1ppm), main chain (alpha) (alpha) (40.2ppm), and main chain (alpha) '(39.6ppm).
(4,1-insert content) = [Iγγ / (Iαα + Iαα _′ + 2 × Iγγ)] × 100 (%)
In the above formula, Iγγ, Iαα and Iαα _′ represent the peak intensities of the main chain γγ (31.1 ppm), the main chain αα (40.2 ppm), and the main chain αα ′ (39.6 ppm), respectively.

  The melt flow rate (MFR) (temperature: 190 ° C., load 2.16 kg) of the 1-butene / α-olefin random copolymer (Y) according to the present invention is not particularly limited, but the melt flow rate (MFR) The lower limit of (190 ° C., 2.16 kg) is preferably 0.1 g / 10 minutes, and the upper limit is preferably 50 g / 10 minutes. Furthermore, the upper limit is more preferably 20 g / 10 minutes. Further, the upper limit is preferably 4 g / 10 minutes. A coating agent containing a modified 1-butene copolymer obtained by modifying a 1-butene / α-olefin random copolymer (Y) having a melt flow rate (MFR) in the above range has good adhesive strength. I can expect.

  The 1-butene / α-olefin random copolymer (Y) according to the present invention has (iv) an elution amount with o-dichlorobenzene at −10 ° C. of 3% by mass or less, more preferably 2% by mass or less. It is. When a 1-butene / α-olefin random copolymer having an elution amount outside the above range was used, the 1-butene / α-olefin random copolymer was modified because there were many low melting point components or amorphous components. In some cases, when graft-modifying with a polar monomer, a gel is generated, or the resulting coating agent made of a modified 1-butene copolymer may have a reduced adhesive strength.

  In the 1-butene / α-olefin random copolymer (Y) according to the present invention, the content of 1-butene is not particularly limited as long as the heat of crystal fusion is in the above range, but usually the 1-butene content is not limited. However, the total of the 1-butene content and the α-olefin (including ethylene) content other than 1-butene is 100 mol%. ).

  Specific examples of the 1-butene / α-olefin random copolymer (Y) according to the present invention include, for example, 1-butene / ethylene random copolymer (Y-1), 1-butene / propylene random copolymer. Compound (Y-2), 1-butene / 1-pentene random copolymer, 1-butene / 1-hexene random copolymer, 1-butene / ethylene / propylene random copolymer, 1-butene / ethylene / 1 -Pentene random copolymer, 1-butene / propylene / 1-pentene random copolymer, 1-butene / ethylene / 1-hexene random copolymer, and the like. Among these, 1-butene / ethylene random copolymer (Y-1) and 1-butene / propylene random copolymer (Y-2) are preferable.

<1-Butene / Ethylene Random Copolymer (Y-1)>
The 1-butene-ethylene random copolymer (Y-1) according to the present invention preferably has a 1-butene content of 99.9 to 85 mol%, more preferably 99 to 95 mol%, and an ethylene content. Is in the range of 0.1 to 15 mol%, more preferably 1 to 5 mol% (the sum of 1-butene and ethylene is 100 mol%).

<1-Butene / propylene random copolymer (Y-2)>
The 1-butene / propylene random copolymer (Y-2) according to the present invention preferably has a 1-butene content of 99.9 to 70 mol%, more preferably 95 to 70 mol%, and a propylene content. It is in the range of 0.1 to 30 mol%, more preferably 5 to 30 mol% (the total of 1-butene and propylene is 100 mol%).

  The 1-butene / propylene random copolymer (Y-2) satisfies the condition of [C4] -5> Tm-II when the propylene content exceeds 20 mol% and up to 30 mol%. Are preferred, or those in which Tm-II is not substantially detected are preferred.

Here, Tm-II of the 1-butene / propylene random copolymer (Y-2) was determined as follows.
The 1-butene / propylene random copolymer (Y-2) was heated from room temperature (usually 23 ° C.) to 200 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC), After holding at 200 ° C. for 5 minutes, the temperature was lowered from 200 ° C. to 0 ° C. at a cooling rate of 20 ° C./minute, held at 0 ° C. for 5 minutes, and the sample was then heated at 0 ° C. to 200 ° C. at a heating rate of 20 ° C./minute. The melting curve was measured by raising the temperature to ° C., and the highest peak temperature among the expressed crystal melting peaks was defined as Tm-II. Further, in the same measurement, a polymer in which no crystal melting peak was expressed was determined as a polymer in which Tm-II was not substantially detected.

<Method for Producing 1-Butene / α-Olefin Random Copolymer (Y)>
As a method for obtaining the 1-butene / α-olefin random copolymer (Y) according to the present invention, a monomer is vapor phase method, bulk method, in the presence of a catalyst such as Ziegler-Natta catalyst, metallocene catalyst, The polymerization is exemplified by a known polymerization method such as a slurry method. Especially, it is desirable to polymerize using the metallocene compound represented by the following general formula (1) or (2).

（式中、Ｒ²は炭化水素基、ケイ素含有炭化水素基から選ばれ、Ｒ¹、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²は水素、炭化水素基、ケイ素含有炭化水素基から選ばれ、それぞれ同一でも異なっていてもよく、Ｒ⁵からＲ¹²までの隣接した置換基は互いに結合して環を形成してもよく、Ａは一部不飽和結合及び／または芳香族環を含んでいてもよい炭素原子数２〜２０の２価の炭化水素基であり、ＡはＹと共に形成する環を含めて２つ以上の環構造を含んでいてもよく、Ｍは周期表第４族から選ばれた金属であり、Ｙは炭素またはケイ素であり、Ｑはハロゲン、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選んでもよく、ｊは１〜４の整数である。）

(In the formula, R ² is selected from a hydrocarbon group and a silicon-containing hydrocarbon group, and R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² is selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different, and adjacent substituents from R ⁵ to R ¹² may be bonded to each other to form a ring. , A is a divalent hydrocarbon group having 2 to 20 carbon atoms which may partially contain an unsaturated bond and / or an aromatic ring, and A represents two or more including a ring formed with Y M may be a ring structure, M is a metal selected from Group 4 of the periodic table, Y is carbon or silicon, and Q is a halogen, hydrocarbon group, anion ligand or lone electron pair. You may choose from the neutral ligand which can be coordinated by the same or different combination, and j is an integer of 1-4.)

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² in the above general formula (1) or (2) are hydrogen, carbonized It is selected from a hydrogen group and a silicon-containing hydrocarbon group, and each may be the same or different.

  The hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. And may contain one or more ring structures. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl. 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl and the like.

  The silicon-containing hydrocarbon group is preferably an alkylsilyl group or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms. Specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, triphenylsilyl. Etc.

R ² is preferably a sterically bulky hydrocarbon group or silicon-containing hydrocarbon group, that is, a secondary or tertiary substituent, and more preferably a substituent having 4 or more carbon atoms. Specific hydrocarbon machines include isopropyl, 1,1-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, Examples thereof include tert-butyl and 1,1-dimethylbutyl. Particularly preferred is tert-butyl. The silicon-containing hydrocarbon machine can be exemplified by a compound having a structure in which part or all of the carbon in the above compound is substituted with silicon.

Adjacent substituents from R ⁵ to R ¹² on the fluorene ring may be bonded to each other to form a ring. Examples of such a substituted fluorenyl group include benzofluorenyl and dibenzofluorenyl. The substituents R ⁵ to R ¹² on the fluorene ring are symmetrical from the viewpoint of ease of synthesis, that is, R ⁵ = R ¹² , R ⁶ = R ¹¹ , R ⁷ = R ¹⁰ , R ⁸ = R ⁹ . Preferably, it is unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene or 2,3,6,7-tetrasubstituted fluorene. Wherein the 3-position on the fluorene ring, 6-position, 2-position, 7-position corresponds to the ^{R 7, R 10, R 6} , R 11 , respectively.

R ³ and R ^{4 in} the general formula (1) are selected from hydrogen and a hydrocarbon group, and may be the same or different from each other. Specific examples of preferred hydrocarbon groups include the same as those described above. Y is carbon or silicon. In the case of general formula (1), R ¹³ and R ¹⁴ are bonded to Y to form a substituted methylene group or a substituted silylene group as a bridging part. Preferable specific examples include methylene, dimethylmethylene, diisopropylmethylene, methyl tert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, dimethylsilylene, diisopropylsilylene and the like. More preferred Y is carbon.

When R ^{2 in the} general formula (1) or (2) is a tert-butyl group, R ¹ is preferably a methyl or ethyl group, preferably a methyl group. In this case, R ³ and R ^{4 in} the general formula (1) are methyl or phenyl groups, preferably methyl groups. R ³ and R ⁴ are preferably the same as each other. Further, when R ^{2 in the} general formula (1) is a tert-butyl group and R ¹ is a methyl group, R ^{5 to} R ¹² may be hydrogen.

Further, when R ^{2 in the} general formula (1) is a tert-butyl group and R ¹ is an ethyl group, R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹² are hydrogen, R ⁶ , R Those in which ¹¹ is a tert-butyl group are preferably used.

  In the case of the general formula (2), Y is bonded to a divalent hydrocarbon group A having 2 to 20 carbon atoms which may partially contain an unsaturated bond and / or an aromatic ring, and a cycloalkylidene group or It constitutes a cyclomethylenesilylene group and the like. Preferable specific examples include cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene and the like.

  M in the general formulas (1) and (2) is a metal selected from Group 4 of the periodic table, and examples of M include titanium, zirconium, and hafnium. Q is selected from the same or different combinations from halogen, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. Specific examples of the halogen include fluorine, chlorine, bromine, and iodine. Specific examples of the hydrocarbon group include the same as those described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. Among these, Q may be the same or different combinations, but at least one is preferably a halogen or an alkyl group.

  Component (B) is at least one selected from an organoaluminum oxy compound (B-1), a compound (B-2) that reacts with the metallocene compound (A) to form an ion pair, and an organoaluminum compound. (B-3). Furthermore, it is comprised from a particulate support (C) as needed.

As the organoaluminum oxy compound (B-1) used, a conventionally known aluminoxane can be used as it is.
Examples of the compound (B-2) that reacts with the metallocene compound (A) to form an ion pair (hereinafter sometimes abbreviated as “ionic compound”) include JP-A-1-501950 and JP-A-2004. And Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-A-51676. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

  Specifically, triphenylboron, tris (o-tolyl) boron, tris (p-tolyl) boron, tris (3,5-dimethylphenyl) boron, trimethylboron, triisobutylboron; tris (4-fluorophenyl) A compound having a halogen-containing aryl group, such as a compound having a fluorine-containing aryl group such as boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron; Illustrative is fluoroboron.

  Examples of the organoaluminum compound (B-3) that forms the polymerization catalyst for olefin include an organoaluminum compound represented by the following general formula (6).

（式中、Ｒ^a及びＲ^bは、互いに同一でも異なっていてもよく、炭素原子数が１〜１５、好ましくは１〜４の炭化水素基を示し、Ｘはハロゲン原子を示し、ｍは０＜ｍ≦３、ｎは０≦ｎ＜３、ｐは０≦ｐ＜３、ｑは０≦ｑ＜３の数であり、かつｍ＋ｎ＋ｐ＋ｑ＝３である。）で表される有機アルミニウム化合物。このような化合物の具体例として、トリメチルアルミニウム、トリエチルアルミニウム、トリｎ−ブチルアルミニウム、ジイソプロピルアルミニウムハイドライド、ジイソブチルアルミニウムハイドライドなどのジアルキルアルミニウムハイドライド、イソブチルアルミニウムメトキシド、イソブチルアルミニウムエトキシドなどのアルキルアルミニウムアルコキシドなどを挙げることができる。

(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is 0 ≦ n <3, p is a number of 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3). Specific examples of such compounds include trialkylaluminum, triethylaluminum, tri-n-butylaluminum, diisopropylaluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride, alkylaluminum alkoxide such as isobutylaluminum methoxide, isobutylaluminum ethoxide, and the like. Can be mentioned.

  As the organoaluminum compound (B-3), tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, and trioctylaluminum, and tri-branched alkylaluminum such as triisobutylaluminum are preferable, and trimethylaluminum and triisobutylaluminum are particularly preferable. Preferably used.

  In the present invention, the polymerization of the 1-butene / α-olefin random copolymer (Y) can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. In the liquid phase polymerization method, an inert hydrocarbon solvent may be used. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, etc .; cyclopentane, cyclohexane, methyl Examples thereof include alicyclic hydrocarbons such as cyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene, or mixtures thereof. Bulk polymerization using 1-butene-containing olefin itself as a solvent can also be carried out.

  Further, in the production of the 1-butene / α-olefin random copolymer (Y) according to the present invention, so-called multistage polymerization in which the polymerization conditions are changed stepwise can also be performed. For example, it is possible to obtain a 1-butene / α-olefin random copolymer (Y) having various molecular weight distributions by carrying out polymerization stepwise under two conditions with different amounts of hydrogen used. Also, 1-butene / α-olefin random copolymer (Y) having a controlled composition distribution is obtained by performing stepwise homopolymerization of 1-butene and copolymerization of 1-butene and other olefins. It is also possible.

In carrying out the polymerization, the component (A) is usually 10 ⁻⁸ to 10 ⁻² mol, preferably 10 ⁻⁷ to 10 ⁻³ mol in terms of Group 4 metal atom in the periodic table per liter of reaction volume. Used in various amounts. In the component (B-1), the molar ratio [(B-1) / M] of the component (B-1) and the transition metal atom (M) in the component (A) is usually 0.01 to 5000, Preferably it is used in such an amount that it is 0.05-2000. Component (B-2) has a molar ratio [(B-2) / M] of component (B-2) to transition metal atom (M) in component (A) of usually 1 to 10, preferably 1. Used in an amount such that it is ˜5. Component (B-3) has a molar ratio [(B-2) / M] of component (B-3) and transition metal atom (M) in component (A) of usually 10 to 5000, preferably 20 It is used in an amount such that it is ˜2000.

  The polymerization temperature is usually in the range of −50 to 200 ° C., preferably 0 to 100 ° C., more preferably 20 to 100 ° C. If the polymerization temperature is too low, there is an industrial disadvantage in terms of polymerization activity per unit catalyst and heat recovery efficiency.

  The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

  Hydrogen can be added for the purpose of controlling the molecular weight and polymerization activity of the 1-butene / α-olefin random copolymer (Y) produced during the polymerization, and the amount is 1-butene / α-olefin random copolymer. (Y) About 0.001 to 100 NL per kg is appropriate.

<Propylene / α-olefin copolymer (X)>
The propylene / α-olefin copolymer (X) which may be included when the 1-butene / α-olefin random copolymer (Y) according to the present invention is graft-modified with a polar monomer has a melting point measured by DSC. It is a copolymer of propylene and α-olefin having a range of 50 to 130 ° C., preferably 65 to 115 ° C.

  In the propylene / α-olefin copolymer (X) according to the present invention, the content of the α-olefin copolymerized with propylene is not particularly limited as long as the melting point is in the above range. %, Preferably in the range of 15-40 mol%. In addition, alpha-olefin content in copolymer (X) is a structural unit resulting from alpha-olefin, and this content is a value calculated | required by infrared spectroscopy.

  The α-olefin to be copolymerized with propylene is usually an α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, specifically, ethylene, 1-butene, 1-pentene, 3-methyl. Examples include -1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and the like. The α-olefin (including ethylene) copolymerized with propylene may be one type or two or more types. Among these α-olefins, 1-butene is preferable.

  When the propylene / 1-butene copolymer is used as the propylene / α-olefin copolymer (X) according to the present invention, the compatibility with the 1-butene / α-olefin copolymer (Y) is improved. A coating agent comprising a modified 1-butene copolymer composition obtained by graft-modifying a 1-butene / α-olefin copolymer (Y) and a propylene / 1-butene copolymer with a polar monomer is excellent. High adhesive strength can be expected.

  The propylene / α-olefin copolymer (X) according to the present invention preferably has a molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) of 1 or more and 5 or less, more preferably 1 It is 3 or less.

  The propylene / α-olefin copolymer (X) according to the present invention is produced by various known production methods, specifically, for example, titanium-based or vanadium-based Ziegler-Natta catalyst, titanium-based, zirconium-based, hafnium-based. Propylene and α-olefin can be produced by a known polymerization method such as a gas phase method, a bulk method, a slurry method, etc. in the presence of a metallocene catalyst and other known stereoregular catalyst used for olefin polymerization.

<Modified 1-butene copolymer and modified 1-butene copolymer composition>
The modified 1-butene copolymer according to the present invention is a polar monomer of 0.1 to 15 parts by mass, preferably 0.5 to 10 parts by mass of the 1-butene / α-olefin copolymer (Y). It is a modified 1-butene copolymer obtained by graft modification.

  The modified 1-butene copolymer composition according to the present invention comprises the propylene / α-olefin copolymer (X) with respect to the 1-butene / α-olefin copolymer (Y): 10 to 90% by mass. ) 90 to 10% by weight [provided that (Y) + (X) = 100% by mass. ) A modified 1-butene copolymer composition obtained by graft-modifying 100 parts by mass with 0.1 to 15 parts by mass, preferably 0.5 to 10 parts by mass of a polar monomer.

  Examples of polar monomers according to the present invention include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, unsaturated carboxylic acids and their anhydrides and derivatives, and vinyl ester compounds. Vinyl chloride and the like, and unsaturated carboxylic acids and anhydrides thereof are preferred.

  Examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono (meta) ) Acrylate, polyethylene glycol mono (meth) acrylate, 2- (6-hydrohexanoyloxy) ethyl acrylate and other hydroxyl group-containing (meth) acrylic acid esters and 10 Undecen-1-ol, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene, N-methylolacrylamide, 2- (meth) acryloyloxyethyl acid phosphate, glycerin monoallyl ether, allyl alcohol, allyloxyethanol, Examples include 2-butene 1,4-diol, glycerin monoalcohol and the like.

Examples of the amino group-containing ethylenically unsaturated compound include vinyl monomers having at least one amino group or substituted amino group represented by the following formula.
-NR ¹ R ^2-
(Wherein R ¹ is a hydrogen atom, a methyl group or an ethyl group, and R ² is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, preferably 8 to 12 carbon atoms, preferably And a cycloalkyl group having 6 to 9. The above alkyl group and cycloalkyl group may further have a substituent.

  Examples of such an amino group-containing ethylenically unsaturated compound include aminomethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, and phenyl methacrylate. Alkyl ester derivatives of acrylic acid or methacrylic acid such as aminomethyl and cyclohexylaminoethyl methacrylate, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, acrylamide, methacrylamide, N-methylacrylamide, N Acrylamide derivatives such as N, N-dimethylacrylamide and N, N-dimethylaminopropylacrylamide, and imides such as p-aminohexyl succinimide and 2-aminoethyl succinimide Can.

  As the epoxy group-containing ethylenically unsaturated compound, a monomer having at least one unsaturated bond group and epoxy group polymerizable in one molecule is used. Examples of such an epoxy group-containing ethylenically unsaturated compound include glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate, or maleic acid, fumaric acid, crotonic acid, tetrahydrophthalic acid, itaconic acid, and citraconic acid. , Monoglycidyl ester of unsaturated dicarboxylic acid such as nadic acid (trade name), methyl nadic acid (trade name) (C1-C12 of alkyl group in the case of monoglycidyl ester), alkyl glycidyl of p-styrene carboxylic acid Ester, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoch There may be mentioned xy 3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide and the like.

Examples of unsaturated carboxylic acids include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, or derivatives thereof. (For example, acid anhydrides, acid halides, amides, imides, esters, etc.) can be mentioned. Examples of this derivative include maleenyl chloride, maleenylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, citracone Examples include diethyl acid, dimethyl tetrahydrophthalate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate and aminopropyl methacrylate. Examples of vinyl ester compounds include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl persate, vinyl laurate, vinyl stearate, vinyl benzoate, and salicylic acid. Examples thereof include vinyl and vinyl cyclohexanecarboxylate.
These polar monomers can be used alone or in combination.

<Method for Producing Modified 1-Butene Copolymer and Modified 1-Butene Copolymer Composition>
The modified 1-butene copolymer and modified 1-butene copolymer composition according to the present invention include the 1-butene / α-olefin copolymer (Y) or the 1-butene / α-olefin copolymer. Examples of the method of graft copolymerizing at least one polar monomer selected from the above polar monomers onto the resin composition containing the polymer (Y) and the propylene / α-olefin copolymer (X) include various methods. Can do.

  Specifically, for example, a method of dissolving the copolymer in an organic solvent, adding the above polar monomer and radical polymerization initiator and heating and stirring to cause graft copolymerization reaction, heating and melting the copolymer, A method in which a polar monomer and a radical polymerization initiator are added to the resulting melt and the mixture is stirred and graft copolymerized, the copolymer, the polar monomer and the radical polymerization initiator are mixed in advance, and the resulting mixture is supplied to an extruder. Examples thereof include a graft copolymerization reaction method while heating and kneading.

  The reaction temperature at the time of grafting is preferably 50 ° C. or higher, particularly in the range of 80 to 200 ° C., and the reaction time is about 1 to 10 hours. The reaction method may be either a batch method or a continuous method, but a batch method is preferred in order to perform graft copolymerization uniformly.

  When obtaining a modified 1-butene copolymer composition, the 1-butene / α-olefin copolymer (Y) and the propylene / α-olefin copolymer (X) are individually grafted. There are two methods, namely, a method of mixing a modified product and a method of blending and modifying each copolymer in advance. The latter method is preferable from the viewpoint of simplifying the process. The optimum blending ratio of each copolymer is preferably 10-90% by mass of 1-butene / α-olefin copolymer (Y) and 90-10% by mass of propylene / α-olefin copolymer (X). More preferably, the 1-butene / α-olefin copolymer (Y) is in the range of 20 to 80% by mass and the propylene / α-olefin copolymer (X) in the range of 80 to 20% by mass.

  When the modified 1-butene copolymer composition is used as a raw material for the coating agent, it can be hybridized by using a specific polar monomer by a known method such as JP-A-2005-325223.

  The radical polymerization initiator used in the graft reaction is not particularly limited as long as it promotes the reaction between the copolymer and the polar monomer, and organic peroxides and organic peresters are particularly preferable. Specifically, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3, 1,4-bis (tert-butyl) Peroxyisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert-butyl peroxide) hexane Tert-butyl benzoate tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate, Other azo compounds, tato For example, there are azobis-isobutylnitrile and dimethylazoisobutylnitrile. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tert-butylperoxy) ) Dialkyl peroxides such as hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.

  The radical polymerization initiator is preferably used in an amount of about 0.001 to 10 parts by mass with respect to 100 parts by mass of the copolymer. As described above, the grafting reaction can be performed in an organic solvent or without a solvent.

<Coating agent>
The coating agent of the present invention comprises the modified 1-butene copolymer or the modified 1-butene copolymer composition.

  The coating agent of the present invention is used as a coating agent by dissolving the modified 1-butene copolymer or the modified 1-butene copolymer composition in an organic solvent. When reacted, the coating agent may be prepared as it is or by adding the same or other organic solvent. When the graft reaction is carried out without using an organic solvent, an organic solvent is added again to dissolve the graft product to obtain a coating agent.

  The organic solvent for preparing the coating agent during the reaction or after the reaction is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, hexane, heptane, octane and decane. Aliphatic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, etc., alcohols such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, phenol, acetone, methyl isobutyl ketone, methyl ethyl ketone , Ketone solvents such as pentanone, hexanone, isophorone, acetophenone, cellsolves such as methyl cellosolve, ethyl cellosolve, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate Esters, mention may be made of trichlorethylene, dichloroethylene, halogenated hydrocarbons such as chlorobenzene. Of these, aromatic hydrocarbons, aliphatic hydrocarbons, and ketones are preferable. These may be used alone or in combination of two or more.

  The concentration of the coating agent varies depending on the type of the modified 1-butene copolymer or the modified 1-butene copolymer composition and the solvent, but the solid content concentration is 3 to 50%, and the solution viscosity by a B-type viscometer Is preferably about 5 to 4000 cps from the viewpoint of workability in the bonding process. In the coating agent of the present invention, pigments, fillers, stabilizers and other compounding agents known per se can be arbitrarily blended within a range not impairing the object of the invention.

  In order to produce the coating agent of the present invention, the modified 1-butene copolymer or the modified 1-butene copolymer composition may be mixed with the above solvent. Alternatively, when the modified 1-butene copolymer composition is not dissolved in a solvent, it is preferably dispersed in fine particles. That is, after adding a modified 1-butene copolymer or a modified 1-butene copolymer composition to a solvent, it is heated and completely dissolved, and then the solution is cooled to obtain a modified 1-butene copolymer. Alternatively, the modified 1-butene copolymer composition is atomized and precipitated. It is necessary to set the solvent composition in advance so as to precipitate at 60 to 100 ° C., and to adjust the average cooling rate during this period to 1 to 20 ° C./hour, preferably 2 to 10 ° C./hour. Or it melt | dissolves only in a parent solvent, and after precipitation to a parent solvent is complete | finished, a poor solvent may be added and it may precipitate further. In the present invention, a coating agent containing a modified 1-butene copolymer or a modified 1-butene copolymer composition is evaluated without chlorination. For example, it is known in JP-B-6-23361. It can also be chlorinated by the method. However, there is a possibility that the adhesive strength with an adherent such as non-polar polyolefin may decrease due to chlorination.

  By using the 1-butene / α-olefin copolymer (Y) having specific properties, the coating agent of the present invention improves the low-temperature baking performance and the low-temperature seal strength as a non-chlorinated coating agent. It was. The coating agent of the present invention can be used as it is, and can of course be blended as a modifier for the propylene-based coating agent.

  The coating agent of the present invention can be used as an adhesive for PTP packaging, an adhesive for laminating, a coating material, or a primer material as an adhesive or heat sealant between metals, between polyolefins, or between metal and polyolefin. In particular, it is preferable that at least one of the adherends is a plastic material, and among them, a polyolefin material, particularly preferably a polybutene-based material or a polypropylene-based material is preferable.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples at all. Each physical property was evaluated as follows.
[Melt flow rate (MFR) (g / 10 min)]
Based on ASTM D1238, the values at 190 ° C. and 230 ° C. were measured under a load of 2.16 kg.

[Intrinsic viscosity ([η] (dl / g))
It measured at 135 degreeC using the decalin solvent.
[ ¹³ C-NMR]
Using an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., a mixed solvent of o-dichlorobenzene / heavy benzene (80/20 vol%) as a solvent, sample concentration 55 mg / 0.6 mL, measurement temperature 120 ° C., observation nucleus is ¹³ C (125 MHz), sequence is single pulse proton decoupling, pulse width is 4.7 μs (45 ° pulse), repetition time is 5.5 seconds, integration number is 10,000 times or more, 27.50 ppm of chemical shift Measured as a reference value.

[Pentad isotacticity (mmmm)]
Pentad isotacticity (mmmm) is 27.5 ppm from the peak area S having 27.5 ppm as the peak top when the chemical shift of the peak top attributed to the pentad expressed in mmmm is 27.5 ppm. The total area S ′ of peaks appearing in the range of 26.3 ppm was determined and calculated by the following formula. (Detection limit: 0.01%)
(Mmmm) = S / (S + S ′) X100 (%)
Here, main peaks appearing in the range of 27.3 ppm to 26.3 ppm are peaks attributed to mmr (27.3 ppm), mmrr and rmmr (27.2 ppm), and mrrm (26.3 ppm).

[Ratio of position irregular units based on 4,1-insertion (content of 4,1-insert)] (unit%)
From the ¹³ C-NMR spectrum, the proportion of regioregular units based on 4,1-insertion, ie, the content of 4,1-insert, was determined from the ¹³ C-NMR spectrum as main chain γγ (31.1 ppm) and main chain αα (40.2 ppm). And by calculating from the following formula using the peak intensity of the main chain αα ′ (39.6 ppm).
(4,1-insert content) = [Iγγ / (Iαα + Iαα _′ + 2 × Iγγ)] × 100 (%)
In the above formula, Iγγ, Iαα and Iαα _′ represent the peak intensities of the main chain γγ (31.1 ppm), the main chain αα (40.2 ppm), and the main chain αα ′ (39.6 ppm), respectively.

[Melting point of polymer (Tm-I), (Tm-II) (° C.)]
The melting point (Tm) of the polymer was measured with a differential scanning calorimeter (DSC) using a DSC220C apparatus manufactured by Seiko Instruments Inc. Samples 7 to 12 mg obtained from the polymerization were sealed in an aluminum pan, heated from room temperature to 200 ° C. at a heating temperature of 10 ° C./min, held at 200 ° C. for 5 minutes, and then a cooling rate of 20 ° C./min. At 200 ° C. to 0 ° C. After maintaining at 0 ° C. for 5 minutes, when the temperature was raised from 0 ° C. to 200 ° C. at a heating rate of 20 ° C./min, the melting curve was measured, and the highest peak temperature among the expressed melting peaks was Tm-II. It was.

  On the other hand, the melting point (Tm-I) was measured as follows. The temperature is raised from room temperature (usually 23 ° C.) to 200 ° C. at a heating rate of 10 ° C./minute, held at 200 ° C. for 5 minutes, then cooled to room temperature at a cooling rate of 10 ° C./minute and brought to room temperature for about 10 days. Leave it alone. Then, after cooling from room temperature to −50 ° C. at a cooling rate of 10 ° C./min and holding at −50 ° C. for 5 minutes, the sample was heated from −50 ° C. to 200 ° C. at a heating rate of 10 ° C./min. At that time, the melting curve was measured, and the largest peak among the melting peaks expressed was defined as the melting point (Tm-I).

[Crystal melting heat amount of polymer (J / g)]
The amount of heat of crystal fusion observed during the measurement of Tm-I was defined as ΔH.
[Molecular weight distribution] (Mw / Mn)
Liquid chromatograph: Waters ALC / GPC150-Cplus type (indicative refractometer detector integrated type) column: Tosoh Corporation GMH6-HT × 2 and GMH6-GMH6-HTL × 2 were connected in series. Mobile phase medium: o-dichlorobenzene Flow rate: 1.0 ml / min Measurement temperature: 140 ° C.
Calibration curve creation method: Standard polystyrene sample used Sample concentration: 0.10% (w / w)
Sample solution volume: 500 μl
Mw / Mn value and Mz / Mw value were calculated by analyzing the obtained chromatogram by a known method. The measurement time per sample was 60 minutes.

[Total elution volume (% by weight)]
It was carried out under the following conditions by cross-fractionation chromatography (CFC), and the solvent-soluble content was measured as the total elution amount. (Detection limit 0.1%)
Apparatus: Cross fractionation chromatograph CFC2 (manufactured by Polymer ChAR)
Detector: IR spectrophotometer IR4 (Polymer ChAR GPC column: Shodex HT-806M x 3 (made by Showa Denko)
GPC column temperature: 140 ° C
Column configuration: Monodisperse polystyrene standard sample (Tosoh Corporation)
Eluent: o-dichlorobenzene Flow rate: 1.0 ml / min Sample concentration: 120 mg / 30 ml
Injection volume 500μl
Temperature drop time: 160 minutes (140 ° C. to −20 ° C., 1 ° C./min)
Elution temperature classification: 45 fractions

[Tensile test]
Using a 2 mm thick press sheet prepared by the following method, in accordance with ASTM D638, the test piece shape is ASTM No. 4 and the tensile speed is 50 mm / min. -The tensile modulus (MPa), tensile breaking strength (MPa) and elongation at break (%) of the olefin copolymer were determined.

<Press molding conditions>
A 1-butene / α-olefin copolymer press sheet prepared under the following conditions was stored for 10 days at room temperature and used in the test.
Press machine: manufactured by Kansai Roll Co., Ltd. (model number: PEWE-70 / 50 35)
Heating time: 5 min
Heating temperature: 190 ° C
Heating pressure: 10 MPa
Cooling rate: 40 ° C./min or more (Pressurized at 10 MPa for 4 minutes with another press set to 20 ° C. and cooled to room temperature)

[Polymerization Example 1]
[1-Butene / propylene random copolymer (BPR-1)]
N-Hexane is supplied at a rate of 19.8 L / h to one supply port of a continuous polymerization vessel having a volume of 300 liters, and diphenylmethylene (2,7-di-tert-butylfluorene-9 is supplied from the other supply port. -Yl) (3-tert-butyl-5-ethylcyclopentadien-1-yl) zirconium dichloride (main catalyst 1), a mixed hexane solution of modified methylaluminoxane and triisobutylaluminum (zirconium equivalent concentration of main catalyst 1 0.5 mmol) / Liter, 125 mmol / liter of aluminum equivalent of modified methylaluminoxane, and triisobutylaluminum were continuously fed at 0.25 liter / h (total hexane 20 liter / h). -25.1 kg / h butene, 5.2 kg / h propylene, water Was continuously supplied at a rate of 14 NL / h, and continuous solution polymerization was carried out under conditions of a polymerization temperature of 55 ° C., a total pressure of 0.7 MPaG, and a residence time of 1.4 hours. The hexane solution of the copolymer was heated to remove hexane, and as a result, a 1-butene / propylene random copolymer was obtained at a production speed of 7.5 kg / h. Polymerization Mileage was 60 kg / mmol-Zr, MFR (190 ° C., 2.16 kgf) of the obtained 1-butene / propylene random copolymer was 3.8 g / 10 min, and propylene content was 26.0 mol%. .

[Polymerization Example 2]
[1-Butene / propylene random copolymer (BPR-2)]
N-Hexane is supplied at a rate of 19.8 liter / h to one supply port of a continuous polymerization vessel having a capacity of 300 liters, and diphenylmethylene (2,7-di-tert-butylfluorene-9 is supplied from the other supply port. -Yl) (3-tert-butyl-5-ethylcyclopentadien-1-yl) zirconium dichloride (main catalyst 1), a mixed hexane solution of modified methylaluminoxane and triisobutylaluminum (zirconium equivalent concentration of main catalyst 1 0.5 mmol) / Liter, aluminum equivalent concentration of modified methylaluminoxane 125 mmol / liter, aluminum concentration of triisobutylaluminum 100 mmol / liter) was continuously supplied at 0.23 liter / h (total hexane 20 liter / h). Simultaneously, 1-butene is continuously fed at a rate of 25.1 kg / h, propylene at 2.2 kg / h and hydrogen at a rate of 14.0 NL / h from another supply port of the polymerization vessel. The polymerization temperature is 50 ° C. and the total pressure is 0. Continuous solution polymerization was performed under the conditions of .59 MPaG and a residence time of 1.6 hours. The hexane solution of 1-butene / propylene random copolymer produced in the polymerization vessel was heated to remove hexane.

  As a result, a 1-butene / propylene random copolymer was obtained at a production speed of 8.2 kg / h. Polymerization Mileage of 1-butene / propylene random copolymer was 71 kg / mmol-Zr, MFR (190 ° C., 2.16 kgf) of the obtained 1-butene / propylene random copolymer was 4.1 g / 10 min, propylene content Was 12.9 mol%.

[Polymerization Example 3]
[1-Butene / propylene random copolymer (BPR-3)]
N-Hexane is supplied at a rate of 19.7 L / h to one supply port of a continuous polymerization vessel having a capacity of 300 liters, and diphenylmethylene (2,7-di-tert-butylfluorene-9 is supplied from the other supply port. -Yl) (3-tert-butyl-5-ethylcyclopentadien-1-yl) zirconium dichloride (main catalyst 1), a mixed hexane solution of modified methylaluminoxane and triisobutylaluminum (zirconium equivalent concentration of main catalyst 2 0.5 mmol) / Liter, aluminum equivalent concentration of modified methylaluminoxane 125 mmol / liter, aluminum concentration of triisobutylaluminum 100 mmol / liter) was continuously supplied at 0.26 liter / h (total hexane 20 liter / h). At the same time, 1-butene was continuously supplied at a rate of 25.1 kg / h, propylene at 5.0 kg / h, and hydrogen at a rate of 7.0 NL / h from another supply port of the polymerization vessel. Continuous solution polymerization was performed under the conditions of .60 MPaG and a residence time of 1.4 hours. The hexane solution of 1-butene / propylene random copolymer produced in the polymerization vessel was heated to remove hexane.

  As a result, a 1-butene / propylene random copolymer was obtained at a production speed of 7.9 kg / h. Polymerization Mileage of 1-butene / propylene random copolymer was 61 kg / mmol-Zr, MFR (190 ° C., 2.16 kgf) of the obtained 1-butene / propylene random copolymer was 2.1 g / 10 min, propylene content Was 25.9 mol%.

[Polymerization Example 4]
[1-Butene / Ethylene Random Copolymer (BER-1)]
N-Hexane is supplied at a rate of 9.7 L / h to one supply port of a continuous polymerization vessel having a capacity of 300 liters, and isopropyldene (3-tert-butyl-5-methylcyclopentadiene is supplied from the other supply port. Enyl-fluorenyl) zirconium dichloride (main catalyst 2), modified methylaluminoxane and triisobutylaluminum mixed hexane solution (main catalyst 2) zirconium equivalent concentration 0.5 mmol / liter, modified methylaluminoxane aluminum equivalent concentration 125 mmol / liter, tri Isobutylaluminum-concentrated aluminum equivalent concentration 100 mmol / liter) was continuously supplied at 0.26 liter / h (total hexane 10 liter / h). At the same time, 1-butene is continuously supplied at a rate of 44.8 kg / h, ethylene is 0.16 kg / h, and hydrogen is supplied at a rate of 10 NL / h from another supply port of the polymerization vessel. The polymerization temperature is 65 ° C. and the total pressure is 0.65 MPaG. Continuous solution polymerization was carried out under the conditions of a residence time of 1 hour.

The hexane solution of 1-butene / ethylene random copolymer produced in the polymerization vessel was heated to remove hexane.
As a result, a 1-butene / ethylene random copolymer was obtained at a production speed of 8.0 kg / h. Polymerization Mileage of 1-butene / ethylene random copolymer was 55 kg / mmol-Zr, MFR (190 ° C., 2.16 kgf) of the obtained 1-butene / ethylene random copolymer was 3.9 g / 10 min, ethylene content Was 2.5 mol%.

[Polymerization Example 5]
[1-Butene / Ethylene Random Copolymer (BER-2)]
N-Hexane is supplied at a rate of 9.8 L / h to one supply port of a continuous polymerization vessel having a capacity of 300 liters, and isopropyldene (3-tert-butyl-5-methylcyclopentadiene is supplied from the other supply port. Enyl-fluorenyl) zirconium dichloride (main catalyst 1), mixed hexane solution of modified methylaluminoxane and triisobutylaluminum (main catalyst 1 zirconium equivalent concentration 0.5 mmol / liter, modified methylaluminoxane equivalent aluminum concentration 125 mmol / liter, triisobutyl The aluminum equivalent concentration of aluminum (100 mmol / liter) was continuously supplied at 0.2 liter / h (total hexane: 10 liter / h). Simultaneously, 1-butene is continuously supplied at a rate of 44.9 kg / h, ethylene is 0.11 kg / h, and hydrogen is supplied at a rate of 3.0 NL / h from another supply port of the polymerization vessel. The polymerization temperature is 55 ° C. and the total pressure is 0. Continuous solution polymerization was carried out under the conditions of .65 MPaG and a residence time of 1 hour. The hexane solution of 1-butene / ethylene random copolymer produced in the polymerization vessel was heated to remove hexane. As a result, a 1-butene / ethylene random copolymer was obtained at a production speed of 8.0 kg / h. The polymerization Mileage of 1-butene / ethylene copolymer was 80 kg / mmol-Zr, the MFR (190 ° C., 2.16 kgf) of the obtained 1-butene / ethylene random copolymer was 0.8 g / 10 min, and the ethylene content was It was 1.5 mol%.

1-butene / propylene random copolymer (BPR-A) obtained by using a conventional titanium-based catalyst, different from the copolymers obtained above and the catalysts used in the above polymerization examples, A butene / ethylene random copolymer (BER-A) was used.
These physical property values are shown in Table 1-1 and Table 1-2.

[1-Butene / α-olefin copolymer (Y) according to the present invention used in Examples]
BPR-1: 1-butene / propylene random copolymer: Tm-II was not detected.
BPR-2: 1-butene / propylene random copolymer BPR-3: 1-butene / propylene random copolymer BER-1: 1-butene / ethylene landako copolymer

[1-Butene / α-olefin copolymer used in Comparative Example]
BPR-A: 1-butene / propylene random copolymer BER-A: 1-butene / ethylene random copolymer

[Propylene / α-olefin copolymer (X) used in Examples and Comparative Examples]
<Propylene / 1-butene random copolymer (X-1)>
In a 2000 ml polymerization apparatus sufficiently substituted with nitrogen by a method known in WO2004 / 487775, 900 ml of dry hexane, 60 g of 1-butene and triisobutylaluminum (1.0 mmol) were charged at room temperature, and then the internal temperature of the polymerization apparatus was adjusted. The temperature was raised to 70 ° C., and the pressure was increased to 0.7 MPa with propylene. Next, 0.002 mmol of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride (main catalyst 2) and 0.6 mmol of methylaluminoxane (produced by Tosoh Finechem Co., Ltd.) in terms of aluminum The toluene solution was brought into contact with the polymerization vessel and polymerized for 30 minutes while maintaining an internal temperature of 70 ° C. and a propylene pressure of 0.7 MPa, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours.

  The resulting propylene / 1-butene random copolymer (X-1) had a 1-butene content of 19.1 mol%, a melting point (Tm-I) of 80.6 ° C., Mw / Mn = 2.0, [η ] = 1.18.

[Example 1]
As the 1-butene / α-olefin copolymer (Y), BPR-1 obtained in Polymerization Example 1 was used, and 350 ml of BPR-1 (110 g) was placed in a 1 liter autoclave equipped with a stirrer. After carrying out nitrogen substitution, it heated up at 130 degree-C / min, stirring, and was made to melt | dissolve completely. Subsequently, 8.8 g of maleic anhydride (dissolved in 50 ml of toluene) and 2.4 g of dicumyl peroxide (dissolved in 40 ml of toluene) were added dropwise over 4 hours while maintaining the temperature. After completion of dropping, the mixture was stirred at 130 ° C. for 3 hours, and post-reaction was performed to obtain modified BPR-1. After completion of the reaction, the solution was cooled to room temperature, and acetone was added to the solution to precipitate modified BPR-1. After repeatedly washing with acetone, it was dried to obtain a sample. Table 2 shows the physical properties of the modified BPR-1.

The modified BPR-1: 60 g was dissolved in methylcyclohexane 240 g to obtain a coating agent containing modified BPR-1: 20% by mass. The coating agent was applied to an aluminum foil using a bar coater, air-dried, and then heated in an air oven set at 200 ° C. for 20 seconds to obtain a uniform transparent coated foil coated with the coating agent. The coated surface of the coating agent of this coated foil and a polypropylene sheet (Mitsui Chemicals Tosero Co., Ltd., # 500T-T) were subjected to a pressure of 1 kg / cm ² at 80 to 150 ° C. for 1 second by a method according to JIS Z1707. The laminate was prepared by heat fusion. Table 2 shows the 180 ° peel strength measured by peeling off the coating surface of the obtained laminate and the polypropylene sheet.

[Example 2]
Example except that BPR-1 (88 g) obtained in Polymerization Example 1 and the propylene / 1-butene random copolymer (X-1) (22 g) were used instead of BPR-1 used in Example 1. 1 and the coating agent was obtained. The results are shown in Table 2.

Example 3
Example except that BPR-1 (55 g) obtained in Polymerization Example 1 and the propylene / 1-butene random copolymer (X-1) (55 g) were used in place of BPR-1 used in Example 1. 1 and the coating agent was obtained. The results are shown in Table 2.

Example 4
As 1-butene / α-olefin copolymer (Y), BPR-2 obtained in Polymerization Example 2 was used instead of BPR-1 used in Example 1, except that BPR-2 (110 g) was used. Was carried out in the same manner as in Example 1 to obtain a coating agent. The results are shown in Table 2.

Example 5
As 1-butene / α-olefin copolymer (Y), BPR-3 obtained in Polymerization Example 3 was used instead of BPR-1 used in Example 1, and BPR-3 (110 g) was used. Was carried out in the same manner as in Example 1 to obtain a coating agent. The results are shown in Table 2.

Example 6
As 1-butene / α-olefin copolymer (Y), BER-1 obtained in Polymerization Example 4 was used in place of BPR-1 used in Example 1, and BER-1 (110 g) was used. Was carried out in the same manner as in Example 1 to obtain a coating agent. The results are shown in Table 2.

Example 7
As 1-butene / α-olefin copolymer (Y), BER-2 obtained in Polymerization Example 5 was used instead of BPR-1 used in Example 1, and BER-2 (110 g) was used. Was carried out in the same manner as in Example 1 to obtain a coating agent. The results are shown in Table 2.

[Comparative Example 1]
As 1-butene / α-olefin copolymer, BPR-A was used instead of BPR-1 used in Example 1, and BPR-A (110 g) was used except that BPR-A (110 g) was used. Got. The results are shown in Table 2.

[Comparative Example 2]
As 1-butene / α-olefin copolymer, BER-A was used in place of BPR-1 used in Example 1, and BER-A (110 g) was used except that BER-A was used. Got. The results are shown in Table 2.

  As shown in Examples 1 to 3, a coating agent containing a modified 1-butene copolymer obtained by modifying BPR-1 as a 1-butene / α-olefin copolymer (Y) is at 80 ° C. Even when heat-sealed, it has good peel strength (adhesiveness). And, as shown in Examples 2 and 3, a coating comprising a modified 1-butene copolymer composition obtained by modifying a composition containing a propylene / 1-butene copolymer (X-1) The agent has improved adhesive strength with the polypropylene sheet.

Example 8
The coating film of the methylcyclohexane solution obtained in Example 1 was dried on a square plate made of polypropylene (product name: X708, manufactured by Prime Polymer Co., Ltd.) whose surface was wiped with isopropyl alcohol. After applying to about 10 μm, it was baked for 30 minutes in an 80 ° C. oven. A test piece with a grid pattern was prepared from the obtained coating film in accordance with the grid peel test method described in JIS K-5400, and an adhesive cellophane tape (cello tape (registered trademark), Nichiban Co., Ltd.) was prepared. )) Was affixed on the grid, and then quickly pulled and peeled in the 90 ° direction, and the peeling performance was evaluated by the number of grids that were not peeled out of 100 grids.

  The peel strength was measured by making a cut with a width of 1 cm in the coating film, peeling off the end portion, measuring the peel strength by pulling the end portion in the 180 ° direction at a speed of 50 mm / min, and the peel strength was 1000 g / Evaluation was made with ◎ for cm or more, ◯ for 500 g / cm or more and less than 1000 g / cm, and Δ for less than 500 g / cm. The results are shown in Table 3.

Example 9
The peeling performance was evaluated in the same manner as in Example 8 except that the coating agent obtained in Example 2 was used instead of the coating agent used in Example 8. The results are shown in Table 3.

Example 10
The peeling performance was evaluated in the same manner as in Example 8 except that the coating agent obtained in Example 3 was used instead of the coating agent used in Example 8. The results are shown in Table 3.

Example 11
The peeling performance was evaluated in the same manner as in Example 8 except that the coating agent obtained in Example 5 was used instead of the coating agent used in Example 8. The results are shown in Table 3.

[Comparative Example 3]
The peeling performance was evaluated in the same manner as in Example 8 except that the coating agent obtained in Comparative Example 1 was used instead of the coating agent used in Example 8. The results are shown in Table 3.

[Comparative Example 4]
The peeling performance was evaluated in the same manner as in Example 8 except that the coating agent obtained in Comparative Example 2 was used instead of the coating agent used in Example 8. The results are shown in Table 3.

  As is apparent from Table 3, the coating agent containing a modified 1-butene copolymer obtained by modifying the 1-butene / α-olefin copolymer (X) according to the present invention is at a baking temperature of 80 ° C. Has good peel strength. Also, as shown in Examples 9 and 10, the peel strength of the coating agent can be adjusted by changing the blending amount of the propylene / 1-butene copolymer (X-1) contained in the resin composition.

Claims (4)

  (I) Ratio (Mw / Mn) of weight average molecular weight Mw and number average molecular weight Mn determined by GPC is in the range of 1.0 to 3.5, and (ii) heat of crystal melting is in the range of 20 to 70 J / g. A coating agent comprising a modified 1-butene copolymer obtained by graft-modifying 100 parts by mass of a certain 1-butene / α-olefin copolymer (Y) with 0.1 to 15 parts by mass of a polar monomer. The coating agent according to claim 1, wherein the 1-butene / α-olefin copolymer (Y) has an isotacticity mmmm, which is an index of stereoregularity obtained from (iii) ¹³ C-NMR, of 80% or more.   The 1-butene / α-olefin copolymer (Y) according to claim 1 has a melting point (Tm-I) determined by differential scanning calorimetry (DSC) of 50 ° C. to 130 ° C. with respect to 10 to 90% by mass. Resin composition containing 90 to 10% by weight of propylene / α-olefin copolymer (X) in the range of ° C. (provided that (Y) + (X) = 100% by mass). ) A coating agent comprising a modified 1-butene copolymer composition obtained by graft-modifying 100 parts by mass with 0.1 to 15 parts by mass of a polar monomer.   The coating agent according to claim 3, wherein the propylene / α-olefin copolymer (X) is a propylene / α-olefin copolymer having a 1-butene content of 5 to 50 mol%.